Biomaterials 24 (2003) 655–665

Study of water sorption, solubility and modulus of elasticity

of light-cured dimethacrylate-based dental resins
I. Sideridou*, V. Tserki, G. Papanastasiou
Department of Chemistry, Aristotle University of Thessaloniki, GR-54006, Thessaloniki, Hellas, Greece
Received 20 November 2001; accepted 1 August 2002

Abstract

Polydimethacrylate resins were prepared by photopolymerization of Bis-GMA, TEGDMA, UDMA or Bis-EMA (4) monomer,
initiated by camphoroquinone/N,N-dimethylaminoethyl methacrylate system. The study of physical properties of these resins
showed that TEGDMA seems to create the most dense polymer network, which however is the most flexible (0.74 GPa), absorbs the
highest amount of water (6.33 wt%) and releases the lowest amount of unreacted monomer (2.41 mg/mm3). UDMA and Bis-EMA
(4) create more rigid networks, which absorb lower water and release higher unreacted monomer than TEGDMA. Bis-EMA (4)
absorbs the lowest water amount (1.79 wt%) and releases the highest amount of unreacted monomer (14.21 mg/mm3). Bis-GMA
leads to the formation of the most rigid network (1.43 GPa), which absorbs lower water than the resin made by TEGDMA but
higher than the resin made by UDMA and Bis-EMA (4). Copolymers of Bis-GMA with the other monomers were also prepared,
using various monomer combinations and molar ratios. Copolymers Bis-GMA/TEGDMA (50/50 and 70/30 wt%) showed
significantly higher values for Young’s modulus (1.83 and 1.78 GPa) than those predicted by the linear dependence of the values on
the copolymer composition. Gradual replacement of TEGDMA with UDMA or/and Bis-EMA (4) in copolymerization with Bis-
GMA resulted in more flexible resins with lower water sorption and higher solubility values, depending on the TEGDMA content.
r 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Water sorption; Solubility; Modulus of elasticity; Dental resins; Dimethacrylates; Copolymers

1. Introduction between silane and filler particles, filler–matrix debond-

Visible light-curable polymeric composites are now
routinely used as filling materials for dental restorations.
These materials are based on polydimethacrylate matrix
resins along with silane-coated inorganic fillers. They
possess many advantages such as mechanical properties
comparable to commercial dental amalgams and dental
ceramics, excellent esthetic quality and the ability to
bond to enamel surface [1]. However, in aqueous
environment they absorb water and release unreacted
monomers. The release of unreacted monomers from
resin composite may stimulate the growth of bacteria
around the restoration [2] and promote allergic reactions
in some patients [3]. Also the water ingress into dental
composites in the oral cavity can, with time, lead to
deterioration of the physical/mechanical properties,
mainly due to a hydrolytic breakdown of the bond
*Corresponding author. Tel.: +30-3199-7825; fax: +30-3199-7769.
E-mail address: siderid@chem.auth.gr (I. Sideridou).
ing or even hydrolytic degradation of the fillers [4].
Negative effects caused by water absorption were shown
e.g. with regard to tensile strength [5], flexural strength,
modulus of elasticity [6] and wear resistance [7]. Some
water ingress may have however a positive side effect,
like the expansion of the composite compensating the
polymerization shrinkage and which leads to improved
marginal sealing [8,9].
Studies have shown that water is absorbed predomi-
nantly within the matrix resin and is most affected by
the structure and the amount of this phase [10,11]; so the
study of the water sorption and solubility of polydi-
methacrylate resins made from neat monomers is
important to understand their behavior in the compo-
sites.
Polydimethacrylate resins are glassy polymers. The
sorption of water in glassy polymers is generally
described by a dual-mode theory, which assumes that
the amount of the sorbed molecules consists of two
populations [12–14]. One is held by ordinary molecular

0142-9612/02/$ - see front matter r 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 6 1 2 ( 0 2 ) 0 0 3 8 0 - 0
656 I. Sideridou et al. / Biomaterials 24 (2003) 655–665

dissolution in the polymer matrix according to the
Henry’s law and the second is trapped in polymer
microvoids following the Langmuir isotherm. A clear
physical picture of this behavior is described by the free
volume theory, which suggests that glassy polymers
generally have a non-equilibrium liquid structure,
containing an equilibrium hole-free volume responsible
for Henry’s sorption and an extra non-equilibrium hole-
free volume, frozen into the polymer (micro-voids)
responsible for Langmuir’s sorption [15,16]. The total
hole-free volume effective for water diffusion depends
on the macromolecular packing density. Flexible poly-
mer chains with polar groups, especially those forming
hydrogen bonds, which increase the intermolecular
attractions, favor high packing density [17]. The sorbed
water which is molecularly dispersed into the polymer
matrix acts as plasticizer, causing the swelling of
polymer. The quantity of thus sorbed water depends
on the available equilibrium hole-free volume, the
physicochemical affinity of polymer groups to water,
and the resistance of polymer chains to a swelling
deformation stress. On the contrary, the water molecules
which are accommodated in micro-voids are hydrogen-
bonded, form clusters and do not cause swelling of
polymer but act rather as filler particles [18,19].
Polydimethacrylates are cross-linked glassy polymers.
The presence of cross-links between polymer chains
generally results in a significant decrease in the solvent
permeability of polymer because they decrease the hole-
free volume and the ability of polymer chains for
swelling [13,20,21].
Among the commercially available dental composites,
the most widely used are composites based on resins
prepared from a combination of bisphenol A glycol
dimethacrylate (Bis-GMA) and triethylene glycol di-
methacrylate (TEGDMA). These monomers are rela-
tively hydrophilic and the water sorption and solubility
behavior of the resins prepared from TEGDMA [22–24]
or Bis-GMA [22,23,25], mixtures TEGDMA/Bis-GMA
[23] have already studied. Also, there are composites
based on urethane dimethacrylate (UDMA; product of
2,2,4(2,4,4)-trimethylhexyl diisocyanate and 2-hydro-
xyethyl methacrylate) and ethoxylated bisphenol A
glycol dimethacrylate, Bis-EMA [26].

