Effect of Water Aging of Adherend Composite on Repair

Bond Strength of Nanofilled Composites

Daiki Naganoa / Masatoshi Nakajimab / Masahiro Takahashic / Masaomi Ikedad / Keiichi Hosakae /
Kento Satof / Taweesak Prasansuttiporng / Richard M. Foxtonh / Junji Tagamii

Purpose: To evaluate the effect of water aging of adherend composite on repair bond strength to nanofilled com-
posites with specific fillers using different bonding agents.
Materials and Methods: Three nanofilled composites – Beautifil II with S-PRG filler (BE) / Filtek Supreme ultra with
nanocluster filler (SP) / Estelite Σ Quick (ES) – and one microhybrid composite, Clearfil APX (AP), were used in this
study. The composite disks were immersed in water for different durations (immediate, 1 week, 2 weeks or 1 month),
and then the polished surfaces were treated with one of three bonding agents – no treatment (control), application of
Clearfil SE One (SE), application of Clearfil SE One plus Clearfil Porcelain Bond Activator (PB) – then filled with a repair
composite. The bonded composite disks were subjected to the microshear bond strength (μSBS) test. Additionally,
water sorption (Wsp) and solubility (Wsl) of the resin composite were measured. The μSBS data were was statistically
analyzed using a three-way ANOVA and t-test with Bonferroni correction for multiple comparisons.
Results: Water aging of adherend composite affected the repair bond strength (p < 0.05). For BE, SP, and ES,
application of an adhesive agent improved repair bond strengths to water-aged composites (p < 0.05), but adding a
silane coupling agent could not (p > 0.05). For AP, the μSBS significantly increased, with control group
< SE group < PB group (p < 0.05).
Conclusion: Microhybrid composite was a more suitable material for composite repair than nanofilled composite,
due to adhesion to exposed, larger silica fillers. S-PRG filler and nanocluster filler in the nanofilled composites
played a slight role in improving their repair bonding performances with the bonding agents tested.
Keywords: bond strength, dental materials, resin composite repair, surface treatments, water solubility, water sorption.

J Adhes Dent 2018; 20: 425–433. Submitted for publication: 06.01.18; accepted for publication: 10.09.18
doi: 10.3290/j.jad.a41331

R esin composite has become an almost universal ma-

terial in clinical practice21 due to its many advan-
tages, such as adhesion to tooth structures, ease of ma-
nipulation, superior mechanical properties, excellent
esthetics, and placement in conservative tooth prepara-
tions.25 Consistent with the philosophy of minimally inva-
sive dentistry, when a resin composite restoration exhib-
its secondary caries or a marginal defect, repair of the

f Clinical Fellow, Cariology and Operative Dentistry, Department of Oral Health

a Graduate Student, Cariology and Operative Dentistry, Department of Oral
Sciences, Graduate School of Medical and Dental Sciences, Tokyo Medical
Health Sciences, Graduate School of Medical and Dental Sciences, Tokyo
and Dental University, Tokyo, Japan. Consulted on and performed statistical
Medical and Dental University, Tokyo, Japan. Experimental design, performed
evaluation, contributed substantially to discussion.
the experiments, wrote the manuscript.
g Assistant Professor, Department of Restorative Dentistry and Periodontology,
b Junior Associate Professor, Cariology and Operative Dentistry, Department of
Faculty of Dentistry, Chiang Mai University, Chiang Mai, Thailand. Proofread
Oral Health Sciences, Graduate School of Medical and Dental Sciences, Tokyo
the manuscript, contributed substantially to discussion.
Medical and Dental University, Tokyo, Japan. Experimental design, analyzed
data, conducted statistical analysis, wrote and proofread the manuscript, con- h Clinical Senior Lecturer, Department of Restorative Dentistry, King’s College
tributed substantially to discussion. London Dental Institute, King’s College London, London Bridge, London, UK.
c Proofread the manuscript, contributed substantially to discussion.
Clinical Fellow, Cariology and Operative Dentistry, Department of Oral Health
Sciences, Graduate School of Medical and Dental Sciences, Tokyo Medical i Professor, Cariology and Operative Dentistry, Department of Oral Health
and Dental University, Tokyo, Japan. Consulted on and performed statistical Sciences, Graduate School of Medical and Dental Sciences, Tokyo Medical
evaluation, contributed substantially to discussion. and Dental University, Tokyo, Japan. Research idea, study design, wrote the
d manuscript.
Junior Associate Professor, Department of oral Prosthetic Engineering, Gradu-
ate School of Medical and Dental Sciences, Tokyo Medical and Dental Univer-
sity, Tokyo, Japan. Consulted on and performed statistical evaluation.
Correspondence: Junior Associate Professor Masatoshi Nakajima, Cariology
e Assistant Professor, Cariology and Operative Dentistry, Department of Oral and Operative Dentistry, Department of Oral Health Sciences, Graduate School
Health Sciences, Graduate School of Medical and Dental Sciences, Tokyo of Medical and Dental Sciences, Tokyo Medical and Dental University, 1-5-45,
Medical and Dental University, Tokyo, Japan. Proofread the manuscript, con- Yushima, Bunkyo-ku, Tokyo, 113-8549, Japan. Tel: +81-3-5803-5483; e-mail:
tributed substantially to discussion. nakajima.ope@tmd.ac.jp

