©

Operative Dentistry, 2010, 35-1, 94-104

Microtensile Bond Strength

and Interfacial Characterization
of 11 Contemporary Adhesives
Bonded to Bur-cut Dentin
M Sarr • AW Kane • J Vreven
A Mine • KL Van Landuyt • M Peumans
P Lambrechts • B Van Meerbeek • J De Munck

Clinical Relevance
In the current study, contemporary adhesives are assessed mechanically and ultra-morpholog-
ically to predict clinical effectiveness. Adhesives with simplified application procedures (in par-
ticular, one-step self-etch adhesives) still underperform as compared to conventional “gold-
standard” multi-step adhesives. “Mild” two-step self-etch adhesives that provide additional
chemical bonding appear to most optimally combine bonding effectiveness with a simplified
application protocol.

Mouhamed Sarr, DDS, PhD, Université Cheikh Anta DIOP,
Faculté de Médecine, Pharmacie et Odontologie, Dakar,
Senegal
Abdoul Wakhabe Kane, DDS, PhD, Maître de conférences,
Université Cheikh Anta DIOP, Faculté deMédecine, Pharmacie
et Odontologie, Dakar, Senegal
José Vreven, Université Catholique de Louvain, Service de
Pathologie et Thérapeutique Dentaires, Bruxelles, Belgium
Atsushi Mine, Katholieke Universiteit Leuven, Leuven BIOMAT
Research Cluster, Leuven, Belgium
Kirsten L Van Landuyt, Katholieke Universiteit Leuven, Leuven
BIOMAT Research Cluster, Leuven, Belgium
Marleen Peumans, Katholieke Universiteit Leuven, Leuven
BIOMAT Research Cluster, Leuven, Belgium
Paul Lambrechts, Katholieke Universiteit Leuven, Leuven BIO-
MAT Research Cluster, Leuven, Belgium
Bart Van Meerbeek, DDS, PhD, full professor, Katholieke
Universiteit Leuven, Leuven BIOMAT Research Cluster,
Leuven, Belgium
*Jan De Munck, DDS, PhD, Katholieke Universiteit Leuven,
Leuven BIOMAT Research Cluster, Leuven, Belgium
*Reprint request: Kapucijnenvoer 7, Leuven, 3000, Belgium:
e-mail: jan.demunck@med.kuleuven.be
DOI: 10.2341/09-076-L
SUMMARY
Objectives: This study evaluated mechanically
and ultra-morphologically 11 different adhesive
systems bonded to dentin. Methods: The
microtensile bond strength (µTBS) of 11 contem-
porary adhesives, including two three-step
etch&rinse, three two-step etch&rinse, two two-
step self-etch and four one-step self-etch adhe-
sives to dentin, were measured. The resultant
interfacial ultra-structure at dentin was charac-
terized by transmission electron microscopy
(TEM). Human third molars had their superficial
dentin surface exposed, after which a standard-
ized smear layer was produced using a medium-
grit diamond bur. The selected adhesives were
applied according to their respective manufac-
De Munck & Others: Bonding Effectiveness of Contemporary Adhesives to Dentin
turer’s instructions for µTBS measurement after
storage in water at 37°C for 24 hours or for TEM
interfacial characterization. Results: The µTBS
varied from 11.1 to 63.6 MPa; the highest bond
strengths were obtained with the three-step
etch&rinse adhesives and the lowest with one-
step self-etch adhesives. TEM evaluation showed
very different interaction patterns, especially for
the self-etch adhesives. “Mild” self-etch adhe-
sives demineralized the dentin surface suffi-
ciently to provide micro-mechanical retention,
while preserving hydroxyapatite within the
hybrid layer to enable additional chemical inter-
action. Conclusions: When bonded to dentin, the
adhesives with simplified application proce-
dures (in particular, one-step self-etch adhesives)
still underperform as compared to conventional
three-step adhesives. “Mild” two-step self-etch
adhesives that provide additional chemical
bonding appear to most optimally combine bond-
ing effectiveness with a simplified application
protocol.
INTRODUCTION
Current adhesives can be categorized by adhesive
approach and clinical application procedure.1 According
to this classification, adhesives belong to either the
etch&rinse group, if a separate etchant is applied and
rinsed off, or to the self-etch group, if an acidic
monomer is used to demineralize and infiltrate the
tooth surface simultaneously. Further categorization is