O O
CH3
H2C CH2
O O O O
CH3 OH OH CH3
CH3

Bis-GMA (MW=512.6)

O CH3
H2C O O
O O CH2
CH3 O

TEGDMA (MW =286.2)

H CH3 CH3 O CH3

O
H2C O N O
O N O CH2
CH3 O CH3 H O

UDMA (MW =470)

O CH3 O
H2C O O CH2
O O O O
CH3 CH3
CH3

Bis-EMA (4) (MW =540)

Scheme 1. Structures of monomers used.

 I. Sideridou et al. / Biomaterials 24 (2003) 655–665
This work is concerned with the study of water
sorption, solubility and modulus of elasticity (a measure
of resin network flexibility) of light-cured resins made
from Bis-GMA, TEGDMA, UDMA, Bis-EMA (4)
(Scheme 1) and mixtures of these monomers with
various monomer combinations and molar ratios,
aiming at the study of the effect of the chemical
structure of the resin on its physical properties. In a
previous work, the effect of the chemical structure of
these monomers and mixtures of monomers on the
limiting degree of double bond conversion was studied
[27].
In this work, two commercial restorative composites
were also studied, the Z100 and Filtek Z250 (a new
product) which contain essentially the same filler but
different matrix resin. In the Z100, the matrix resin
consists of Bis-GMA and TEGDMA, while in the Filtek
Z250 the majority of TEGDMA has been replaced with
a blend of UDMA and Bis-EMA(6) (hexaethoxylated
bisphenol A glycol dimethacrylate). The results of this
study would help in the better understanding of the
behavior of the composites, which contain these
polydimethacrylate resins and also in the improvement
of present commercial materials or the development of
better composite resins.
2. Materials and methods
2.1. Materials
The dimethacrylates used were Bis-GMA (Poly-
sciences Europe GmbH, Lot no. 495282), Bis-EMA
(Aldrich Chem. Co., Lot no. 03514HF), UDMA
(Ivoclar AG, Lot no. B00338) and TEGDMA (95%,
Aldrich Chem. Co., Lot no. 461111). They were used as
received without further purification. Nine mixtures of
these monomers were prepared, the compositions of
those are shown in Table 1 and they are same as those
used in our previous work [27]. To make the samples
light curing, 2 mol% of camphoroquinone (CQ) (Poly-
sciences, Lot no. 497117) used as photosensitizer, and
2 mol% of N,N-dimethylaminoethyl methacrylate
(DMAEMA) (Riedel-de Haen, Lot no. 20770) used as
reducing agent, were added to each sample. All samples,
except TEGDMA, were viscous liquids. So the CQ and
DMAEMA were first dissolved in dichloromethane,
then certain amount of this solution was added to the
sample and the solvent was subsequently evaporated
under vacuum.
The commercial composites studied, Z100 (Lot no.
3021A3.5) and Filtek Z250 (Lot no. 6020A2) are both
products of 3M Company (St Paul, MN, USA).
According to the data given by the Company, the
matrix resin (15.5% wt/wt, 29% v/v) in Z100 consists of
Bis-GMA/TEGDMA. In the new composite, Filtek
657
Z250 the majority of TEGDMA has been replaced with
a blend of UDMA and Bis-EMA (6). Bis-EMA (6)
contains, on average, 6 ethylene oxide groups per Bis-
phenol A groups in contrast to neat Bis-EMA (4) used in
this work which contains correspondingly 4 ethylene
oxide groups. The filler in Z100 is zirconia/silica
particles with a particle size range 3.5–0.01 mm and
an average particle size of 0.6 mm. The filler in Filtek
Z250 remains essentially the same as in Z100, but
there have been significant processing changes to
maximize filler consistency. The particle size distri-
bution for Filtek Z250 is also from 3.5 to 0.01 mm,
with an average particle size of 0.6 mm, but contains a
larger number of finer particles than found in Z100
composite.
2.2. Water sorption and solubility
Water sorption and solubility tests were determined
according to the method described in ADA Specification
No. 27 based filling materials. Specimen discs 12 mm in
diameter and 1 mm in thickness were fabricated in an
aluminum mold between two glass slides covered with
polyethylene film. They were irradiated for 200 s on each
side with a XL 3000 dental photo-curing unit from 3M
Company (St Paul, USA). This source consisted of a
75 W tungsten halogen lamp, a series of optical filters
and lenses and a fused fiber optic light guide with a
7 mm exit-window. This unit emitted radiation predo-
minantly in the 420–500 nm range, which also absorbs
CQ (lmax ¼ 470 nm, e ¼ 3:8  104 cm2/mol [28]). The
light and heat (infrared) intensity was monitored
regularly by a Hilux curing light meter. The unit was
used without the light guide, at a distance from the
sample, 1.5 cm. Five specimen discs were prepared for
each resin. On removal the specimens were placed in a
desiccator containing freshly dried silica gel. After 24 h
they were removed, stored in a desiccator at 231C for 1 h
and weighed with a precision of 0.01 mg. This cycle was
repeated until a constant mass (m1 ) was obtained. The
discs were immersed in distilled water at 371C for 7 days,
then removed, blotted dry and weighed (m2 ). After this
weighing, the specimens were reconditioned to a
constant mass (m3 ) in the desiccators using the above-
described cycle. The diameter and the thickness of the
specimen were measured at five points and the volume
(V ) was calculated in cubic millimeters. The values of
water sorption (WS) and solubility (SL) were calculated
for each disc using the following formulae:
m2  m3 m1  m3
WS ¼ ; SL ¼ : ð1Þ
V V
Water sorption and solubility were also calculated using
the following extensive molar quantities:
WS  V SL  V
½WS ¼ ; ½SL ¼ ; ð2Þ
ðm1 =MWÞ ðm1 =MWÞ
658 I. Sideridou et al. / Biomaterials 24 (2003) 655–665