Vol 20, No 5, 2018 425

Nagano et al
restoration is recommended rather than complete removal
and replacement.41
The success of composite repair depends on the chemi-
cal composition of the resin composite to be repaired, as
well as its surface roughness and wetness. It has been re-
ported that unreacted monomer in the matrix of resin com-
posite plays an important role for the immediate repair
bonding performance.2,11,14,31 However, during aging in the
oral environment, the unreacted monomer leaches from the
resin composite, and the resin matrix absorbs water.11,40
Water sorption is dependent upon the hydrophilicity of the
resin composite material, cross-linking density and porosity
of the resin matrix, and/or different filler components.12 Ab-
sorbed water can reduce the wettability of freshly-filled hy-
drophobic composite on water-aged, cured composite.
These alterations lead to reductions in their repair bond
strengths.3,7,37 Application of one-step self-etch adhesive to
water-aged cured composite might improve surface wettabil-
ity of freshly-filled composite. However, there is little infor-
mation about the effect of absorbed water in the resin ma-
trix on the repair bond strengths using an adhesive agent.
On the other hand, it has been reported that chemical
treatment of the exposed fillers on the surface of the aged
resin composite could improve repair bond strengths.18,22
Previously, microfilled hybrid resin composites composed of
silica microfillers with organic fillers have been developed.
Therefore, application of a silane coupling agent has been
shown to significantly increase repair bond strength to
these resin composites,4 because it enhances the chemi-
cal bonding to exposed silica fillers on the surface of aged
resin composite.4,11,18,20,24,28,29,40 In the last few years,
nanofilled resin composites with silica or silica-zirconia filler
have been introduced, being accompanied with using vari-
ous unique fillers, such as S-PRG (Giomer) filler or nanoclu-
ster filler. Some researchers have demonstrated that in
SEM images of ground composite surfaces, nearly all of the
smaller fillers were covered by resin matrix, although the
large fillers were clearly not covered;15-17 this indicates that
surface treatment with silane did not contribute to an in-
crease of repair bond strength to nanofilled compos-
ites.15,16,26 However, it is still unclear whether surface
treatment with a silane coupling agent is effective in repair-
ing nanofilled composites containing these specific fillers
when the adherend composite was water aged.
The purpose of this study was therefore to evaluate ef-
fect of water aging of adherend composite on repair bond
strength to nanofilled composites with specific fillers and
microhybrid composite, using two bonding approaches: ap-
plication of an adhesive agent or a silane coupling agent,
with subsequent examination of their water sorption and
solubility.
MATERIALS AND METHODS
Study Materials Used
Three commercially available nanofilled resin composites –
Beautifil II (BE, Shofu; Kyoto, Japan) / Filtek Supreme ultra
426
(SP, 3M Oral Care; St Paul, MN, USA) / Estelite Quick (ES,
Tokuyama Dental Japan; Tokyo, Japan) – and one microhy-
brid resin composite, Clearfil APX (AP, Kuraray Noritake
Dental), were used in this study (Table 1).
Microshear Bond Strength Test
Specimen preparation for the microshear bond strength
(μSBS) test is illustrated in Fig 1. Thirty-six resin composite
disks of each material were fabricated using a washer mold
(15.0 mm in internal diameter and 1.0 mm in thick). Un-
cured composite resin was packed into the mold and then
covered with transparent celluloid strips (KerrHawe Striproll,
KerrHawe; Bioggio, Switzerland) on glass plates on the top
and bottom surfaces. Light curing was performed from one
side for 40 s using a halogen light-curing unit (Optilux501,
Kerr; Orange, CA, USA) at an intensity of 600 mW/cm2 in
contact with the cover-glass plate, and then the cured resin
was carefully removed from the mold with the strips and
glass plates. The specimens were divided into four experi-
mental groups and individually immersed in distilled water
in glass vials at 37°C for the designated storage periods
(immediate, 1 week, 2 weeks or 1 month). After completing
each designated water-storage period, the resin disk sur-
faces were polished with 1000-grit silicon carbide (SiC)
paper for 30 s. The surface of each resin disk was divided
into four areas, and each area was treated with a bonding
application randomly selected from three methods as fol-
lows; 1. no surface treatment (control group); 2. application
of one-step self-etch adhesive (Clearfil SE One, Kuraray
Noritake Dental; Tokyo, Japan) (SE group); 3. application of
silane coupling adhesive agent (mix of Clearfil SE One with
Clearfil Porcelain Bond Activator, Kuraray Noritake Dental)
(PB group) (Table 1). After the treated surface was air dried
for 5 s, four microbore Tygon tubes (Saint-Gobain Perfor-
mance Plastics; Nagano, Japan) with an internal diameter
and height of 0.79 mm and 0.5 mm, respectively, were
placed on the four adhesive areas on each cured resin
composite disk to make resin composite cylinders. Subse-
quently, the adhesives were light cured using a halogen
light-curing unit (Optilux501, Kerr) at an intensity of
600 mW/cm2 for 10 s. Resin composite (APX) was carefully
placed into the tubes, then light cured for 40 s. After 1-h
storage at room temperature (23°C), the Tygon tubes were
carefully removed using a sharp blade, and the bonded
specimens were stored in water at 37°C for 24 h.
Prior to the microshear bond strength test, all the inter-
faces were checked using Swept Source Optical Tomogra-
phy (SS-OCT, Santec; Aichi, Japan) for any bonding defects.
Any resin cylinders which showed interfacial gap formation,
bubble inclusion, or any other defects were excluded. The
bonded specimens were attached to the testing device
(EZ test 500N, Shimadzu; Kyoto, Japan) and subjected to
microshear bond strength testing at a crosshead speed of
1 mm/ min until failure (n = 12), as previously described by
Shimada et al.33
After testing, the debonded specimens were mounted on
brass tablets and gold sputter-coated. The fractured areas
were observed using a scanning electron microscope (SEM,
The Journal of Adhesive Dentistry
 Nagano et al