based on the number of clinical application steps. The
more conventional adhesives have a separate
hydrophobic bonding resin that involves an additional
clinical application step and are referred to as three-
step etch&rinse and two-step self-etch adhesives. The
alternative adhesives combine the priming and bond-
ing functions to reduce the number of clinical steps,
resulting in the two-step etch&rinse and one-step self-
etch adhesives. All these simplifications have repercus-
sions on bonding durability,2 at least for the older gen-
eration of simplified adhesives. Clinically, the most
attractive are the self-etch adhesives, because an addi-
tional rinse and drying step is no longer needed. This
reduces the risk of contamination on the surface, elim-
inates over- and under-drying issues3 and does not
require the cotton rolls to be refreshed (in case no rub-
ber dam is used). With respect to bond strategy, the con-
cept of simultaneously demineralizing and infiltrating
the tooth surface is advantageous,4 though so far,
hydrophilic resins have been employed that make the
bond sensitive to hydrolytic degradation.5
As adhesive technology is rapidly evolving, on the
dental market, commercial adhesive formulations are
replaced frequently. As a result, many adhesives that
are available today have no independent clinical vali-
95
dation for their use. Therefore, laboratory-screening
tests remain indispensable in providing data that, to a
certain degree, predict clinical effectiveness. Although a
direct correlation between laboratory and clinical
research has not yet been shown, a clear trend exists
that adhesives that present repeatedly and repro-
ducibly with relatively high bond strengths and appear
resistant to diverse forms of “aging” also present with
high retention rates in clinical Class-V studies.2,6-9
Currently, the best screening method is a combination
of quantitative bonding effectiveness measurements
and knowledge of the interfacial interaction of new
adhesives. Therefore, mechanically and ultra-morpho-
logically, the current study evaluated different contem-
porary adhesives bonded to dentin. A three-step
etch&rinse (OptiBond FL) and a two-step self-etch
(Clearfil SE Bond) adhesive, both of which have repeat-
edly been shown to be excellent performers in clinical
and laboratory studies, served as “gold-standard” adhe-
sives for their class. The hypothesis tested was that
recently launched, simple-to-use adhesives have a sim-
ilar bonding effectiveness to dentin as control gold-
standard multi-step adhesives.
METHODS AND MATERIALS
Selection of Adhesives and Tooth Preparation
Eleven adhesives, all currently available on the dental
market, including two three-step etch&rinse, three
two-step etch&rinse, two two-step self-etch and four
one-step self-etch adhesives, were chosen (Table 1).
Fifty-five sound human molars (33 for µTBS and 22 for
TEM), gathered following informed consent approved
by the Commission for Medical Ethics of the Catholic
University of Leuven, were used. The teeth, stored in a
0.5% chloramine solution, were used within three
months of extraction. Flat dentin surfaces were pre-
pared by removing the coronal tooth part with an
Isomet low-speed diamond saw (Isomet 1000, Buehler,
Lake Bluff, IL, USA). Then, a standardized smear layer
was prepared using a regular-grit diamond bur (842,
Komet, Lemgo, Germany) mounted in the
MicroSpecimen Former (University of Iowa, Iowa City,
IA, USA). The dentin surfaces were verified for the
absence of enamel and/or pulp tissue exposition using a
stereo-microscope (Wild M5A, Heerbrugg,
Switzerland).
Bonding Procedures
Three teeth were used per adhesive. The adhesives
were applied strictly following the manufacturer’s
guidelines (Table 1). A composite build-up was then
made using a single resin composite (Z100, 3M ESPE,
St Paul, MN, USA), which was applied in five incre-
ments with a height of approximately 1-mm and light-
cured for 40 seconds with an Optilux 500 light-curing
device (Demetron, Kerr, Danbury, CT, USA) with a
light output of not less than 550 mW/cm2.
96 Operative Dentistry

