Adhesive Layer Properties as a Determinant of Dentin Bond

Strength
Ji-Hyun Bae,1 Byeong-Hoon Cho,1–3 Jong-Soon Kim,1 Min-Soo Kim,1 In-Bog Lee,1,2 Ho-Hyun Son,1,2
Chung-Moon Um,1,2 Chang-Keun Kim,4 Oh-Young Kim5
1
Department of Conservative Dentistry, College of Dentistry, Seoul National University, Seoul, Korea

2
Dental Research Institute, Seoul National University, Seoul, Korea

3
Intellectual Biointerface Engineering Center, Seoul National University, Seoul, Korea

4
Department of Chemical Engineering, Choongang University, Seoul, Korea

5
Department of Chemical Engineering, Dankook University, Seoul, Korea

Received 6 October 2004; revised 3 January 2005; accepted 7 February 2005

Published online 30 June 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/jbm.b.30320

Abstract: The goal of this study is to evaluate the hypothesis that the properties of the resin
adhesive might affect the microtensile bond strength (MTBS) of multibottle dental adhesive
system. In order to alter the properties, the experimental resin adhesives containing 2,2-bis
(4-2-hydroxy-3-methacryloyloxypropoxyphenyl)propane (Bis-GMA) and triethylene glycol
dimethacrylate (TEGDMA) at various ratios were prepared. Degree of conversion immedi-
ately after curing (DC-immed), degree of conversion at 48 h after curing (DC-48h) of a thin
coat of the experimental adhesives, the flexural strength (FS) of the bulk specimens made of
the experimental adhesives, pH, viscosity at shear rate of 1 Sⴚ1, and the microtensile bond
strength (MTBS) values of the adhesives to dentin were investigated. The maximum MTBS
and FS values of the resin adhesives were observed when the ratio of Bis-GMA/TEGDMA was
60/40. However, pH and viscosity values increased with increasing Bis-GMA content in the
adhesives. When Bis-GMA content was more than 60 wt %, the viscosity increased exponen-
tially and restricted the DC and FS, and accordingly decreased the bond strength. The
stronger the resin adhesives were, the higher the bond strength to dentin could be obtained.
© 2005 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 74B: 822– 828, 2005

Keywords: viscosity; adhesion; polymer; properties of adhesive layer; microtensile bond

strength

INTRODUCTION the complexity of dentin substrate and the technique sensi-

Micromechanical retention through the formation of resin-
reinforced hybrid layer has been widely accepted as the
primary source of bond strength of the adhesive resins to
dentin.1 Several variables such as the quality,2,3 thickness4 – 6
and elastic modulus of the hybrid layer7 and the chemical
bonds8 between the collagen and the adhesive within the
layer have been suggested as the mechanism of the adhesion
through the hybrid layer. Other possible variables such as
intimate contact into dentinal tubules and lateral branches,9,10
and the thickness11,12 and mechanical properties13–15 of the
adhesive layer have also been studied. However, because of
Correspondence to: Byeong-Hoon Cho (e-mail: chobh@plaza.snu.ac.kr)
Contract grant sponsor: Basic Research Program of the Korea Science and Engi-
neering Foundation; contract grant number R01-2003-000-10216-0
© 2005 Wiley Periodicals, Inc.
822
tivity of bonding systems, there have been controversies
about the effect of each variable on the bond strength.
As the component overlying the hybrid layer, the adhesive
layer may assist to preserve the integrity of the hybridized
dentin, protect it from polymerization shrinkage stresses,16
act as a stress absorbing layer,7 and contribute to improving
and maintaining bond strength.11 When the thickness of the
adhesive layer was increased by applying additional coats of
adhesive, the early marginal leakage was reduced signifi-
cantly by relieving the contraction stress of polymerizing
composite resin through low-stiffness adhesive.17 However,
as a physical variable of the adhesive layer, the effect of its
thickness on the bond strength still remains controver-
sial.11,12,18,19 On the other hand, because the elastic modulus
of the adhesive layer is the lowest among the components of
the bonded assembly including the hybrid layer, the adhesive
layer was regarded as the weakest link.7,20 The bond strength,
 ADHESIVE LAYER AND BOND STRENGTH 823

TABLE I. Materials Used for Preparation of Experimental Resin Adhesivesa

Compound Acronym Supplier Batch No.