Table 1 Compositions and lot No. of the materials used in this study

Materials Lot No. Composition Filler type Filler particle size Filler content
Clearfil SE One 4E0046 MDP, bis-GMA, HEMA, hydrophobic DMA,
(Kuraray Noritake sodium fluoride, silanated colloidal
Dental; Tokyo, silica, accelerators, initiators, CQ,
Japan) ethanol, water (pH 2.3)

Clearfil Porcelain 6A0013 J-MPTS, hydrophobic aromatic

Bond Activator dimethacrylate
(Kuraray Noritake
Dental)

Cleafil AP-X (APX) 01143A Bis-GMA, TEG-DMA, barium glass filler, microfilled 0.1-15 μm 66%vol
(Kuraray Noritake silica filler, photoinitiator, catalyst, hybrid
Dental) accelerator, pigment, others

Beautifil II 071530 Bis-GMA, TEG-DMA, glass filler, S-PRG nanofilled/ 0.01-4 μm 69%vol
(Shofu; Kyoto, filler, photoinitiator, pigment, others S-PRG(Giomer)
Japan)

Filtek Supreme Ultra N721635 Bis-GMA, bis-EMA, UDMA, TEG-DMA, nanofilled/ 0.01-0.02 mm 56%vol
(Supreme) PEGDMA, zirconia filler, silica filler, nanocluster
(3M Oral Care; St photo initiator, catalyst, accelerator,
Paul, MN, USA) pigment, others

Estelite 6 Quick JO9 Bis-GMA, TEG-DMA, silica-zirconia filler, supra-nanofilled 0.2 μm 71%vol
(Estelite) photoinitiator, catalyst, accelerator, hybrid
(Tokuyama Dental pigment, others
Japan; Tokyo, Japan)

Abbreviations: bis-GMA: bis-phenol A diglycidylmethacrylate; CQ: camphorquinone; DMA: dimethacrylate; HEMA: 2-hydroxyethyl methacrylate; MDP: 10-methac-
ryloyloxydecyl dihydrogen phosphate; MEP: methacryloyloxyethyl dihydrogen phosphate; J-MPS: J-trimethoxysilylpropyl methacrylate; TEG-DMA: triethylene glycol
dimethacrylate.

Microshear bond strength test

Immediate
Composite disk
No treatment (control group)
1-week SE One (SE group)
1 mm

2-week SE One + Activator (PB group)

1-month Placement of 4 plastic
15 mm
tubes (height 0.5 mm,
polish with Surface treatment internal diameter 0.79 mm)
Water storage
#1000 SiC Light cure
for 10 s

Failure mode
analysis by SEM

stored in water at remove the tubes Light cure fill with

37°C for 24 h for 40 s composite resin

microshear bond
test at a crosshead
speed of 1 mm/min

Fig 1 Schematic illustration of specimen preparation and microshear bond strength test.