Table 1: Composition and Instructions for Use of the Adhesives Studied

Adhesives Category Composition Instructions for Use
Manufacturer
Batch #
Adper Prompt L-Pop one-step water, methacrylic esters of phosphoric Activate blister. Apply the adhesive on
3M ESPE, Seefeld, self-etch acid, fluorides with zinc, photoinitiators. the air-dried dentin surface and rub for
Germany 15 seconds. Gently air blow. Apply again
[230220] for three seconds. Gently air blow. Light
cure for 10 seconds.
G-Bond GC, one-step UDMA, 4-META, glutardialdehyde, Apply G-Bond on the air-dried dentin
Tokyo, Japan self-etch acetone, water, photoinitiators, stabilizers. surface. Leave undisturbed for 10
[0511041] seconds. Dry thoroughly under maximum
air pressure for 5 seconds. Light cure for
10 seconds.
Xeno III, one-step Liquid A: HEMA, purified water, ethanol Dispense equal amounts of liquids A and
Dentsply, Konstanz, self-etch (BHT), silicon dioxide. B into the dish. Mix for 5 seconds. Apply
Germany Liquid B: phosphoric acid modified onto the dentin surface. Leave for at least
[0602000338] methacrylate (Pyro-EMA) mono fluoro 20 seconds. Uniformly spread adhesive
phosphazene modified methacrylate (PEM-F), by a gentle stream of air pressure until
UDMA, BHT,camphorquinone, ethyl-4- the resin does not flow anymore. Light
dimethylaminobenzoate. cure for 10 seconds.
Clearfil S³ Bond one-step 10-MDP,Bis-GMA,HEMA, hydrophobic Apply the adhesive on the dentin surface.
Kuraray, Tokyo, Japan self-etch dimethacrylate, dicamphorquinone, ethyl Leave undisturbed for 20 seconds. Dry
[00042A] alcohol, water, silinated colloidal silica. thoroughly with high-pressure for 5 sec-
onds. Light cure for 10 seconds.
Clearfil Protect Bond two-step Primer: 10-MDP, 12-MDPB, HEMA, Apply primer on the dentin surface and
Kuraray, Tokyo, Japan self-etch hydrophylic dimethacrylate, water. leave undisturbed for 20 seconds. Gently
[41112] Bond: 10 MDP, Bis-GMA, HEMA, hydrophobic air blow. Apply bond. Air thin and light
dimethacrylate, di-camphorquinone, cure for 10 seconds.
N,N-diethanol-p-toluidine silinated colloidal
silica, surface treated sodium fluoride.
Prime&Bond NT two-step Di and tri-methacrylate resins, functionalized Apply the conditioner for 15 seconds on
Dentsply, Konstanz, etch&rinse amorphous silica, PENTA, photoinitiators, the dentin surface. Rinse the surface and
Germany stabilizers, cetylamine hydrofluoride, acetone. dry the surface slightly leaving a visible
[0602000196] moist surface. Apply the adhesive and
leave undisturbed for 20 seconds. Gently
air blow for 5 seconds. Light cure for 10
seconds.
Scotchbond MP three-step Etchant: phosphoric acid 35%, water, silica. Apply the conditioner for 15 seconds on
3M ESPE, etch&rinse Primer: water, HEMA, polycarboxylic acid. the dentin surface. Rinse the surface and
Seefeld, Germany Bond: BisGMA, HEMA, camphorquinone, and dry the surface slightly leaving a
[20051006] EDMAB, DHEPT. visible moist surface. Apply the primer for
30 seconds. Dry gently for 5 seconds.
Apply the bond and light cure for 20
seconds.
Scotchbond 1 XT two-step Etchant: phosphoric acid 35%. Apply etchant to the dentin surface for 15
3M ESPE, Seefeld, etch&rinse Primer: BisGMA,HEMA, dimethacrylate seconds. Rinse for 10 seconds. Gently air
Germany ethanol, water, photoinitiators, nanofillers, dry for 2 seconds. Apply 2 consecutive
[5ET] copolymer of methacrylic acid (10%). coats of the adhesive. Gently air thin for
5 seconds. Light cure for 10 seconds.
Clearfil SE Bond two-step Primer: HEMA, hydrophilic dimethacrylate, Apply primer for 20 seconds. Gently air
Kuraray, Tokyo, Japan etch&rinse MDP, N,N-diethanol-p-toluidine, blow. Apply bond. Air thin. Light cure for
[41184] D,L-camphorquinone, water. 10 seconds.
Bond: colloidal silica, bisphenol A diglycidyl-
methacrylate, HEMA, MDP, hydrophobic
dimethacrylate, N,N-diethanol-p-toluidine,
D,L-camphorquinone.
XP Bond, two-step Carboxylic acid modified dimethacrylate Apply conditioner to the dentin surface
Dentsply, Konstanz, etch&rinse (TCB resin), Phosphoric acid modified for 15 seconds. Rinse thoroughly for 10
Germany acrylate resin (PENTA), UDMA, TEGDMA, seconds and air-dry. Apply the adhesive
[0605002535] HEMA, butylated benzendiol (stabilizer), and leave undisturbed for 20 seconds. Air
ethyl-4-dimethylaminobenzoate, camphorquinone, blow for min 5 seconds. Light cure for 20
functionalized amorphous silica, t-butanol. seconds.
De Munck & Others: Bonding Effectiveness of Contemporary Adhesives to Dentin 97

Table 1: Composition and Instructions for Use of the Adhesives Studied (cont.)
Adhesives Category Composition Instructions for Use
Manufacturer
Batch #
Optibond FL three-step Conditioner: phosphoric acid 32%. Apply the conditioner to the dentin
Kerr, Orange, CA, USA etch&rinse Primer: HEMA, GPDM, PAMM, surface for 15 seconds. Rinse for 15
[Primer 435490] camphorquinone, ethanol, water. seconds. Gently air dry for 5 seconds.
[Bond 439114] Bond: Bis-GMA, HEMA, GDMA, Barium Scrub the surface for 30 seconds with the
aluminoborosilicate, silica, camphorquinone. primer. Air dry gently. Apply a thin coat of
the bond and light cure for 30 seconds.