Bisphenol-A-glycidyl dimethacrylate Bis-GMA Shin-Nakamura Chemical Co., Inc. 1030M
Triethyeneglycol dimethacrylate TEGDMA Shin-Nakamura Chemical Co., Inc. 1118P
Camphoroquinone CQ Aldrich Chemical Co., Inc. 00703MN
Ethyl 4-dimethylaminobenzoate 4E Aldrich Chemical Co., Inc. 11920PA
a
Other ingredients, such as inhibitors or stabilizers, were not added to the experimental resin adhesives.

when it is measured in a universal testing machine (UTM) or (DC), flexural strength (FS), pH, and viscosity (V) of the
at which the bond fails in a clinical situation, may be deter- resin adhesives was also evaluated.
mined by the mechanical properties, such as the strength or
elastic modulus, of the adhesive layer itself.15
In this study, as a potential determinant, it was hypothe- MATERIALS AND METHODS
sized that improving the mechanical properties of the resin
adhesive itself by changing the ratio of base monomers would Preparing Experimental Adhesives
increase the microtensile bond strength (MTBS) of the adhe-
The experimental resin adhesives were prepared with the use
sive to dentin. 2,2-bis(4-2-hydroxy-3-methacryloxypropoxy-
of the compounds listed in Table I. Seven experimental
phenyl)propane (Bis-GMA) is used as a base monomer in
adhesives formulated with various Bis-GMA/TEGDMA ra-
most current dental composite resins and adhesives, and its
tios were prepared, and their compositions are shown in
rigid bisphenol-A backbone leads to a rigid polymer with
Table II. The ratios of Bis-GMA/TEGDMA were 20/80
high mechanical properties and low polymerization shrink-
(B20), 30/70 (B30), 40/60 (B40), 50/50 (B50), 60/40 (B60),
age. However, because of its high viscosity, Bis-GMA has to
70/30 (B70), and 80/20 (B80) by weight. 1.0 wt % of cam-
be used with a diluent, triethyleneglycol dimethacrylate
phoroquinone and 1.0 wt % of ethyl 4-dimethylaminobenzo-
(TEGDMA), for adjusting handling properties. When the
ate were added to each mixture. Except for the diluent mono-
ratios of Bis-GMA/TEGDMA are altered, the properties of
mer TEGDMA, no other solvent, such as acetone, ethanol, or
the mixtures, such as the viscosity, strength, elastic modulus,
water, was used. The resin adhesive (bonding resin) of
and hardness, were also changed.21,22 In order to evaluate the
Scotchbond Multi-Purpose adhesive system (SBMP, 3M
net effect of the properties of the adhesive resin itself on bond
ESPE Dental Products, St. Paul, MN) was used as a control
strength, the hybrid layers having the same quality in all the
material.
experimental groups were obtained by treating dentin sur-
faces with the same etchant and primer of a commercial
Measuring the Degree of Conversion
adhesive system, and then the assigned experimental adhe-
with FTIR Spectroscopy
sives containing various ratios of Bis-GMA/TEGDMA were
applied. The MTBS of the experimental adhesives to dentin After collecting a background spectrum with a press-molded
was measured as a function of various Bis-GMA/TEGDMA potassium bromide (KBr) disk, the spectrum of uncured ad-
ratio and its interdependence on the degree of conversion hesive was obtained from the resin adhesive painted on the

TABLE II. The Compositions of the Experimental Adhesives Used in this Study, Degree of Conversion Immediately
After Curing and at 48 h After Curing (DC, n ⴝ 3), Flexural Strength (FS, n ⴝ 17–20), viscosity (V), pH (n ⴝ 3),
and microtensile bond strength to dentin (MTBS, n ⴝ 20 – 24)