Vol 20, No 5, 2018 427

Nagano et al

Table 2 Shear bond strength (MPa) of resin composite after designated water storage periods

Adhesive Immediate 1 week 2 weeks 1 month

APX Control 20.7 (3.4)Aa 11.7 (3.2)Ba 11.2 (3.0)Ba 11.7 (1.3)Ba

SE 27.7 (2.3)Ab 24.2 (4.3)ABb 20.9 (3.8)Bb 14.6 (1.2)Cb

PB 39.2 (3.7)Ac 37.4 (5.0)Ac 37.3 (3.2)Ac 33.1 (4.1)Bc

Beautifil II Control 14.0 (4.0)Aa 13.3 (2.5)Aa 12.8 (3.7)Aa 13.2 (1.9)Aa

SE 24.4 (1.7)Ab 21.6 (2.4)ABb 19.7 (4.9)Bb 17.7 (2.5)Bb

PB 20.0 (5.6)Ac 22.5 (5.0)Ab 19.7 (3.1)ABb 15.5 (3.4)Bab

Estelite Control 20.9 (1.3)Aa 14.1 (1.3)Ba 11.2 (2.0)Ba 11.6 (2.6)Ba

SE 22.4 (3.2)Aa 19.9 (2.7)Ab 17.0 (2.7)Bb 15.8 (3.6)Bb

PB 20.9 (2.1)Aa 16.1 (0.9)Bc 16.0 (2.1)Bb 14.5 (2.3)Bb

Supreme Control 10.2 (1.3)Aa 8.2 (2.1)Aa 7.4 (2.4)Aa 7.1 (1.1)Aa

SE 17.2 (2.8)Ab 17.0 (2.3)Ab 16.8 (3.9)Ab 17.6 (3.2)Ab

PB 25.1 (3.0)Ac 12.9 (2.1)Bc 13.0 (2.4)Bc 15.4 (4.5)Bb

Values are mean (SD) (n =12). Same superscript letters indicate no statistically significant difference (p > 0.05). Upper case letters refer to rows, and lower
case letters refer to columns in same resin composite.

JSM-5310, JEOL; Tokyo, Japan) at magnifications of 100X
and 500X to determine the failure mode. The failure modes
were classified as follows:
y adhesive (interfacial): failure at the interface between
freshly-filled composite and cured resin composite
y cohesive: failure within cured resin composite
y mixed: a combination of the two.
Water Sorption/Solubility Test
Sixteen polymerized resin composite disks of each material
were prepared as described above for the μSBS test. The
diameter and thickness of the resin disks were measured
at three different points using a digital caliper with a preci-
sion of 0.01 mm (Mitutoyo; Tokyo, Japan) and the volume
(V) was calculated in mm3.
The resin disks were stored in a dry condition, and
weighed daily until a constant dry mass (m1) was obtained.
When the initial mass had stabilized, the disks were im-
mersed in distilled water in glass vials at 37°C for the des-
ignated water storage periods (1 week, 2 weeks, 1 month).
At the end of each water storage period, the resin disks
were taken out of the glass vial using tweezers, gently
wiped with absorbent paper, and weighed immediately to
record the wet mass (m2). Then they were stored in a des-
iccator containing freshly dried silica gel, and weighed daily
until a constant dry mass (m3) was recorded.
The values of water sorption (Wsp) and solubility (Wsl)
were measured and calculated in μg/mm3 using the follow-
ing formula:
Wsp = (m2- m3)/V
Wsl = (m1- m3)/V
where m1 is the mass of the resin disk in μg before immer-
sion in water, m2 is the mass of the resin disk in μg after
immersion in water, m3 is the mass of the resin disk in μg
after desiccation, and V is the resin disk volume in mm3.
Statistical Analyses
All statistical analyses were performed at a significance
level of 5% using PASW version 18 (SPSS; Chicago, IL,
USA). The μSBS data were analyzed using a three-way
ANOVA and t-test with Bonferroni correction for multiple
comparisons. The failure mode data were analyzed using
the Kruskal-Wallis rank test. The Wsp and Wsl data were
analyzed using two-way ANOVA and t-test with Bonferroni
correction for multiple comparisons.
RESULTS
Microshear Bond Strength (μSBS)
The mean μSBS and standard deviations for all groups are
presented in Table 2. Three-way ANOVA results (Table 3)
show that μSBS was significantly influenced by all three fac-
tors (resin composite: p < 0.001; water storage period:
p < 0.001; surface treatment: p < 0.001). In addition, sig-
nificant interactions existed between two factors in each
combination (resin composite x water storage period:
p < 0.001; water storage period x surface treatment:
p < 0.05; resin composite x surface treatment: p < 0.001).
Control Group (No Treatment)
In the no-treatment control group with APX, Estelite, and
Filtek Supreme, the water storage groups exhibited reduced
μSBS compared to the immediately tested groups, whereas