Table 2: µTBS and Failure Analysis

Microtensile Bond Strength Data Failure Analysis

Adhesives Mean µTBS (MPa) ptf/n* Interfacial Mixed Cohesive Cohesive

in Dentin in Resin

Adper Prompt L-Pop 11.1 ± 9.1a 4/18 11 2 - 1

G-Bond 20.4 ± 6.3a,b 0/18 10 6 - 2

Xeno III 29.6 ± 17.8b,c 0/18 11 5 - 2

Clearfil S³ Bond 30.7 ± 12.5c 0/19 9 7 - 3

Clearfil Protect Bond 31.0 ± 9.7 c

0/19 8 7 3 1

Prime&Bond NT 31.1 ±14.4c 0/18 8 10 - -

ScotchBond MP 34.6 ± 11.7c 0/21 5 5 3 8

ScotchBond 1XT 37.1 ± 14.4 c,d

0/19 9 6 1

Clearfil SE 44.3 ± 26.4d,e 0/18 6 5 5 2

XP Bond 52.2 ± 10.6e 0/18 5 6 4 3

OptiBond FL 63.6 ± 14.2f 0/18 6 7 3 2

*ptf= pre-testing failures, n= number of specimens, values with the same superscript are not statistically significantly different.

Microtensile Bond Strength (µTBS) Testing
After 24-hour storage in water, the resin-dentin bonded
specimens were sectioned with a water-cooled diamond
saw (Isomet 1000, Buehler Ltd, Lake Bluff, IL, USA) in
both the x and y directions to obtain rectangular sticks
(six to seven) from the central part of the coronal dentin
surface. The dimensions of the sticks were then meas-
ured by means of a digital caliper (CD-15CPX,
Mitutoyo, Kanagawa, Japan) from which the cross-sec-
tional area was calculated (approximately 0.9 mm2).
The non-trimmed micro-specimens8 were fixed to a
modified microtensile bond testing jig8 with cyanocry-
late glue (Model Repair II Blue, Dentsply-Sankin,
Tokyo, Japan) and tested in tension at a crosshead
speed of 1.0 mm/minute using an LRX testing machine
(Lloyd, Hampshire, UK) equipped with a load cell of
100 N. The bond strength values were calculated in
MPa by dividing the imposed force (in N) at the time of
fracture by the bond area (in mm2).
The failure modes were evaluated with a stereo-
microscope (Wild M5A) at a magnification of up to 50x
and categorized as “interfacial,” “cohesive” (dentin or
composite) or “mixed.” The data were statistically eval-
uated by one-way ANOVA and Tukey’s Multiple com-
parisons test at a significance level of α=0.05.
Transmission Electron Microscopy (TEM)
The bonding mechanism to dentin was morphologically
assessed by TEM (JEM-1200EX II, JEOL, Tokyo,
Japan). Two dentin surfaces were prepared for each
adhesive in the same way as for µTBS testing.
Following adhesive treatment, the resin-bonded dentin
specimens were cross-sectioned perpendicular to the
resin-dentin interface to obtain 0.8-mm wide sticks
using the slow speed diamond saw. Half of the speci-
mens were then demineralized and fixed simultaneous-
ly in a 10% formaldehyde-formic acid solution (Gooding
and Stewart Fluid, Prosan, Gent, Belgium) for at least
36 hours. TEM sample preparation of both the dem-
ineralized and non-demineralized sections was then
performed in accordance with common procedures used
for ultra-structural TEM examination of biological tis-
sues.11 Eventually, 70-90-nm thick sections through the
98
Figure 1. Bar graph presenting the µTBS in MPa. Bars connected with a horizontal line are not
statistically significantly different. Error bars denote the 95% confidence interval.
resin-dentin interface were cut using a diamond knife
(Diatome, Bienne, Switzerland) in an ultramicrotome
(Ultracut UCT, Leica, Vienna, Austria).
RESULTS
The µTBS of the 11 adhesives to dentin are shown in
Table 2 and Figure 1. The mean µTBS values ranged
from 11 to 63 MPa. The lowest value was obtained for
the one-step self-etch adhesive (Adper Prompt L-Pop)
and the highest was obtained for the three-step
etch&rinse adhesive (OptiBond FL). The one-step self-
etch adhesive tended to have lower µTBS values than
the two-step self-etch and etch&rinse adhesives, though
a product-related dependency also existed. The three-
step etch&rinse adhesive OptiBond FL had not only the
highest µTBS, it was also statistically different from all
the others. Pre-testing failures (mainly failures during
sectioning with the slow-speed diamond saw) occurred
only with the one-step self-etch adhesive Adper Prompt
L-Pop (4 out of 18). No pre-testing failures were record-
ed for any other adhesive tested.
Failure analysis showed interfacial, cohesive and/or
mixed fractures, depending on the adhesive tested
(Table 2). A general trend was observed: specimens that
presented with lower bond strength failed more at the
resin-dentin interface (interfacial failure). On the other
hand, specimens with higher bond strengths failed more
cohesively in dentin or resin.
Regarding self-etch adhesives, the interfacial-ultra-
structure differed, depending on the actual self-etch
approach and, thus, the specific adhesive, especially
when the degree of interaction at the interface was more
Operative Dentistry
intense with adhesives that provided a rel-