Table 1
Monomers, mixtures of monomers and commercial composites used in this study

Abbreviation Composition of samples in mole fractions (X )

Bis-GMA (X1 ) TEGDMA (X2 ) UDMA (X3 ) Bis-EMA (4) (X4 )

G 1.00 0.00 0.00 0.00

T 0.00 1.00 0.00 0.00
U 0.00 0.00 1.00 0.00
E 0.00 0.00 0.00 1.00
G–T (1) 0.3582a 0.6418a 0.0000 0.0000
G–T (2) 0.5659b 0.4341b 0.0000 0.0000
G–U (1) 0.3582 0.0000 0.6418 0.0000
G–U (2) 0.5659 0.0000 0.4341 0.0000
G–E (1) 0.3582 0.0000 0.0000 0.6418
G–E(2) 0.5659 0.0000 0.0000 0.4341
G–T–U–E (1) 0.5660 0.2340 0.1000 0.1000
G–T–U–E (2) 0.5660 0.1340 0.1500 0.1500
G–U–E 0.5660 0.0000 0.2170 0.2170
Composite Z100c + +  
Composite Z250c + + + Bis-EMA (6)
a
This molar composition corresponds to 50/50 (wt%).
b
Corresponds to 70/30 (wt%).
c
The accurate molar composition of matrix resin is unknown.

where MW is the molecular weight of the monomer. In the equation

the case of mixtures of n monomers, the MWmix was
calculated from the equation:
MWmix ¼ X1 MW1 þ X2 MW2 þ y þ Xn MWn
Xn
¼ Xi MWi ;
i¼1
where Xi (with i ¼ 1; 2; y; n) are the mole fractions of
the monomers reported in Table 1 and MWi (with
i ¼ 1; 2; y; n) the corresponding molecular weights.
A relatively simple calculus shows that both [WS] and
[SL] are additive properties. So under ideal behavior
related properties of a copolymer prepared from n
monomers M1 ; M2 ; y; Mn can be calculated by means
of the following relationships:
½WSideal ¼ X1 ½WS1 þ X2 ½WS2  þ y þ Xn ½WSn
Xn
¼ Xi ½WSi ;
i¼1
where [WS]i and [SL]i (with i ¼ 1; 2; y; n) are the
relative molar quantities of the corresponding homo-
polymers of M1 ; M2 ; y; Mn ; respectively.
These quantities were used for the calculation of the
corresponding excess properties of copolymers as
reported below.
2.3. Modulus of elasticity
It was determined by using a loaded rectangular
specimen bar fixed horizontally at one end (cantilever)
[29]. If a cantilever has a load W suspended at the
extreme end, the deflection h of the end is given by
 3
4L
h¼ W ¼ BW ; ð5Þ
Eab3
where L is the length of the specimen beyond the clamp
ð3Þ used, a its breadth and b the thickness. Specimens were
prepared by filling a Teflon mold (2 mm  2 mm 
70 mm) with the un-polymerized material, taking care
to minimize entrapped air. The upper and lower surface
of the mold was overlaid with glass slides covered with
vaseline to avoid adhesion with the resin. The completed
assembly was held together with spring clips and
irradiated using a Suntest apparatus of Original Hanau
for 400 s on each side. A Xenon burner (1.1 kW) is
installed in the top section of this apparatus, which
emits radiation between 300 and 830 nm and has the
maximum peak at 470 nm. After curing the mold was
dismantled, the resin was carefully removed by flexing
ð4Þ the Teflon mold and the specimen bar was placed in
distilled water and aged at 371C for 24 h. The specimen
was then dried with tissue paper and allowed to return
to room temperature for 15 min. It was fixed horizon-
tally at one end and the length beyond the clamp was
measured with accuracy of 0.01 mm. The breadth and
the thickness of the specimen were measured with a
micrometer screw gauge (accuracy 0.001 mm), while L
was measured with accuracy of 0.01 mm. At the extreme
end various loads were hung and the deflection of this
end for each of the loads applied was measured with a
vernier with accuracy of 0.01 mm. In the elastic range,
Eq. (5) predicts a linear relationship between h and W :
Alternatively, the experimental confirmation of such a
correlation permits the determination of the values of
 I. Sideridou et al. / Biomaterials 24 (2003) 655–665 659

E from the slopes B of the corresponding lines. In all between the experimental values of E and the predicted
cases studied in this investigation it was found indeed ones from the linear law of mixing.
that the plots of h vs. W were always linear (R2 > 0:999). Finally, the percent excess values of a quantity M of
Five specimen bars were prepared for each resin and the copolymers were calculated by
obtained values of E were averaged. The error (standard  E
E M
deviation) of the obtained E values (dE) was estimated M %¼ 100: ð12Þ
M exp
using the method of propagation of errors [30]. Indeed,
it follows from Eq. (5) that E depends upon several
observed quantities L; a; b and B; according to the 2.5. Cross-link density (q) and network parameter (Mc)
following equation:
4L3 Recently it was reported in the literature that for a
E¼ : ð6Þ polymer prepared by polymerization of a dimethacrylate
ab3 B
monomer, the cross-link density q; defined as the
The error dE resulting from errors dL; da; db and dB can fraction of polymer chain units that is cross-linked,
be represented as can be related to the degree of conversion of the double
       