428 The Journal of Adhesive Dentistry

 Nagano et al

Table 3 Three-way ANOVA results of shear bond strength, tests of between-subjects effects

Source Type III Sum df Mean Square F Sig.

of Squares

Resin 6756.620 3 2252.207 242.499 < 0.0001

Water storage 2617.157 3 872.386 93.931 < 0.0001

Surface treatment 8384.517 2 4192.258 451.388 < 0.0001

Resin x water storage 574.489 9 63.832 6.873 < 0.0001

Resin x surface treatment 5935.726 6 989.288 106.518 < 0.0001

Water storage x surface treatment 135.693 6 22.615 2.435 0.0250

Resin x water storage x surface treatment 1070.259 18 59.459 6.402 < 0.0001

Table 4 Percentage of failure patterns for each adhesive group at each storage period for the control, SE, and PB
groups

APX A:M:C Beautifil A:M:C Estelite A:M:C Supreme A:M:C

Ctrl immediate 100:0:0 Aa immediate 90:10:0 Aa immediate 100:0:0 Aa immediate 100:0:0 Aa

1 week 90:10:0 Aa 1 week 100:0:0 Aa 1 week 100:0:0 Aa 1 week 100:0:0 Aa

2 weeks 100:0:0 Aa 2 weeks 90:10:0 Aa 2 weeks 90:10:0 Aa 2 weeks 100:0:0 Aa

1 month 100:0:0 Aa 1 month 90:10:0 Aa 1 month 100:0:0 Aa 1 month 100:0:0 Aa

SE immediate 40:20:40 Aa immediate 20:0:80 Ba immediate 10:30:60 Ba immediate 10:20:70 ABa

1 week 60:20:20 Ab 1 week 20:0:80 Ba 1 week 10:20:70 Ba 1 week 20:20:60 ABb

2 weeks 40:30:30 Aa 2 weeks 10:0:90 Ba 2 weeks 0:30:70 Bb 2 weeks 10:40:50 Abb

1 month 40:30:30 Aa 1 month 20:0:80 Ba 1 month 0:30:70 Bb 1 month 10:40:50 ABb

PB immediate 0:0:100 Aa immediate 0:20:80 Aa immediate 10:0:90 Aa immediate 10:20:70 Aa

1 week 0:0:100 Aa 1 week 20:0:80 Ab 1 week 0:30:70 Aa 1 week 0:20:80 Ab

2 weeks 0:0:100 Aa 2 weeks 20:0:80 Ab 2 weeks 0:30:70 Aa 2 weeks 10:0:90 Ab

1 month 0:0:100 Aa 1 month 0:0:100 Aa 1 month 10:0:90 Aa 1 month 10:0:90 Ab

Comparisons are valid for each row and column of each substrate. Means represented by the same superscript upper and lowercase letters indicate no statis-
tically significant differences in rows and columns, respectively (p > 0.05). A: adhesive (interfacial) failure; M: mixed failure, C: cohesive failure in cured resin.

increasing the duration of water storage periods did not sig-
nificantly change their μSBS (p > 0.05). For Beautifil II, there
were no significant differences in μSBS between the immedi-
ate group and all the water storage groups (p > 0.05).
Surface Treatment Group (SE, PB)
For APX, μSBS significantly increased in both the immediate
and water storage groups, with control group < SE
group < PB group (p < 0.05), although 1-month water stor-
age reduced μSBS in the SE and PB groups. In immediately
tested Filtek Supreme specimens, the μSBS in each group
followed the same pattern as that of APX (p < 0.05), while
water storage significantly reduced μSBS in the PB group
(p < 0.05) but not in the SE group, in which the PB group
had lower μSBS than the SE group.
For Estelite in the immediate group, there were no sig-
nificant differences in μSBS between the control group, the
SE group, and the PB group (p > 0.05), while water storage
produced significantly higher μSBS in the SE and PB group
than in the control group (p < 0.05). For Beautifil II, in the
immediate and water storage groups, the SE and PB groups
exhibited significantly higher μSBS than in the control group
(p < 0.05), although the water storage reduced μSBS in the
SE and PB groups.
Failure Mode Analysis
The failure patterns for all groups are shown in Table 4. In
the control groups with all the resin composite materials,
adhesive failure was the predominant failure mode. In the
SE group, for APX, adhesive failure predominantly occurred,

Vol 20, No 5, 2018 429

Nagano et al

Table 5 Water sorption values (Wsp) (μg/mm3) of the resin composite after designated water storage periods

1 week 2 weeks 1 month

APX 13.3 (0.8)Aa 14.9 (0.9)Aba 16.0 (0.7)Ba

Beautifil II 18.3 (1.6)Ab 19.4 (1.5)Ab 20.6 (1.6)Ab

Estelite 17.3 (0.5)Ab 17.6 (0.6)Bb 17.9 (0.4)Bb

Supreme 25.4 (0.9)Ac 26.5 (0.7)Ac 26.8 (0.8)Ab

Values are means (SD) (n = 4). Same superscript letters indicate no statistically significant difference (p > 0.05). Upper case letters refer to rows, and lower
case letters refer to columns.