atively low pH primer. The one-step self-
etch adhesive Adper Prompt L-Pop is a
strong self-etch adhesive, since its interac-
tion with dentin was very similar to that of
etch&rinse adhesives. A thick (3-5 µm)
hybrid layer, wide resin tags and removal
of all residual hydroxyapatite within the
hybrid layer was observed (Figure 2a). The
one-step self-etch adhesive Xeno III inter-
acted somewhat less intensely with dentin;
the hybrid layer was about 2 µm thick and,
in the bottom part, some hydroxyapatite
was preserved (Figure 2c). The two-step
self-etch adhesives Clearfil SE (gold stan-
dard) and Protect Bond are typical mild
(pH of the primer is around 2) self-etch
adhesives; the hybrid layer was less than 1
µm thick and only partially demineralized
over its full width (Figures 2e and 2f). The
remaining one-step self-etch adhesives G-
Bond and Clearfil S³ Bond were typical
ultra-mild self-etch adhesives; their inter-
action with the underlying dentin was
rather superficial (100-200 nm) and cannot
be distinguished from a potentially resin-impregnated
smear layer (Figures 2c and 2d).
Regarding etch&rinse adhesives, the interfacial-ultra-
structure was very similar for all adhesives (Figure 3).
As all the adhesives made use of phosphoric acid to ini-
tially etch dentin, they presented with thick (3-5 µm),
completely demineralized, hydroxyapatite-free hybrid
layers with wide open tubules filled with resin tags that
extend even into the small lateral tubule branches.
Marked differences were observed in the appearance of
the adhesive resin itself and, in particular, its filler.
Some adhesives had no filler at all, such as Scotchbond
Multi-Purpose (Figure 2d), while others contained
nanofillers (Prime&Bond NT, Scotchbond 1 XT and XP
Bond; Figures 3a, 3b and 3d, respectively) in different
densities. The adhesive resin of OptiBond FL (gold stan-
dard) was heavily loaded with conventional glass filler,
with particles up to several micrometers (Figure 3e).
DISCUSSION
In the current study, the bonding effectiveness of 11
adhesives to dentin was comparatively investigated.
The hypothesis, that recently launched simple-to-use
adhesives had a similar bonding effectiveness to dentin
as control gold-standard multi-step adhesives, was
rejected, as most simplified adhesives, and especially
the one-step self-etch adhesives, revealed a significant-
ly lower bond strength than that of the gold-standard
three-step etch&rinse control adhesive (Table 2).
In the current study, the authors used the µTBS test
to mechanically assess the strength of the resin-dentin
De Munck & Others: Bonding Effectiveness of Contemporary Adhesives to Dentin 99

strate variables. Also, the stress

is more uniformly distributed
during loading across the inter-
face, again as compared to the
more traditional bond strength
test methods.3,14 Many modifica-
tions to this µTBS method have
been proposed in the literature,15
especially as the final prepara-
tion of the interface area appears
important, since cracks can be
introduced at this level.
Aggressive and insufficiently-
controlled trimming of these
micro-specimens may introduce
interfacial defects that may lead
to premature failures and a
reduction in the observed bond
strengths by the early onset of
crack propagation during tensile
loading of the specimen.
Originally, the rectangular con-
striction at the interface of these
micro-specimens was prepared
by hand using a dental hand-
piece.16 This method is not only
laborious, it also largely depends
on the skills of the operator,
thereby introducing a non-negli-
gible factor of technique sensitiv-
ity. Theoretically, circular con-
striction leads to a better stress
distribution at the interface
area.17,19 This additional micro-
specimen milling is best per-
formed using a more-or-less
Figure 2. TEM photomicrographs of the self-etch adhesives bonded dentin. (a) Non-demineralized, non- automated device, such as the
stained section of Adper Prompt L-Pop. A thick hybrid layer of about 4 µm was produced, similar to MicroSpecimen Former (Univer-
etch&rinse adhesives. Inside the oxygen-inhibited adhesive resin layer, phase-separations of hydrophilic sity of Iowa), so that the speci-
and hydrophobic components can be observed. (b) Non-demineralized, non-stained section of Xeno III. men preparation is better stan-
Dentin was demineralized and impregnated for about 2 µm. At the bottom of the hybrid layer, some hydrox-
dardized and less operator spe-
yapatite crystals (hand pointer) can still be observed. (c) Non-demineralized, non-stained section of G-
Bond. A relatively thin, filled adhesive resin layer is produced. At the interface (hand pointer), a relatively cific. Also, other variables, such
20