qE  qE  qE  qE  bonds (a) by the simple equation [31]:
dE ¼  dL þ  da þ  db þ  dB:
      ð7Þ
qL qa qb qB 2a  1
q¼ : ð13Þ
Combining Eqs. (6) and (7) one obtains a
  This equation was derived under the assumption that
4L2 L 3L L
dE ¼ 3 3dL þ da þ db þ dB : ð8Þ each monomer molecule reacted with at least one double
ab B a b B bond, so it can be used only in systems where there are
The values of dL; da; db can be approximated by the no totally unreacted monomer molecules and the degree
accuracy of the measurements of L; a; b; while dB by the of conversion is higher than 50%. In real systems,
standard deviation of the slope B determined by least however, this assumption is not quite true, and cured
squares. dimethacrylates almost always contain residual un-
reacted monomer [32,33]. If x0 is the moles of the
2.4. Excess properties of copolymers unreacted monomer molecules, then
2ax0 þ ð2a  1Þðn  x0 Þ
q¼ ; ð14Þ
In liquid mixtures, the excess thermodynamic value na
M E of an extensive molar quantity M is defined by where n are the initial moles of the monomer. If x0 -0
M E ¼ M exp 2M ideal ; ð9Þ then Eq. (14) turns again to Eq. (13).
We applied Eq. (14) for the monomer mass m1 of the
where M exp denotes the actual value of M; while M ideal disc used in our experiments for the determination of
is defined for each composition by applying the additive water sorption and solubility (n ¼ m1 =MW), and we
rule. considered in a first approximation that all the
In the case of a copolymer, prepared from a mixture unreacted monomer was extracted by the water after
of n monomers M1 ; M2 ; y; Mn ; on the analogy of liquid immersion of the disc in distilled water at 371C for 7
mixtures, we can define the excess values of the extensive days, i.e. x0 ¼ ðm1  m3 Þ=MW (m3 is the mass of the
molar quantities [WS] and [SL] by disc after drying). So finally we obtained the equation
½WSE ¼ ½WSexp 2½WSideal ; 2am1  m3
q¼ : ð15Þ
½SLE ¼ ½SLexp 2½SLideal ; ð10Þ am1

where [WS] ideal

and [SL] ideal
are defined by Eqs. (4).
The modulus of elasticity (E) is not an extensive
molar quantity. So, it is not possible to apply the
additive rule in order to determine its ideal behavior.
However, we can define the quantity
E E ¼ E exp  ðX1 E1 þ X2 E2 þ y þ Xn En Þ
Xn
¼ E exp  Xi Ei ;
i¼1
where Ei (with i ¼ 1; 2; y; n) are the relative values of E
of the corresponding homopolymers of M1 ; M2 ; y; Mn
respectively. Evidently, E E expresses the differences
By using this equation and the values of percent
limiting degree of conversion of double bonds (a) !
determined by FT-IR technique on thin films in our
previous work [27], the q parameter of the prepared
polymers were calculated.
The network parameter (Mc) of the prepared poly-
mers, which is the average molecular weight of the
segment of the polymer chain between two cross-links,
ð11Þ was also calculated using the following equation [31]:
Mc ¼ MW=q; ð16Þ
where MW the molecular weight of the monomeric unit
of polymer.
660 I. Sideridou et al. / Biomaterials 24 (2003) 655–665

3. Results and discussion 3.1. Polydimethacrylate resins

The results of water sorption and solubility of
homopolymers, copolymers and composites studied,
are given in Table 2. According to ISO 9000s standard
for dental restorative resins, a resin in order to be
suitable for use as dental material must show water
sorption lower than 50 mg/mm3 and solubility lower than
5 mg/mm3 [34]. The values of water sorption for all
studied polymers, except that prepared from TEGD-
MA, are within the range of the ISO’s standard. On the
contrary, the values of solubility are within the range of
the ISO’s standard only for copolymers prepared from
mixtures of Bis-GMA and TEGDMA. The value of
solubility for copolymer prepared from the mixture G–
T–U–E (1) is in the limit of this range (5.07 mg/mm3).
In Table 2 the determined values of modulus of
elasticity of materials, which is a measure of their
flexibility under the action of a stress are also shown.
In Table 3 the calculated values of the cross-link
density (q) and the network parameter (Mc), which both
characterize the structure of the prepared polymer
networks, are shown. When the degree of conversion
of double bonds is lower than 50%, the value of q is
negative, revealing that our approximation made for the
calculation of q; which predicts that all the residual
unreacted monomer is extracted by the water when the
polymer discs are immersed in distilled water at 371C for
7 days, is not quite correct and the discs still contain
unreacted monomer. The above approximation, how-
ever, could be considered satisfactory for materials with
degree of conversion higher than 50%, and the values of
parameters q and (Mc) could be used as indicative for
describing the form of the polymer network. The
network is tighter as higher is the value of q and lower
is the value of Mc:
The water sorption of homopolymers studied, is in the
following order:
Poly-TEGDMA (6.33 wt%)>poly-Bis-GMA
(2.93 wt%)>poly-UDMA (2.59 wt%)>poly-Bis-EMA
(4) (1.79 wt%). The values obtained for polymers
prepared from TEGDMA or Bis-GMA are in good
agreement with the values reported for them in the
literature, 6 wt% [22,23] and 6.22 wt% [24] or 3.05 wt%
[22,23,25] correspondingly. The water sorption of poly-
TEGDMA is much higher than that of poly-Bis-GMA,
while the water sorption of TEGDMA monomer is
reported to be slightly higher (2.74 wt%) than that of
Bis-GMA monomer (2.35 wt%) [24]. These results show
that the hydrophilic character of the monomer units of
polymers derived by these monomers is about the same,
and that the much higher water absorption of poly-
TEGDMA than that of poly-Bis-GMA is not due to the
different chemical structure of the polymer networks,
but most probably to their different physical structure.
According to the data shown in Table 3, TEGDMA
creates a much more dense network than Bis-GMA, so
initially it seems strange how it absorbs a much higher
water amount. However these networks are not homo-
geneous. Generally, polymer networks prepared by free-
radical polymerization of dimethacrylates show a spatial
heterogeneity, and some parts are densely cross-linked
and some parts are loosely cross-linked. The seeds of
heterogeneity are shown almost from the beginning of
polymerization with the formation of microgels domains
of high cross-linking density dispersed in a pool of
unreacted monomers. The final network morphology is
the result of microgels agglomeration into clusters and
connection with those clusters [35–37]. Studies on the
structural heterogeneity of polydimethacrylate based