DC (%) DC (%) at
Groups (Bis- Immediately 48 h After V MTBS
GMA/TEGDMA) After Curing Curing FS (MPa)* (Pa 䡠 s) pH (MPa)*
B20 (20/80) 51.2 (3.6)**,c 55.8 (3.0)d,e 69.9 (8.7)e 0.028 3.38 (0.04)e 23.1 (8.2)d
B30 (30/70) 56.1 (2.1)a,b,c 67.4 (7.4)a,b,c 76.1 (6.3)c,d 0.039 5.55 (0.02)d 25.1 (10.1)d
B40 (40/60) 57.8 (2.1)a,b 69.9 (2.3)a,b 76.9 (8.0)b,c,d 0.071 6.03 (0.01)c 32.8 (9.2)a,b,c
B50 (50/50) 59.9 (1.9)a 72.3 (2.3)a 79.0 (9.2)a,b,c 0.16 6.05 (0.01)c 35.6 (14.1)a,b
B60 (60/40) 54.5 (3.2)b,c 68.8 (1.5)a,b,c 83.3 (9.9)a 0.45 6.20 (0.04)b 38.9 (11.5)a
B70 (70/30) 51.9 (3.0)c 62.7 (1.3)b,c,d 79.6 (7.7)a,b 1.32 6.24 (0.02)b 36.8 (10.7)a,b
B80 (80/20) 49.4 (3.6)c,d 51.7 (6.2)c 64.6 (8.9)e 5.24 6.55 (0.05)a 28.1 (11.2)c,d
SBMP† adhesive 52.6 (3.8) 70.0 (2.5) 83.3 (6.1) 0.38 7.4§ 33.6 (10.4)
* The FS and MTBS were measured at 48 h after curing.
†
SBMP: Scotchbond Multi-Purpose Plus adhesive system (3M ESPE, USA).
§
Reference: http://www.cranews.com/newsletter/highlights/2000/00-11/pH meth
** The numbers in parentheses are standard deviations. Mean values with the same superscript are not significantly different (P ⬎ 0.05).
824 BAE ET AL.