Table 6 Two-way ANOVA results for water sorption, tests of between-subjects effects

Source Type III sum of squares df Mean square F Sig.

Resin 979.124 3 326.375 293.068 < 0.0001

Water storage 57.350 2 28.675 25.749 < 0.0001

Resin x water storage 23.289 6 3.882 3.485 0.0080

while for Beautifil II, Estelite, and Filtek Supreme, cohesive
failure in cured resin was the most frequent mode of fail-
ure. In the PB group, for APX, Beautifil II, and Estelite, cohe-
sive failure in cured resin predominated, in which there
were no significant differences between water storage peri-
ods (p > 0.05). On the other hand, for Filtek Supreme, in
the PB group, cohesive failure in cured resin significantly
increased after more than 1-week water storage compared
with the immediate group (p < 0.05).
Water Solubility and Sorption
Water sorption
The water sorption (Wsp) results of all the resin composites
are presented in Table 5. Two-way ANOVA (Table 6) revealed
that Wsp was significantly affected by the materials
(p < 0.001) and the storage period (p < 0.001), and that
there was a significant interaction between the materials
and the storage period (p < 0.05).
For APX, Beautifil II, and Estelite, Wsp increased over time.
Filtek Supreme exhibited the highest Wsp among the four
resin composites (p < 0.05), but there was no significant dif-
ference in Wsp between water storage periods (p > 0.05).
Water solubility
The water solubility (Wsl) results of all resin composites are
presented in Table 7. Two-way ANOVA (Table 8) revealed
that the Wsl values were significantly affected by the stor-
age period (p < 0.001), and that there was no significant
interaction between the materials and the storage period
(p > 0.05).
For all the resin composites, there were no significant
differences in Wsl during water storage periods from 1 week
to 1 month (p > 0.05). Estelite had significantly higher Wsl
than did APX, Beautifil II, and Filtek Supreme (p < 0.05,
p < 0.05 and p < 0.05, respectively). On the other hand,
Beautifil II had significantly lower Wsl than did APX, Estelite,
and Filtek Supreme (p < 0.05, p < 0.05 and p < 0.05, re-
spectively).
DISCUSSION
The repair bonding performance of freshly-filled composite
to cured composite could be influenced by three distinct
bonding strategies: 1) co-polymerization of unreacted mono-
mers in cured composite with resin monomers in freshly-
filled uncured composite, 2) micromechanical retention by
monomer diffusion into the cured composite, and 3) chemi-
cal bonding to exposed filler particles on the cured compos-
ite surface.4,14,31 When placing resin composite on cured
composite without any surface treatment, unreacted mono-
mer in the cured composite would play an important role for
the repair bond strengths.2,11,14,31,35 In the no-treatment
control group of this study, for APX, Estelite, and Filtek Su-
preme, repair bond strengths to the water-aged, cured com-
posite decreased compared with those of their immediate
repair bond strengths. Additionally, the repair bond
strengths did not change during the water storage periods
longer than 1 week; neither did their water solubility values
during the water storage periods from 1 week to 1 month.
These results would indicate that after 1 week of water stor-
age, most of the remaining unreacted monomers in the
cured composites have eluted and that there are insuffi-
cient quantities remaining for bonding due to water infiltra-
tion/contamination. These findings are in agreement with
previous studies, which stated that the elution of unreacted
monomer was almost complete within 1 week of water stor-