Table 2
Values of water sorption, solubility and Young’s modulus of materials studied

Material Water sorption Solubility Young’s modulus

3 3
WS (mg/mm ) [WS] (g/mol) SL (mg/mm ) [SL] (g/mol) (GPa)

Bis-GMA 33.4970.20 15.0270.08 10.4470.21 4.6970.12 1.42770.019

TEGDMA 69.5170.32 18.1170.13 2.4170.14 0.6370.04 0.74470.005
UDMA 29.4670.16 12.1570.23 6.6270.12 2.7370.07 1.40570.011
Bis-EMA (4) 20.1070.19 9.67 70.04 14.2170.26 6.8370.07 1.13470.009
G–T (1) 45.2170.21 15.1170.09 1.55 70.15 0.5270.05 1.82670.012
G–T (2) 40.2570.19 15.2770.12 2.7070.22 1.0270.09 1.77970.015
G–U (1) 32.2770.31 13.9970.10 8.3670.19 3.6270.08 1.40470.010
G–U (2) 33.5270.14 15.5470.32 11.5670.07 5.3670.06 1.35070.013
G–E (1) 23.0270.07 11.1670.09 12.5170.26 6.0770.17 1.31570.010
G–E (2) 27.2770.25 12.6970.19 13.2470.30 6.1670.12 1.16770.009
G–T–U–E (1) 34.0370.26 14.4570.24 5.0770.42 2.1670.20 1.51970.010
G–T–U–E (2) 31.4270.37 13.9470.19 5.9970.30 2.6670.15 1.50270.010
G–U–E 26.8070.55 12.4570.41 6.7070.37 3.1170.15 1.49170.011
Composite Z100 16.85 — 0.73 — 8.517
Composite Z250 13.02 — 0.25 — 14.200
 I. Sideridou et al. / Biomaterials 24 (2003) 655–665 661

Table 3 monomer inside the microgels [32]. The values of

Degree of conversion, cross-link density and network parameter for solubility presented in Table 2 show that these depend
materials studied
mainly on the degree of conversion. The higher the
Material Degree of Cross-link Network degree of conversion and thus higher the amount of the
conversiona density parameter unreacted monomer, the lower the solubility value.
a (%) q Mc
The Young’s modulus of the prepared homopolymers
Bis-GMA 39.0 0.541 — follows the order: poly-TEGDMA (0.744 GPa)opoly-
TEGDMA 75.7 0.682 419.7 Bis-EMA (4) (1.134 GPa)opoly-UDMA (1.405 GPa)o
UDMA 69.6 0.572 822.3
poly-Bis-GMA (1.427 GPa). It is noteworthy that poly-
Bis-EMA (4) 52.2 0.109 4975.4
G–T (1) 60.9 0.360 1019.5 TEGDMA with the highest cross-link density is the
G–T (2) 54.9 0.183 2263.9 most flexible polymer, due to its flexible aliphatic
G–U (1) 57.1 0.262 1853.8 monomer units. Poly-UDMA consists also of aliphatic
G–U (2) 50.6 0.045 10944.0 monomer units, but it is a relatively rigid polymer, due
G–E (1) 45.4 0.177 —
G–E (2) 42.3 0.336 —
to the existence of hydrogen bonds between them. This
G–T–U–E (1) 47.6 0.091 — significant effect of hydrogen bonds on the rigidity of
G–T–U–E (2) 44.9 0.215 — polymer network is also shown comparing the Young’s
G–U–E 44.5 0.193 — modulus of poly-Bis-GMA and poly-Bis-EMA (4). The
Composite Z100 24.3 — — monomer units of these polymers have about the same
Composite Z250 40.1 — —
chemical structure (Scheme 1), but the former has in
a
It was determined in a previous work [27] by the FT-IR technique addition two hydroxyl groups, which can form strong
on thin films of materials. hydrogen bonds and increase the rigidity of the polymer
network.
Copolymers prepared from mixtures of Bis-GMA/
networks showed that the more densely cross-linked the TEGDMA (50/50 or 70/30 wt%) showed significantly
network the more heterogeneous is its structure [38,39]. high values for the Young’s modulus (1.826 or
So the poly-TEGDMA network is more heterogeneous 1.779 GPa correspondingly) which were much higher
than poly-Bis-GMA and this higher heterogeneity seems than those predicted by the linear law of mixing. This
to favor the higher water sorption of the former. In a behavior is most probably due to the formation of
more heterogeneous network, the space created between hydrogen bonds between the –OH– groups of Bis-GMA
the polymer clusters (microporous) is larger and can and >C=O or –O– groups of TEGDMA monomer
accommodate a larger quantity of water. units, which are not taken into account in the law of
The higher water sorption of poly-TEGDMA than mixing describing an ideal behavior. The value of
that of poly-Bis-GMA may also be due, to some extent, Young’s modulus is higher for the copolymer containing
to the higher flexibility of the network of the former higher amount of TEGDMA monomer units, revealing
(E ¼ 0:744 GPa) than the latter (E ¼ 1:427 GPa) which that the presence of these units in the polymer network
permits the higher swelling of polymer chains by water. causes an antiplastication effect. Copolymers prepared
Poly-UDMA and especially poly-Bis-EMA (4) from mixtures of Bis-GMA, TEGDMA, UDMA and
showed lower water sorption than poly-Bis-GMA. Bis-EMA (4) showed also Young’s modulus values
Taking into account the possible effects of chemical higher than those predicted by the law of mixing,
and physical structure of the polymer network on the especially that with the higher content in TEGDMA
moisture absorption, it seems that the higher water (Table 2) confirming the antiplastication effect of this
sorption of poly-Bis-GMA is most probably due to the monomer. On the contrary, copolymers prepared from
higher hydrophilic character of its monomer units. mixtures of Bis-GMA and UDMA or Bis-GMA and
Hydroxyl groups form stronger hydrogen bonds with Bis-EMA (4) showed Young’s modulus values slightly
the water molecules than urethane groups of poly- lower than those predicted, indicating that UDMA and
UDMA or ether groups of poly-Bis-EMA (4). The Bis-EMA (4) act as internal plasticizers of the polymer
cohesive energy density of –OH– groups is 2980 J/cm3, network. So, although UDMA and Bis-EMA (4) create
of urethane groups 1425 J/cm3, and of ether groups homopolymer networks more rigid than TEGDMA, the
881 J/cm3 [40]. copolymers Bis-GMA/UDMA and Bis-GMA/Bis-EMA
The solubility of polymers is concerned to the (4) are softer than Bis-GMA/TEGDMA copolymers.
leachable by the water amount of unreacted monomer. The differences of the determined values for
This is trapped during the polymerization inside the copolymer properties, from those predicted by the
microgels between the polymer chains and it is adsorbed linear law of mixing for Young’s modulus, or by the
to the surrounding network, or it is trapped in the additive rule for water sorption and solubility, defined
micropores (monomer pools). The monomer in micro- as the corresponding excess properties are shown in
pores is more susceptible to leaching out than the Table 4.
662 I. Sideridou et al. / Biomaterials 24 (2003) 655–665