KBr disk with Fourier transformation infrared spectroscopy

(FTIR; Spectrum One, Perkin-Elmer Instruments, Shelton,
CT). Then the sample was covered with a sheet of celluloid
strip (GC Co., Tokyo, Japan) and irradiated for 20 s with a
dental light-curing unit (Hilux™ Ultra⫹, Benlioglu Dental
Inc., Ankara, Turkey; power density more than 500 mW/
cm2). After removal of the celluloid strip, the FTIR spectrum
of the cured adhesive immediately after light curing was
collected. Because the MTBS was measured at 48 h after
bonding, the cured sample was stored in a dark plastic con-
tainer for 48 h and the FTIR spectrum of cured adhesive at
48 h after curing was also obtained. All the spectra were
obtained in a transmission mode with 16 scans at a resolution
of 4 cm⫺1. Three measurements were performed for each
experimental adhesive. The intensities of the aliphatic CAC
absorbance peak at 1638 cm⫺1 and the aromatic COC ab-
sorption peak at 1608 cm⫺1 as an internal reference were
measured in an absorbance mode with the use of a standard
baseline technique. After the peak height of aliphatic CAC
absorbance peak was corrected with that of the aromatic
reference peak, DC value was determined from the ratio of
corrected absorbance peak obtained before and after poly-
merization with the following equation.23
[Abs(C ⫽ C)/Abs(C-C)]monomer
⫺ [Abs(C ⫽ C)/Abs (C-C)]polymer
D.C. (%) ⫽ ⫻ 100
[Abs(C ⫽ C)/Abs(C-C)]monomer
Measuring the Flexural Strength
The specimen for FS measurement was made from a rectan-
gular bar-shaped stainless-steel mold with a dimension of 2 ⫻
2 ⫻ 25 mm. It was attached on a glass slide with double-sided
adhesive tape, filled with experimental resin adhesive, and
precisely covered with another glass slide preventing en-
trapped air, and clamped the entire assembly with spring-
loaded binder clamps. The adhesive resin was cured with
three overlapping 20 s irradiations with the use of a wide
light-guide tip (11 mm in diameter) of a Hilux light-curing
unit. In the same manner, the specimen was cured from the
opposite side. Then the specimen was removed from the mold
and stored for 48 h in a dark container with 100% relative
humidity. After the specimen was polished with P500 silicon-
carbide (SiC) paper and dimensions of the specimen were
measured with a digital micrometer, the FS was measured
with the use of a three-point bend test in a UTM (Instron
model 4466, Instron Corp., Canton, MA) at a crosshead speed
of 1 mm/min, in accordance with the International Standard
Organization (ISO) Specification No. 4049. The maximum
load was obtained by pressing the center of the cured rect-
angular bar mounted between supports (20 mm in length) of
UTM.
Measuring the pH
After the pH meter was calibrated (Accumet威 Research
AR25, Fisher Scientific, Pittsburgh, PA) with 2.0 and 1.0
Figure 1. Specimen preparation for microtensile bond strength test.
standard buffer solution, the probe was rinsed with distilled
water, shaken, blotted of excess water, and put into the test
tube containing the experimental adhesive. The pH measure-
ment was recorded after 2 min. After each measurement, the
probe was rinsed with acetone and distilled water, shaken,
and blotted of excess water in order to remove any traits of
previously measured monomer; then calibration was per-
formed.
Measuring the Viscosity
The viscosity of the experimental adhesives was measured
with the use of a rotational rheometer (AR 2000, TA instru-
ment, New Castle, DE). Because the viscosity of the exper-
imental adhesives ranged from liquid TEGDMA to highly
viscous Bis-GMA, two geometries were used for steady shear
test—a cone and plate for the adhesives showing the viscosity
higher than 0.1 Pa 䡠 s and a concentric cylinder for those
lower than 0.1 Pa 䡠 s. The shear rate range tested was
0.01–100 S⫺1. All the tests were done in a dark room at 25°C.
Measuring the Microtensile Bond Strength
Thirty-two freshly extracted noncarious human molars were
cleaned and immersed in a 0.5% chloramine-T solution for a
week and then stored in distilled water at 4°C. The tooth was
mounted in cubic-shaped steel mold with direct resin (Figure
1). In order to align the adhesive interface perpendicular to
the applying tensile load, the occlusal enamel was ground
away perpendicular to the long axis of the tooth with the use
of a low-speed diamond saw (Isomet; Buehler Ltd., Lake
Bluff, IL) and polished with the use of an automatic polishing
machine (Rotopol-V, Struers Ltd., Glasgow G60 5EU, UK)
with P500 SiC paper under running water until the last
remnant of enamel was removed. In order to ensure that the
hybrid layer has the same quality among the groups, the
etching and priming steps were performed with a commercial
dentin bonding system. The exposed flat occlusal dentin
 ADHESIVE LAYER AND BOND STRENGTH 825

Figure 2. Degree of conversion immediately after curing (DC-immed) and at 48 h after curing
(DC-48h), flexural strength (FS), viscosity (V), pH, and microtensile bond strength to dentin (MTBS)
with the increase of Bis-GMA content.