thick and irregular interaction zone can be observed, consisting of a thin nano-interaction zone and a more as grip, loading speed and align-
irregular resin-impregnated smear layer. (d) Non-demineralized, non-stained section of Clearfil S³ Bond. An ment, are very important and
interface complex, typical of an ultra-mild self-etch adhesive, can be observed with a thin nano-interaction should be standardized.4,21 In the
zone and a more irregular resin impregnated smear layer. (e) Non-demineralized, non-stained section of current study, the authors opted
Clearfil SE. A 1-µm thick, partially demineralized hybrid layer can be observed. (f) Non-demineralized, non- for non-trimmed µTBS speci-
stained section of Protect Bond. A 0.5-µm thick, partially demineralized hybrid layer can be observed.
Ar=Adhesive resin, C=Composite; O-I= Remnants of the oxygen-inhibition layer mixed with the resin com-
mens that combine a good stress
posite and cured; Hy=Hybrid layer, D=Dentin, Rt=Resin tag. distribution at the interface17
with a minimal amount of pro-
interface complex. Today, the µTBS test is one of the cessing; the 1x1 mm resin-
most commonly used methodologies, since it has sever- dentin sticks are cut out of the restored tooth and
al advantages over the more traditional macro-tensile directly transferred to the universal testing machine.
and shear-bond test methodologies.4,12-13 The µTBS test Only the central dentin portion that is located direct-
is more versatile, as, for example, multiple specimens ly above the pulp was used in the current study in
can be obtained from a single tooth, enabling more order to minimize any regional variation between the
sophisticated study setups and better controlled sub- periphery and central dentin substrate.4,22-23 (This, how-
100 Operative Dentistry

ever, reduced the number of specimens

available for testing [6-7, instead of up to
30 in other studies15]) but was thought to
increase the validity of the results.
In the currrent study, as in several
other studies,2,14 the highest µTBS was
obtained with the conventional three-
step etch&rinse adhesive OptiBond FL.
There was a marked, statistically signif-
icant difference between OptiBond FL
and the other three-step etch&rinse
adhesives tested, namely Scotchbond
MP. In addition to a difference in the
actual bonding effectiveness, the µTBS
also reflects the whole strength of the
interface complex. The higher µTBS of
OptiBond FL should probably also be
attributed to the high filler loading of
the adhesive resin and high mechanical
strength, as proven by its relatively high
e-modulus, comparable to that of several
flowable composites.24 On the other
hand, the adhesive resin of Scotchbond
MP does not contain any filler and has
previously been shown to be less effec-
tive.11 Nevertheless, the µTBS of
Scotchbond MP remains comparable to
that of the two-step etch&rinse adhe-
sives Scotchbond 1 XT and Prime&Bond
NT. XP Bond, which is relatively densely
filled with silica (even accumulating in
the resin tag, Figure 3d) and makes use
of ter-butanol as a solvent, scored bond
strengths intermediate to the non-filled
and highly filled resin. Ter-butanol has a
similar vapor pressure to ethanol but
without the risk on esterification of func- Figure 3. TEM photomicrographs of the etch&rinse adhesives bonded to dentin. (a)
Demineralized, stained section of Prime&Bond NT. The phosphoric acid demineralized the sur-
tional monomers. XP Bond also per- face up to 5 µm deep. Also, the lateral wall of the tubules and some lateral canals (hand point-
formed well when tested following a con- er) were deminereralized and infiltrated by resin. (b) Non-demineralized, non-stained section of
ventional shear bond strength method Scotchbond 1 XT. A similar demineralization pattern was observed as for Prime&Bond NT. In
test performed by general practitioners the adhesive resin, typical globular structures (hand pointer) can be observed, suggesting
in a so-called battle of the adhesives phase-separations between the hydrophilic and hydrophobic components. (c) Non-demineral-
series by Degrange and others.25 ized, non-stained section of Scotchbond MP. Note the deposition on top of the hybrid layer (hand
pointer), which is the polyalkenoic-acid co-polymer being filtered out by the collagen network.11
Another issue that is relevant to all (d) Non-demineralized, non-stained section of XP Bond. Note the accumulation of filler particles
etch&rinse adhesives is the manner in within the resin tags, as they cannot infiltrate the hybrid layer itself. (e) Non-demineralized, non-
which dentin is treated after the etch- stained section of OptiBond FL. Note that the adhesive resin is highly filled with conventional
and-rinse procedure. This is a very tech- filler (hand pointer). Ar=Adhesive resin, Hy=Hybrid layer, D=Dentin, Rt=Resin tag.
nique-sensitive step, where the operator
should take care not to “under-“ or “over-dry” the the degree of dentin wetness.28 The only water-free ace-
dentin surface, as both are known to result in impaired tone-based adhesive tested in the current study was
bonding effectiveness.3,26 In the first place, the window Prime&Bond NT, which scored the lowest bond
of opportunity to achieve optimal hybridization is strengths of all the etch&rinse adhesives.
dependent on the solvent used in the primer and is Two-step etch&rinse adhesives combine the primer
considerably smaller for (water-free) acetone-based and adhesive resin in order to reduce the number of
primers27 than for water/ethanol-based primers—the clinical application steps from three to two. In the cur-
latter being obviously more forgiving with regard to rent study, three two-step etch&rinse adhesives (XP
De Munck & Others: Bonding Effectiveness of Contemporary Adhesives to Dentin 101