It is observed that all the copolymers containing copolymers Bis-GMA/TEGDMA is presented. It is

TEGDMA monomer units exhibit a high negative
deviation from the predicted values for the solubility,
and a small negative deviation for water sorption also.
This deviation in both cases is increased as the
TEGDMA content in the copolymer increases. In
Fig. 1 the dependence of the solubility on the TEGDMA
content of copolymers Bis-GMA/TEGDMA is pre-
sented. Taking into account that an increase in the
degree of conversion of these copolymers was not
observed, the lower solubility of copolymer with the
higher content of TEGDMA could be explained
suggesting the formation of hydrogen bonds between
the unreacted Bis-GMA (–OH–) and the small-sized
TEGDMA (>C=O, –O–) monomer or/and between
these monomers and the surrounding polymer network,
which prevent their leaching by water.
In Fig. 2 the dependence of excess water sorption and
excess of Young’s modulus on the TEGDMA content of
clearly seen that the increase of the TEGDMA content
results in an increase of the rigidity of the copolymer
network and in a corresponding decrease of water
sorption. The hydrogen bonds formed in these copoly-
mers, as has been previously described, could be
considered responsible for this decrease of the water
sorption by causing a decrease of the packing density of
polymer chains.
Copolymers of Bis-GMA/UDMA or mainly of Bis-
GMA/Bis-EMA (4) showed lower water sorption and
higher solubility than copolymers of Bis-GMA/TEGD-
MA. Gradual replacement of TEGDMA with UDMA
and Bis-EMA (4) in copolymerization with Bis-GMA
gave copolymers with lower Young’s modulus (softer
networks) lower water sorption and higher solubility,
depending on the TEGDMA content (Table 2).
In Table 5, the results obtained from the statistic
comparison of properties of all the studied polymers

Table 4
Excess properties (M E ) for materials prepared from mixtures of dimethacrylate monomers (copolymers)

Material (copolymer) Excess water sorption Excess solubility Excess Young’s Excess degree conv.
[WSE ] (%) [SLE ] (%) modulus E E (%) aE (%)

G–T (1) 12.6 302.7 45.8 2.71

G–T (2) 7.2 185.3 36.4 0.057
G–U (1) 5.8 5.3 0.61 2.70
G–U (2) 11.4 28.4 5.0 3.33
G–E (1) 3.9 0.03 5.8 4.56
G–E (2) 0.1 8.78 11.4 5.75
G–T–U–E (1) 3.3 74.0 18.6 9.18
G–T–U–E (2) 1.9 56.8 14.2 12.4
G–U–E 6.3 52.2 8.9 9.00

4 ideal behavior

3
[SL] (g/mol)

2
E
[SL]

0
0.0 0.2 0.4 0.6 0.8 1.0
Mole fraction of TEGDMA in copolymer
Fig. 1. Solubility vs. mole fraction of TEGDMA of copolymer prepared from mixture of Bis-GMA/TEGDMA. The excess solubility ½SLE is defined
as the difference of the determined value from that predicted by the additive rule (ideal behavior).
 I. Sideridou et al. / Biomaterials 24 (2003) 655–665 663

0 50

E
-2 E %
E
[WS] % 40
-4

-6 30
[WS] %
E

E %
-8

E
20
-10

-12 10

-14
0
0.0 0.2 0.4 0.6 0.8 1.0
Mole fraction of TEGDMA in copolymer
Fig. 2. Correlation between the percent excess water sorption ½WSE % and the percent excess Young’s modulus E E %; with the mole fraction of
TEGDMA of copolymer prepared from mixture of Bis-GMA/TEGDMA.

Table 5
Statistical data of the correlation (Fisher’s z-transformation) of the quantitiesa: a (%), E; [WS] and [SL]. Hypothesized correlation coefficient R ¼ 0

R Count Z-value P-value Confidence Limits

95% lower 95% upper

E–[WS] 0.030 13 0.096 0.92 0.572 0.530

E–[SL] 0.333 13 1.093 0.27 0.747 0.267
[WS]–[SL] 0.668 13 2.554 0.01 0.891 0.185
A (%)–E 0.275 13 0.891 0.37 0.717 0.326
A (%)–[WS] 0.370 13 1.228 0.22 0.228 0.765
A (%)–[SL] 0.568 13 2.039 0.04 0.852 0.025
a
a (%)—the limiting degree of conversion percent, E—Young’s modulus in GPa, [WS]—water sorption in g/mol and [SL]—solubility in g/mol.