430 The Journal of Adhesive Dentistry


Table 7 Water solubility values (Wsl) (μg/mm3) of the resin composite after designated water storage periods
1 week
APX 1.7 (0.3)Aac
Beautifil II 0.7 (0.3)Aa
Estelite 2.8 (0.6)Ab
Filtek Supreme 1.7 (1.0)Ac
Values are means (SD) (n = 4). Same superscript letters indicate no statistically significant difference (p > 0.05). Upper case letters refer to rows, and lower
case letters refer to columns.
Table 8 Two-way ANOVA table of water solubility, tests of between-subjects effects
Source Type III sum of squares
Resin 23.326
Water storage 0.084
Resin x water storage 0.396
age.23,27,34,38,39,42 Furthermore, water contamination could
inhibit the polymerization of resin monomer in freshly-filled
composite.10 These effects would lead to no significant dif-
ferences in the repair bond strengths to cured APX, Estelite,
or Filtek Supreme composite among all the water storage
periods. For Beautifil II, there were no significant differ-
ences in repair bond strengths between the immediate,
1-week, 2-week, and 1-month water storage groups, and the
water solubility value was significant lower than those of
the other composites. These results may indicate that even
in the immediate group, unreacted monomers in cured
Beautifil II composite were ineffective for adequate repair
bonding performance.
In the SE group with APX and Filtek Supreme, repair
bond strengths increased in the immediate and all water
storage groups compared with the control. Application of
the one-step self-etch adhesive, SE One, enhanced mono-
mer diffusion into the cured composite, especially in water-
absorbed composite, because SE One contains the hydro-
philic monomer HEMA, and improves surface wettability for
application of the freshly-filled hydrophobic composite.5 Ad-
ditionally, it has been reported that the acidic functional
monomer MDP, present in SE One, can interact with the
oxide film on the surface of zirconia fillers in Filtek Supreme
and barium fillers in APX.18,21,22 This could explain why ap-
plication of SE One significantly increased immediate repair
bond strengths to APX and Filtek Supreme. On the other
hand, the effect of water storage was different on repair
bond strengths of the SE group between APX and Filtek Su-
preme. That is, APX exhibited a reduction in repair bond
strength in the SE Group and an increase of water sorption
as the water storage periods increased. For APX, absorbed
water caused a reduction in repair bond strengths with ex-
tension of water storage periods, which presented interfer-
Vol 20, No 5, 2018
Nagano et al
2 weeks 1 month
1.6 (0.7)Aab 1.8 (0.7)Aac
0.8 (0.6) Aa 0.6 (0.9)Ab
2.6 (0.7) Ab 2.7 (0.8)Ac
1.6 (1.1)Aab 1.5 (0.8)Aab
df Mean square F Sig.
3 7.775 16.115 < 0.0001
2 0.042 0.087 0.917
6 0.066 0.137 0.990
ence for monomer diffusion and/or polymerization of SE
One. On the other hand, for Filtek Supreme, there were no
significant differences in repair bond strengths of the SE
Group between immediate and water storage groups. Never-
theless, the water sorption value was higher than those of
the other composites, which could be due to lower filler
load and/or different monomer composition in Filtek Su-
preme. For Filtek Supreme, absorbed water did not affect
the repair bond strength in the SE group. The effect of SE
One application on repair bond strength might be also influ-
enced by the morphological and chemical characteristics of
the resin matrix, such as porosity and monomer density.
Many studies have demonstrated that application of
silane coupling agent improved adhesion to silica-based
resin composite by chemical interaction with exposed silica-
filler particles on the surface of the cured compos-
ite.4,11,18,20,24,28,29,40 In the present study, application of a
silane coupling adhesive agent (mixture of J-MPTS and SE
One: PB group) further increased repair bond strengths to
APX and Filtek Supreme in the immediate group. APX, a
microfilled hybrid composite, contains larger silica fillers
(maximum size: 15 μm), barium glass fillers, and organic
fillers, while Filtek Supreme, a nanofilled composite, in-
cludes not only nano-size silica and zirconia fillers, but also
nanocluster fillers up to 10 μm.43 The nanocluster fillers
are loosely bound agglomerates of nano-size silica parti-
cles.1,6,9,30 In previous studies with nanofilled composite,
nearly all of smaller fillers were covered with resin matrix on
ground composite surfaces; therefore, the surface treat-
ment with silane did not contribute to an increase in repair
bond strength.15-17 Presumably, for Filtek Supreme, the
nanofiller particles in nanocluster fillers, which are not cov-
ered with resin matrix, would be exposed on ground com-
posite surfaces, leading to improvement of repair bond
431
Nagano et al
strength in the immediate PB group. However, the water
storage periods had different influences on repair bond
strengths in the PB group compared to APX and Filtek Su-
preme. The repair bond strength of APX slightly decreased
during the 1-month water storage period. Presumably, adhe-
sion to larger silica fillers on resin composite with a silane
coupling agent would not be influenced by the presence of
water in the matrix resin. On the other hand, the repair
bond strength of Filtek Supreme significantly decreased and
was accompanied by an increase in the number of cohesive
failures in cured composite, even after 1-week water stor-
age. The loosely bound nanocluster filler might be degraded
during water storage, leading to a reduction in repair bond
strengths to water-aged, cured Filtek Supreme in the PB
group.
For Estelite, a suprananofilled hybrid composite, the SE
and PB groups did not exhibit improved immediate repair
bond strengths compared with the control group. These re-
sults indicate that MDP and the silane coupling agent