Bond, Scotchbond 1 XT and

Prime&Bond NT) were tested.
Their µTBS were significantly
lower than that of the three-step
etch&rinse adhesive OptiBond
FL, as corroborated by former
studies conducted using a simi-
lar protocol in the laboratory of
the current authors.20,29-30 The
immediate bond strength is
expected to primarily originate
from the micro-mechanical inter-
locking of resin in the collagen
fibril mesh. Therefore, in gener-
al, there is no difference in bond-
ing effectiveness of two- and
three-step etch&rinse adhesives Figure 4. Schematic overview of the interaction of different self-etch adhesives with dentin (bar at the left
when tested to flat surfaces and represents approximately 5 µm). On the left, unaffected dentin is represented with a typical smear layer
and a smear plug occluding a dentinal tubule. On the right, interaction of the four classes of self-etch adhe-
in the short-term. As soon as one
sives with this smear layer covered dentin is represented. The ultra-mild self-etch adhesives do not remove
tests these adhesives in complex the smear layer and their interaction with the underlying dentin is rather superficial (100-200 nm). Residual
cavities19 or in the longer-term,31 hydroxyapatite in the resin-impregnated smear and hybrid layer remains available for chemical interaction.
three-step etch&rinse adhesives The mild self-etch adhesives do not completely remove the smear layer, but form a submicron hybrid layer.
easily outperform their two-step Throughout the whole depth of the hybrid layer, residual hydroxyapatite remains attached to the exposed
equivalents.2 collagen fibrils and remains available for chemical interaction. The intermediately strong self-etch adhe-
sives dissolve the smear layer and plug, forming short (± 10 µm) resin tags. Some residual hydroxyapatite
Self-etch adhesives are clinical- can be found only in the bottom third of the hybrid layer. Also, limited lateral tubule wall hybridization can
ly most attractive, because they be observed. The strong self-etch adhesives present with a morphology very much like that produced by
do not need a rinse step, thus etch-and-rinse adhesives, with a 3-5 µm thick hybrid layer, extensive resin tags, tubule-wall and lateral
avoiding the technique-sensitive tubule-wall hybridization.
drying of etched dentin. Self-etch
adhesives differ, not only because of the number of clin- surface.33 Therefore, these adhesives bond well to some
ical steps (two- and one-step self-etch adhesives), but dentin surfaces but less effectively to others, by which
also because of the wide interaction intensity that can another kind of technique sensitivity is introduced.
be observed. A clear correlation between the pH of self- Clinically, an adhesive that can bond to any surface is
etch primer and the depth of interaction with dentin preferred, as can mild self-etch adhesives.34 This clear
was observed in the current study and is graphically correlation between the pH of self-etch primer and
summarized in Figure 4. Today, four categories can be interaction intensity is graphically represented in
distinguished:1,29 1) strong self-etch adhesives have a Figure 4, showing all the key morphological features of
pH lower than 1 and an interfacial micro-morphology the different self-etch approaches.
(3-4 µm deep fully demineralized hybrid layers) that is In light of bond durability, mild and ultra-mild self-
very similar to that of etch&rinse adhesives; 2) they etch adhesives have some unique properties that other,
are intermediately strong self-etch adhesives with a more aggressive approaches, such as etch&rinse adhe-
pH of around 1.5. These adhesives have a hybrid layer sives, lack. Since not all hydroxyapatite is removed
of about 1-2 µm, wherein, at the bottom part, some from the interaction zone, much calcium is available
hydroxyapatite is preserved; 3) they are mild self-etch for additional chemical interaction with specific adhe-
adhesives with a pH of around 2. The hybrid layer is sive functional monomers.35-36 Some of these bonds are
less than 1 µm thick and is only partially demineral- stable, even in an aqueous environment,36 so that the
ized; 4) recently, a category of ultra-mild self-etch interface can better withstand the hydrolytic break-
adhesives was added for self-etch adhesives that come down of its components. This mechanism is supposed
with a primer pH higher than 2.5.32 These adhesives do to prolong the clinical lifetime of restorations.7
not remove the smear layer and interact with smear Adper Prompt L-Pop is a strong one-step self-etch