surface was etched with 35 wt % phosphoric acid (the etchant was done at a 5% level of significance. The polynomial
of SBMP; 3M ESPE Dental Products) for 15 s and rinsed regression analysis was performed in order to compare the
with copious amounts of distilled water for 15 s. The primer patterns in the change of the DC, FS, and MTBS values with
of SBMP was applied on the moist dentin surface of the tooth increasing Bis-GMA/TEGDMA ratios. Statistic calculations
and dried with gentle air flow. In order to equalize the were done using SigmaStat (Version 2.03; Jandel Scientific
thickness of the adhesive layer among all the experimental Software, Chicago, IL).
adhesives, 20 ␮L of each experimental adhesive was applied
with a micropipette, spread with the micropipette tip, and
cured for 20 s. Z-250 hybrid composite resin (A3 shade, 3M RESULTS
ESPE Dental Products) was built up in three increments to
approximately 3.5 mm in height. Each layer was light cured
The experimental results of DC immediately after curing
for 20 s according to the manufacturer’s recommendation.
(DC-immed), DC at 48 h after curing (DC-48h) of a thin coat
After storing the sample in distilled water for 24 h, the sample
of the experimental adhesives, the FS of the bulk specimens
was at first trimmed to rectangular shape with the use of a
made of the experimental adhesives, the viscosity at shear
low-speed diamond saw. With a diamond burr fixed in a
rate of 1 S⫺1, pH, and the MTBS values of the adhesives to
low-speed press drill, notches were made along the dentin–
dentin are shown in Table II. One-way ANOVA showed that
adhesive interface line, so that the sample would be an
when the DC, FS, and MTBS were measured at 48 h after
hourglass shape. The narrowest neck of the hourglass-shaped
curing, there were statistically significant differences among
specimen should meet with both ends of the adhesive inter-
the adhesives containing various ratios of Bis-GMA/TEG-
face and be approximately 1 mm wide. Then, the specimen
DMA (p ⬍ 0.05). From the polynomial regression analysis,
was sliced with the low-speed diamond saw into 0.6 mm-
the changes of the DC, FS, and MTBS according to the
thick sections perpendicular to the interface. After measuring
increase of Bis-GMA/TEGDMA ratio fit better for the third-
the thickness and width of the neck of the specimen with a
order cubical relation than the linear or the second-order
digital micrometer, the specimen was attached to a measuring
quadratic relation. Although there were no statistically sig-
apparatus with cyanoacrylate cement (Super Glue Gel, 3M,
nificant differences in the MTBS within the range of 40 –70
St. Paul, MN). The whole assembly was set in a UTM
wt % Bis-GMA content, the MTBS obtained with the exper-
(Instron model 4466) and the strength value at breakage was
imental adhesives increased along with the increase of the
measured at a crosshead speed of 1 mm/min.19
Bis-GMA content in the experimental adhesives, reached the
maximum value when Bis-GMA concentration was 61.5 wt
Statistical Analysis
% from the polynomial regression curve, and then decreased
All the data of the DC, FS, pH, and MTBS were analyzed by (Table II, Figure 2). The polynomial regression curves of the
one-way ANOVA, and as post hoc tests, the Duncan’s test FS, DC-immed and DC-48h also demonstrated a pattern
826 BAE ET AL.

Figure 3. Plotting parameters against the pH and viscosity. (a) When Bis-GMA content in the adhesive
was below 40 wt %, with the increase of Bis-GMA content, the pH increased quickly. When the
Bis-GMA content was over 40 wt %, the pH increased steadily and approached 6.5, but all the
properties (DC, FS, and MTBS) decreased when Bis-GMA was increased to more than 60 wt %. (b)
With the increase of Bis-GMA content in the adhesive up to 60 wt %, the values of DC, FS, and MTBS
increased along with increasing viscosity in a relatively proportionate manner. However, when the
Bis-GMA content was over 60 wt %, the viscosity increased exponentially, which corresponded with
the decrease of the properties. All the properties were plotted against the logarithmic scale of viscosity
values.