(J-MPTS) were not effective in improving adhesion to the
spherical silica-zirconia fillers (0.2 μm in diameter) con-
tained in Estelite. These results might indicate insufficient
exposed areas of uncovered silica-zirconia filler surface on
ground, cured Estelite for improving the repair bond
strengths. Estelite exhibited significantly higher water solu-
bility than the other composite materials, therefore for im-
mediate repair bonding, sufficient quantities of unreacted
monomer may exist in the cured Estelite, making adhesive
agent application less advantageous. On the other hand, the
SE and PB groups exhibited increased repair bond strengths
to water-stored, cured Estelite compared with the control
group, although adding silane coupling agent was ineffective
for improving repair bonding performance. These results in-
dicate that monomer diffusion of SE One into the resin ma-
trix of water-stored Estelite may have played an important
role in improving repair bond strengths to cured Estelite.
For Beautifil II, a surface-prereacted glass ionomer
(S-PRG)/nanofilled composite, the SE and PB groups im-
proved repair bond strengths in the immediate and all water
storage groups compared with the control group. However,
adding silane coupling agent (PB group) was ineffective in
terms of repair bond strength compared with the SE group.
Presumably, most nanofillers in Beautifil II were not ex-
posed on matrix-uncovered surfaces of ground resin com-
posite. On the other hand, Beautifil II is a multiple ion-re-
leasing resin composite, utilizing S-PRG filler.19,44 The
S-PRG filler has a three-layered structure, consisting of a
fluroboroaluminosilicate glass core, reacted layers forming
a glass-ionomer phase on the surface of the core, and a
reinforced layer covering the surface of the pre-reacted
phase. Presumably, acidic functional monomers such as
MDP, could produce glass-ionomer reactions (acid-base re-
action)8,13,32,45 with the surface of S-PRG filler. The applica-
tion of SE One containing MDP could contribute to this reac-
tion, leading to improved adhesion to S-PRG filler-based
composite. However, Beautifil II reduced repair bond
strengths in the SE Group with increased water sorption as
the water storage periods increased. These results indicate
432
that in the SE group, the repair bond strengths to water-
aged, cured Beautifil II was influenced by absorbed water in
the resin matrix, interfering with monomer diffusion of SE
One. Additionally, the advantage of SE one application be-
came less important in the repair bond strength to cured
Beautifil II with 1-month water storage when compared to
the no-treatment control group. The chemical reaction of
MDP with S-PRG fillers may have a weaker effect in terms of
repair bond strength.
In this study, APX, when applied with a silane coupling
adhesive agent, exhibited significantly higher repair bond
strength than the newer nanofilled resin composites Filtek
Supreme, Estelite, and Beautifil II. Additionally, absorbed
water had little effect on the repair bond strength of APX
with silane coupling adhesive agent. These results indicate
that APX is a superior material for composite repair treat-
ment. The repair bonding performance was dependent upon
the material, in which filler composition and size are the
most important factors when composite absorbs water. The
contribution of resin matrix to repair bonding performance is
influenced by water sorption/solubility. In this study, APX
was used as freshly-filled composite in all the experimental
groups. The homogeneity of cured composite and freshly-
filled composite may be advantageous for copolymerization
performance between their resin matrix monomers.36 There-
fore, when the same material was used as both the cured
and freshly-filled composite, Filtek Supreme, Estelite, and
Beautifil II might exhibit increased immediate repair bond
strengths in the no treatment control group, because the
unreacted monomer in cured composite plays a paramount
role for immediate repair bonding performance. On the
other hand, in shear bond strength test, when different
kinds of freshly-filled resin composite were used in the dif-
ferent experimental groups, the stress distribution under
loading could change at their adhesive interfaces due to
their different elastic moduli, leading to an increase or de-
crease of bond strength values. Further research is required
on the effect of homogeneous materials on the repair bond-
ing performance to cured-resin composites in immediate
and/or long-term water storage conditions.
CONCLUSIONS
The performance of composite repair with different bonding
approaches was dependent upon the composite material,
in which filler components and size are an important influ-
encing factors. Water-aged adherend composite affected
the repair bond strengths. Application of a one-step self-
etch adhesive with MDP/HEMA improved repair bond
strengths to water-aged nanofilled resin composites with
silica/zirconia particles, but adding silane coupling agent
did not, in which S-PRG filler and nanocluster filler contrib-
uted slightly to improving the repair bonding performance.
On the other hand, for silica-based microfilled hybrid com-
posite, adding silane coupling agent further increased re-
pair bond strengths.
The Journal of Adhesive Dentistry

ACKNOWLEDGMENTS
This work was supported by the Ministry of Education, Culture,
Sports, Science and Technology of Japan (grant numbers,
15K11108, 18K09571).
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Clinical relevance: Silica-based microfilled hybrid com-
posite was a more suitable material for composite re-
pair than nanofilled composite with silica/zirconia
particles, because application of silane coupling agent
can more effectively enhance the repair bonding perfor-
mance due to adhesion to larger, exposed silica fillers.
433