(homopolymers and copolymers, 13 samples) are given.
Significant coefficients of correlation were found only
between water sorption and solubility (R ¼ 0:67) and
between degree of conversion and solubility (R ¼ 0:57).
Statistic comparison of the percent excess properties
of the nine copolymer resins studied showed significant
coefficients of correlation between them. No correlation
was established between the excess properties and the
excess degree of conversion (Table 6).
3.2. Composites
The organic matrix resin of the composites studied in
this work Z100 and Z250, consists correspondingly of
Bis-GMA/TEGDMA copolymer and Bis-GMA/
TEGDMA/UDMA/Bis-EMA (6) copolymer. These
composites showed significantly high values for Young’s
modulus, 8.5 GPa (Z100) and 14.2 GPa (Z250). The
value of Z100 is 4.7 times higher than that of copolymers
Bis-GMA/TEGDMA (1.8 GPa) and the value of Z250
about 9.5 times higher than that of copolymers of the
four monomers (1.5 GPa) (Table 2). Taking into
account that an exponential dependence of Young’s
modulus with the percent filler fraction has been found
for several composites [41] it can be concluded that Z250
must contain a higher amount of filler than Z100.
Composite Z250 showed lower water sorption than
Z100. This result may be due to the lower hydrophilicity
of its organic matrix resin but also to its lower content in
organic resin. Z250 showed also a smaller solubility than
Z100. Taking into account that copolymers of the four
monomers showed a much higher solubility than
copolymers Bis-GMA/TEGDMA, the lower solubility
of Z250 is probably due to the lower content in organic
resin and also to the higher degree of conversion
(40.1%) than that of Z100 (24.3%).
664 I. Sideridou et al. / Biomaterials 24 (2003) 655–665

Table 6
Statistical data of the correlation (Fisher’s z-transformation) of the excess properties of copolymers. Hypothesized correlation coefficient R ¼ 0

R Count Z-value P-value Confidence Limits

95% lower 95% upper

E
E E %–½WS % 0.727 9 2.259 0.02 0.938 0.121
E E %–½SLE % 0.961 9 4.787 o0.0001 0.992 0.819
½WSE %–½SLE % 0.793 9 2.646 o0.01 0.273 0.955
AE ð%Þ–E E % 0.185 9 0.460 0.65 0.546 0.756
AE ð%Þ–½WSE % 0.044 9 0.109 0.91 0.639 0.688
AE ð%Þ–½SLE % 0.276 9 0.693 0.49 0.794 0.476