similar to that of the MTBS; that is, the maximum values of
the FS, DC-immed, and DC-48h were predicted at 57.2 wt %,
42.0 wt %, and 47.0 wt %, respectively.
With an increase of Bis-GMA content in the adhesives, the
pH and viscosity values were dramatically increased (Table
II, Figure 2). When the mean values of each parameter were
plotted against the pH or viscosity, the viscosity started to
increase steeply where the values of the DC-48h, FS, and
MTBS were going to decrease significantly, but the pH did
not change [Figures 3(a,b)]. When the viscosities of the
experimental adhesives were lower than 0.16 Pa 䡠 s, the
DC-immed and DC-48h increased with increasing Bis-GMA
content in the adhesives, but until the viscosity approached to
0.45 Pa 䡠 s, the FS and MTBS increased continuously [Figure
3(b)]. When the viscosity of the adhesives that contained over
50 wt % Bis-GMA increased exponentially, the DC-48h
stared to decrease. However, FS and MTBS values decreased
a little later when Bis-GMA was added at more than 60 wt %.
With the adhesive containing 80 wt % Bis-GMA, the changes
became significant.
DISCUSSION
In previous studies on the variables affecting bond strength,
the authors became interested in the adhesive layer as a
potential determinant of the bond strength in the UTM test or
at the time when the bond failed in clinical situations. When
the shrinkage stress of the polymerizing composite resin
confined in a Class I cavity was applied on the previously
cured adhesive layer, a poorly cured adhesive layer failed to
maintain the bond integrity and resulted in gap formation
within the adhesive layer.24 The FS of the adhesive cured for
only 10 s, which was recommended for curing most current
dental adhesives, was very low, and suggested as the cause of
the crack development within the adhesive layer when the
polymerization shrinkage stress was applied.15 Most of the
specimens fractured by nearly pure tension in the microten-
sile test showed fractures within the adhesive layer extending
toward the interfaces with the hybrid layer or the composite
resin or fractures at the top of the hybrid layer.19 This phe-
nomenon was consistent with the lowest mechanical proper-
ties of the adhesive resin layer reported by Van Meerbeek et
al.,7 and the concept of the bond quality reported by Versluis,
Tantbirojn, and Douglas,25 describing the properties of bond-
ing layer as boundary condition. Takahashi et al. also re-
ported a significant correlation between the ultimate micro-
tensile strength of the resins and their microtensile bond
strength to dentin.14
Concerning the fracture plane, when bond strength was
measured in a shear mode, the fracture modes were classified
into three categories, that is, adhesive fracture, cohesive frac-
ture of dentin, and cohesive fracture of composite resin.
However, when bond strength was measured with the use of
the MTBS test or the fracture toughness test, the fracture
planes were observed to be wandering between the top of the
hybrid layer and within the adhesive layer.19,26 –28 Whether
the adhesive system was a one-bottle or a multistep one,
during the application of the system, defects or voids may
remain at the interface between the hybrid layer and the
adhesive layer. If there are any defects at the top of the
hybrid, the bond failure may initiate from it and can be
explained by the crack initiation and the brittle fracture mech-
anism. However, if there is no defect, the fracture may occur
within the weakest adhesive layer among the components of
the bonded complex. Therefore, the debonded surfaces after
MTBS test were described as a mixed type of fracture with a
combination of interfacial failure and cohesive failure within
 ADHESIVE LAYER AND BOND STRENGTH
the adhesive layer.14 As to the variables related to the adhe-
sive layer, both the above-mentioned mechanical properties
and the defects working as cracks would be considered to
affect the bond strength.
In this study, it was hypothesized that, if all the other
variables could be held steady, the properties of the resin
adhesive itself would be a potent determinant of the bond-
strength measurements. In order to evaluate the net effect of
the properties of the resin adhesive itself on bond strength,
first, the hybrid layers having the same quality in all the
experimental groups were obtained by treating the dentin
surfaces with the same etchant and primer of a commercial
adhesive system, and then the assigned experimental adhe-
sives were applied. Second, in order to obtain the adhesive
layer having same thickness in all the groups, a micropipette
was used to apply the same amount of experimental resin
adhesives. Because of the difference in the viscosity of the
solvent-free experimental adhesives, the thickness of the ad-
hesive layer would be affected with conventional brush ap-
plication; that is, the thicker experimental adhesive coated
with a brush would result in a thicker adhesive layer. There is
still controversy concerning the relationship between the
thickness of the adhesive layer and bond strength measure-
ments.11,12,18,19 However, in order to exclude the effect of the