layer covered dentin only up to a few hundredths of a adhesive. This adhesive scored the lowest bonding
nanometer. As interaction with intact dentin is almost effectiveness of all the adhesives tested (11.1 MPa),
non-existent, the micro-mechanical resistance of the and it was also the only adhesive for which pre-testing
interface complex is very dependent on impregnation failures were recorded (4 out of 18 specimens). A more
and stabilization of the smear layer. As a result, the detailed long-term study revealed that, most probably,
µTBS is far more dependent on the preparation of the less optimal polymerization and mono-polymer stabili-
102
ty are the basis for these less favorable results.2 This
poor in vitro performance is corroborated with several
clinical Class-V studies that report less favorable in
vivo performance for this strong self-etch adhesive.6,37-38
Xeno III is a typical intermediately strong self-etch
adhesive. The smear layer was completely removed
and a 2-µm thick hybrid layer was produced (Figure
2b). Although its µTBS was the third lowest of all the
adhesives tested, it was not significantly different from
the µTBS measured for several multi-step adhesives,
such as Scotchbond MP (Table 2); clinically, up to 10%
of the Class V restorations de-bonded after only two
years of clinical service, as reported in two randomized
Class V studies.18,39 This is considerably worse than the
100% retention rate at five years for the control adhe-
sive OptiBond FL and the 94% retention rate at seven
years.8
Clearfil SE and Protect Bond are very similar adhe-
sives in composition. The most important composition-
al differences are inclusion of the antibacterial
monomer MDPB and sodium fluoride, which are
deemed beneficial for the long-term performance of
adhesive bonds. The anti-bacterial properties of
Clearfil Protect Bond have been proven in vitro,40 but
the potential clinical benefit is difficult to assess and,
therefore, it remains uncertain. The clinical perform-
ance of both adhesives in randomized Class V studies
is excellent,9,41 and even approaches that of the gold-
standard three-step etch&rinse adhesive OptiBond
FL.8 These excellent in vitro and in vivo results must
be ascribed to their unique two-fold bonding mecha-
nism related to the mild self-etch approach, which
comprises a micro-mechanical bonding component
through the formation of a 1 µm thick hybrid layer
that may provide resistance to acute debonding stress
(as imposed during µTBS testing). Additionally, these
adhesives contain the functional monomer 10-MDP,
which enables an intensive and stable chemical bond
with hydroxyapatite,36 which was left around the colla-
gen fibrils within the hybrid layer (Figures 2e and 2f).
Such primary chemical interaction improves the
resistance to hydrolytic breakdown42 and, thus, clini-
cally keeps the restoration margins sealed for a longer
period.
Also, both of the ultra mild self-etch adhesives that
were tested, G-Bond and Clearfil S³ Bond, contain
functional monomers with additional chemical bond-
ing potential, suggesting a similar two-fold bonding
mechanism. TEM revealed that the interaction with
dentin is much shallower (Figures 2c and 2d) and is
limited to a few hundred nanometers.32 Therefore, as
mentioned above, this twofold bonding mechanism
might be compromised for these ultra-mild self-etch
adhesives by interference of the surface smear. Short-
term clinical evaluation of these adhesives in Class V
Operative Dentistry
restorations suggests, however, adequate bonding per-
formance to this lightly prepared, highly mineralized
dentin tissue.1,43 Long-term clinical follow-up and adhe-
sion to different substrates, such as carious dentin, are
therefore of concern to this adhesive approach and
should be investigated in future research.
CONCLUSIONS
The bonding effectiveness of current commercial adhe-
sives is not equal. The highest µTBS obtained in the
current study was with the three-step etch&rinse adhe-
sive OptiBond FL, which remains the gold standard.
Mild two-step self-etch adhesives that also provide
additional chemical bonding appear to be the best com-
promise, as they combine optimal bonding effectiveness
with a simplified application protocol.
Acknowledgements
The authors thank the manufacturers for supplying the mate-
rials for this study. KL Van Landuyt has been granted a post-
doctoral fellowship by the Research Foundation-Flanders
(FWO). This study was supported in part by the FWO No
G.0206.07 and KULeuven OT/06/55 research grants.
(Received 4 March 2009)
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