4. Conclusions References

The study of the physical properties of light-cured
resins made from Bis-GMA, TEGDMA, UDMA and
Bis-EMA (4) showed that TEGDMA seems to create
the most dense polymer network, which however is the
most flexible, absorbs the highest amount of water and
releases the lowest amount of unreacted monomer.
UDMA and Bis-EMA (4) create more rigid networks
than TEGDMA, which absorb less water and release
higher unreacted monomer. Bis-GMA leads to the
formation of the most rigid network, which absorbs
less water than the resin made by TEGDMA but higher
than the resins made by UDMA and Bis-EMA (4).
Resins prepared by the copolymerization of Bis-
GMA/TEGDMA showed significantly higher values
for Young’s modulus than those predicted by the linear
dependence of the values on the copolymer composition
(antiplastication effect). On the contrary, the resins of
Bis-GMA/UDMA and Bis-GMA/Bis-EMA (4) showed
Young’s modulus values slightly lower than those
predicted (plastication effect). Bis-GMA/UDMA and
Bis-GMA/Bis-EMA (4) resins are more flexible than
Bis-GMA/TEGDMA resins. The former absorbs lower
water amount and releases higher unreacted monomers
than the latter. Gradual replacement of TEGDMA with
UDMA and Bis-EMA (4) in copolymerization with Bis-
GMA results in more flexible resins with lower water
sorption and higher solubility values, depending on the
TEGDMA content.
Composite Z250 showed higher Young’s modulus,
lower water sorption and solubility than Z100. These
differences in composite properties are the result of the
higher most probable filler content of Z250 and the
different structure of the organic matrix resin.
Acknowledgements
We would like to thank A.G. Ivoclar for the generous
gift of UDMA monomer used in this work and in our
previous work [27].
[1] Craig RG, editor. Restorative dental materials. 10th ed. St. Louis,
Missuri: C.V. Mosby Combany, 1997.
[2] Hansel C, Leyhausen G, Mai UEH, Geurtsen W. Effects of
various resin composite (co)monomers and extracts on two caries-
associated micro-organisms in vitro. Dent Mater 1998;77:60–7.
[3] Spahl W, Budzikiewicz H, Geursten W. Extractable residual
monomers from various resin materials—a qualitative study.
J Dent Res 1994;73:295.
[4] Soderholm K-JM, Zigan M, Ragan M, Fischlschweiger W,
Bergman M. Hydrolytic degradation of dental composites.
J Dent Res 1984;63:1248–54.
.
[5] Soderholm K-JM, Roberts MJ. Influence of water exposure on
the tensile strength of composites. J Dent Res 1990;69:1812.
.
[6] Oysaed H, Ruyter I. Composites for use in posterior teeth:
mechanical properties tested under dry and wet conditions.
J Biomed Mater Res 1986;20:261.
.
[7] Scarret DC, Soderholm K-JM, Ybatich CD. Water and abrasive
effects on three-body wear of composites. J Dent Res
1991;70:1074.
[8] Bowen RL, Rapson JE, Dickson G. Hardening shrinkage and
hygroscopic expansion of composite resins. J Dent Res
1982;61:654.
[9] Torstenson B, Br.annstrom. M. Contraction gap under composite
resin restorations. Effect of hygroscopic expansion and thermal
stress. Oper Dent 1988;13:24.
[10] Fan PL, Edahl A, Leung RL, Stanford JW. Alternative
interpretations of water sorption values of composite resins.
J Dent Res 1985;64:78–80.
[11] Santos C, Clarke RL, Braden M, Guitian F, Davy KWM.
Water absorption characteristics of dental composites
incorporating hydroxyapatite filler. Biomaterials 2002;23:
1897–904.
[12] Vieth WR, Sladek KJ. A model for diffusion in a glassy polymer.
J Colloid Sci 1965;20:1014–33.
[13] Frisch HL. Sorption and transport in glassy polymers. Rev Polym
Eng Sci 1980;20:2–13.
[14] Wang B, Yamaguchi T, Nakao S. Solvent diffusion in amorphous
glassy polymers. J Polym Sci Polym Phys Ed 2000;38:846–56.
[15] Vrentas JS, Duda JL. Diffusion in polymer–solvent systems. I.
Reexamination of the free volume theory. J Polym Sci Polym
Phys Ed 1977;15:403–16.
[16] Vrentas JS, Duda JL. A free volume interpretation of the
influence of the glass transition on diffusion in amorphous
polymers. J Appl Polym Sci 1978;22:2325–39.
[17] Tager A. Polymer chain flexibility. In: Physical chemistry of
polymers. 2nd ed. Moscow: Mir Publ., 1978. p. 146.
[18] Ping ZH, Nguyen QT, Chen SM, Zhou JQ, Ding YD. States of
water in different hydrophilic polymers-DSC and FTIR studies.
Polymer 2001;42:8461–7.
 I. Sideridou et al. / Biomaterials 24 (2003) 655–665
[19] Patil RD, Mark JE, Apostolov A, Vassileva E, Fakirov S.
Crystallization of water in some crosslinked gelatins. Eur Polym J
2000;36:1055–61.
[20] Andrady AL, Sefcik MD. Transport of hydrogen and carbon
monoxide in highly crosslinked poly(propylene glycol) networks.
J Polym Sci Polym Phys Ed 1984;22:237–43.
[21] Ajithkumar S, Patel NK, Kansara SS. Sorption and diffusion of
organic solvents through interpenetrating polymer networks
(IPNs) based on polyurethane and unsaturated polyester. Eur
Polym J 2000;36:2387–93.
[22] Kalachandra S, Taylor DF, DePorter CD, McGrath JE.
Polymeric materials for composite matrices in biological environ-
ments. Polymer 1993;34:778–82.
[23] Kalachandra S, Turner DT. Water sorption of polymethacrylate
networks: bis-GMA/TEGDM copolymers. J Biomed Mater Res
1987;21:329–38.
[24] Kalachandra S, Kusy RP. Comparison of water sorption by
methacrylate and dimethacrylate monomers and their corre-
sponding polymers. Polymer 1991;32:2428–34.
[25] Sankarapandian M, Shobha HK, Kalachandra S, McGrath JE,
Taylor DF. Characterization of some aromatic dimethacrylates
for dental composite applications. J Mater Sci Mater Med
1997;8:465–8.
[26] Moszner N, Ulrich S. New developments of polymeric dental
composites. Prog Polym Sci 2001;26:535–76.
[27] Sideridou I, Tserki V, Papanastasiou G. Effect of chemical
structure on degree of conversion in light-cured dimethacrylate
based dental resins. Biomaterials 2002;23:1819–29.
[28] Cook W. Photopolymerization kinetics of dimethacrylates using the
camphoroquinone/amine initiator system. Polymer 1992;33:600–9.
[29] Allen HS, Moore H. Textbook of practical physics. 3rd ed.
London: Macmillan, 1949. p. 92.
[30] Young HD. Statistical treatment of experimental data. New
York: McGraw-Hil, 1962. p. 96–101.
[31] Barszczewska-Rybarek I, Gibas M, Kurcok M. Evaluation of the
network parameter in aliphatic poly(urethane dimethacrylate)s by
dynamic thermal analysis. Polymer 2000;41:3129–35.
665
[32] Simon GP,, Allen PEM, Bennett DJ, Williams DRG,
Williams EH. Nature of residual unsaturation during cure of
dimethacrylates examined by CPPEMAS 13C NMR and simula-
tion using a kinetic gelation model. Macromolecules 1989;22:
3555–61.
[33] Elliot JE, Bowman CN. Kinetics of Primary Cyclization Reac-
tions in Cross-Linked Polymers: an analytical and numerical
approach to heterogeneneity in network formation. Macromole-
cules 1999;32:8621–8.
[34] Nie J, Lovell LG, Bowman CN. Synthesis and characterization of
N-methacryloxyethyl methacrylamide as a possible dental resin.
Biomaterials 2001;22:535–40.
[35] Kloosterboer JG, Van de Hei GMM, Boots HMJ. Inhomogeneity
during the photopolymerization of diacrylates: d.s.c. experiments
and percolation theory. Polym Commun 1984;25:354–7.
[36] Allen PEM, Bennett DJ, Haglias S, Hounslow AM, Ross GS,
Simon GP, Williams DRG, Williams EH. The radical polymer-
ization of dimethacrylate monomers—the use of NMR spectro-
scopy to follow the development of network structure. Eur Polym
J 1989;25:785–9.
[37] Anseth KS, Anderson KJ, Bowman CN. Radical concentrations,
environments and reactivities during crosslinking polymeriza-
tions. Macromol Chem Phys 1996;197:833–48.
[38] Elliot JE, Lovell LG, Bowman CN. Primary cyclization in the
polymerization of bis-GMA and TEGDMA: a modeling
approach to understanding the cure of dental resins. Dent Mater
2001;17:221–9.
[39] Rey L, Duchet J, Galy J, Sautereau H, Vouagner D, Carrion L.
Structural heterogeneities and mechanical properties of vinyl/
dimethacrylate networks synthesized by thermal free radical
polymerization. Polymer 2002;43:4375–84.
[40] Van Krevelen DW. Properties of polymers. 3rd ed. Amsterdam:
Elsevier Science Publishers BV, 1990. p. 196–7.
[41] Williams G, Lambreches P, Braem M, Celis JP, Vanherle G. A
classification of dental composites according to their morpho-
logical and mechanical characteristics. Dent Mater 1992;8:
310–9.