thickness on the bond strength, the thickness was controlled
with the volume of the bonding agent applied. Although the
viscosities of bonding resins were different, because the teeth
were randomly divided into eight groups and the resins were
spread on the entire surface, it was assumed that the same
volume divided by the same area make the thickness roughly
the same. Third, the experimental adhesives were formulated
as solvent-free ones. Although the phase separation resulting
from the difference in the viscosity of the major monomers
may act as defects or flaws,11,29,30 the adhesive layer made
from the solvent-free adhesives can be supposed to have
minimal even flaws because the drying step was skipped.
Additionally, because the amine peroxide ratio can also affect
the properties of the experimental adhesive resins,31 the ratio
of camphoroquinone and ethyl 4-dimethylaminobenzoate was
fixed at 1:1 by weight in all the experimental adhesives.
To increase the mechanical properties of the resin adhe-
sive, in general, the improvement of the base monomers or
loading fillers into the adhesive has been adopted. When the
ratios of Bis-GMA/TEGDMA were altered, the properties of
the mixtures, such as the viscosity, conversion, pH, and
shrinkage stress, were also changed.22 Loading fillers in a
micron scale increased the bond strength.13 In this study,
although there were no statistically significant differences in
the MTBS within the range of Bis-GMA content of 40 –70 wt
%, the MTBS increased significantly with increasing ratios of
Bis-GMA/TEGDMA from 20/80 to 60/40, reached the max-
imum when Bis-GMA content was 60 wt %, and then de-
creased dramatically when Bis-GMA content was 80 wt %.
The DC and FS with increasing ratios of Bis-GMA/TEG-
DMA from 20/80 to 80/20 also exhibited a similar pattern.
This experimental result suggested that the present hypothesis
might be accepted.
827
From the results, the decrease in the DC and FS of the
adhesives containing more than 60 wt % of Bis-GMA were in
accordance with that of the MTBS of those adhesives. In
order to investigate the reason the values of these parameters
decreased in the adhesives with higher Bis-GMA content, the
pH and viscosity values were evaluated. The activity of the
amine accelerator commonly used in the dental polymeric
materials was known to be retarded in an acidic condition.
Like the connection between the increments in the incremen-
tal filling of composite resin,32 the copolymerization between
the top of the hybrid layer and the adhesive layer or between
the adhesive layer and the composite resin will be mediated
by the oxygen-inhibited layer of unpolymerized matrix
monomers. The acidity of the resin adhesive may obstruct the
acceleration of the polymerization at the interface between
the top of the adhesive layer and the composite resin. But in
the present research, under weakly acidic conditions (pH ⫽
3.38 – 6.55), there was no significant effect of pH on DC, FS,
and MTBS.
From the viewpoint of the polymerization kinetics, the
viscosity might cause the decrease of DC, FS, and MTBS of
the thick adhesives. Bis-GMA is a very reactive molecule and
its polymerization reaction is diffusion controlled. On the
other hand, TEGDMA reduces the viscosity of the mixture
and increases the mobility of the reactants that can delay the
diffusion-controlled termination.21,22 Within the range of low
viscosity [less than 0.16 Pa 䡠 s of the adhesive containing 50
wt % of Bis-GMA, Table II and Figure 3(b)], the increase of
highly reactive Bis-GMA within a mixture resulted in the
increase of the DC. With an increase of the DC value of the
system, the high molecular weight (MW) and abundant
crosslinking of Bis-GMA resulted in the higher FS until the
Bis-GMA concentration reached 60 wt % within the adhe-
sive, and in turn, contributed partly to the increase of the
MTBS [Figure 3(b)]. However, because the polymerization
kinetics of each monomer can be attributed to the mobility
and crosslinking density of the reactant, the extreme increase
of Bis-GMA in the mixture increases the viscosity of the
system, results in autodeceleration of the reaction, and causes
lower conversion.21 Even with the high MW and abundant
crosslinking of Bis-GMA, when mixtures had extremely high
viscosity, the high viscosity might also decrease the FS and
MTBS by lowering the DC.
CONCLUSION
The bond strength (MTBS) of the experimental dentin adhe-
sives increased with increasing mechanical properties (FS) by
varying the Bis-GMA/TEGDMA ratios. Therefore, the
present hypothesis was accepted. Increasing DC as a physical
property affected the bond strength indirectly through the
increase in FS due to high molecular weight and abundant
crosslinking of Bis-GMA. Clinically, stronger resin adhesives
would improve the integrity of the dentin adhesive bond.
However, extremely increased viscosity of the resin adhe-
sives resulted in decreased DC, because the reactivity of the
828 BAE ET AL.
major monomers was restricted. As a result, the mechanical
property (FS) and bond strength (MTBS) were also de-
creased.
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