Dent Clin N Am 51 (2007) 333357

New Developments in Dental Adhesion

Jorge Perdigao, DMD, MS, PhD
Division of Operative Dentistry, Department of Restorative Sciences,
University of Minnesota, 8-450 Moos Health Sciences Tower,
515 Delaware Street SE, Minneapolis, MN 55455, USA

Adhesion or bonding is the process of forming an adhesive joint, which

consists of two substrates joined together. In dentistry, the adherend is the
substrate to which the adhesivedenamel and dentin, rarely cementumd
is applied. Dental adhesives are solutions of resin monomers that join a
restorative material with a dental substrate after the monomers set by polymerization. While most adhesive joints involve only two interfaces, dental
adhesive joints may be more complex such as the enameladhesivecompositeadhesiveporcelain interface formed when a clinician bonds a porcelain
restoration (Fig. 1). A bonded composite restoration is another example of
a complex adhesive joint.
In 1955, Buonocore [1] reported the use of 85% phosphoric acid to
improve the retention of an acrylic resin on enamel. The micromechanical
nature of the interaction of dental adhesives with enamel is a result of the
infiltration of resin monomers into the microporosities left by the acid
dissolution of enamel and subsequent enveloping of the exposed hydroxyapatite crystals with the polymerized monomers within the pores on the
enamel surface [2].
The ultimate goal of a bonded restoration is to attain an intimate adaptation of the restorative material with the dental substrate [3]. This task is
difficult to achieve as the bonding process for enamel is different from
that for dentin. That is, dentin is more humid and more organic than enamel
[4]. While enamel is composed of 96% hydroxyapatite (mineral) by weight,
dentin contains a significant amount of water and organic material, mainly
type-I collagen [5]. This humid and organic nature of dentin makes bonding
to this hard tissue extremely difficult.
When tooth structure is cut with a bur or other instrument, the residual
components form a smear layer of debris on the surface [6]. This debris

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Porcelain etched with HF

Silane
Dental adhesive

Composite (resin cement)

Dental adhesive

Etched enamel

Fig. 1. Adhesive joint formed between enamel and etched porcelain. HF, hydrofluoric acid.

forms a uniform coating on enamel and dentin and plugs the entrance of the
dentinal tubules, reducing the permeability of dentin (Fig. 2). The smear
layer is porous and permeable as a result of submicron channels that allow
the dentinal fluid to pass through [4]. The basic composition of the smear
layer is hydroxyapatite and altered collagen with an external surface formed
by gellike denatured collagen [7]. The morphology of the smear layer is determined to a large extent by the type of instrument that creates it and by the
site of dentin where it is formed [8,9].

Fig. 2. Field emission scanning electron micrograph of dentin smear layer and smear plug.

DENTAL ADHESION

335

As the smear layer constitutes a true physical barrier, it must be dissolved or made permeable so the monomers in the adhesives can contact
the dentin surface directly. In spite of different classifications of adhesive
systems, the current adhesion strategies depend exclusively on how dental
adhesives interact with this smear layer. One strategy involves etch-andrinse adhesives, which remove the smear layer and superficial hydroxyapatite through etching with a separate acid gel (Fig. 3). The second strategy
involves self-etch adhesives, which make the smear layer permeable without
removing it completely (Figs. 4 and 5). Fig. 6 summarizes the current bonding strategies.

Etch-and-rinse strategy
With the etch-and-rinse strategy, dentin and enamel are treated with an
acid gel (commonly phosphoric acid) to remove the smear layer and demineralize the most superficial hydroxyapatite crystals (Fig. 7). Following this
chemical etching, a mixture of resin monomers (primer/adhesive) dissolved
in an organic solvent is applied to infiltrate etched dentin [10]. The resin
monomers permeate the water-filled spaces between adjacent dentin collagen fibers that used to be occupied by hydroxyapatite crystals. This infiltration results in a hybrid tissue composed of collagen, resin, residual
hydroxyapatite, and traces of water (see Fig. 3) known as the resindentin
interdiffusion zone, first described in 1982 as the hybrid layer [11]. This intimate micromechanical entanglement of resin monomers with etched dentin

Fig. 3. Interaction of one-bottle etch-and-rinse adhesives with dentin.

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Fig. 4. Interaction of two-bottle self-etch adhesives with dentin.

may result in decreased postoperative sensitivity, may make for a better

marginal fit, and may even act as an elastic buffer that compensates for
the polymerization shrinkage stress during contraction of the restorative
composite [1214].

Fig. 5. Interaction of all-in-one self-etch adhesives with dentin.

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337

Fig. 6. Summary of current adhesion strategies.

Self-etch strategy
The latest development in dental adhesion is based on simplification and
reduced application time. These self-etch (nonrinsing) adhesives do not
require a separate acid-etch step as they condition and prime enamel and
dentin simultaneously by infiltrating and partially dissolving the smear layer

Fig. 7. Field emission scanning electron micrograph of dentin etched with 40% phosphoric acid
for 15 seconds. Note the collagen fibers deprived from hydroxyapatite crystals as a result of acid
demineralization. The more intense decalcification around the peritubular area may be a result
of both the high mineral content of the peritubular region and the easier penetration of the acid
through the tubular lumen.

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and hydroxyapatite to generate a hybrid zone that incorporates minerals

and the smear layer [15].
The first self-etch nonrinsing adhesives were composed of two solutions, an
acidic primer and a bonding resin (see Fig. 4). Recently, many clinicians have
shifted to one-step self-etch systems (also named all-in-one adhesives) in
which manufacturers have attempted to incorporate all the primary components of an adhesive system (etchant, primer, and bonding resin) into a single
solution (see Fig. 5). Both the acidic primer of two-step self-etch adhesives and
the all-in-one solution are composed of aqueous mixtures of acidic functional
monomers, generally phosphoric-acid or carboxylic-acid esters, with a pH
higher than that of phosphoric acid gels [16]. Water is an essential component
of self-etch adhesives as it participates in the ionization of the acidic moieties.
All-in-one adhesives are user-friendly in that fewer steps are required for
the bonding protocol. The elimination of separate etching and rinsing steps
simplified the bonding technique, making these systems more popular in
daily practice [17].
Self-etch adhesives differ in their aggressiveness. Therefore they are classified in three categories according to acidity: mild, moderate, and aggressive
[16,18]. Because self-etch adhesives are not as aggressive as the phosphoricacid gel in etch-and-rinse adhesives, most do not remove the smear layer
(Fig. 8). Adper Prompt L-Pop (3M ESPE) is considered an aggressive
self-etch adhesive (pH 0.91.0), while other all-in-one adhesives, such asClearfil S3 Bond, iBond, and G-Bond, are mild or moderate (pH O1.5)
(Table 1) [1922].
Enamel bonding with self-etch adhesives
The enamel bond strengths of the earliest self-etch adhesives were lower
than those associated with adhesives that rely on a separate etching step [23].

Fig. 8. Field emission scanning electron micrograph of a resindentin interface formed with
Clearfil S3 Bond (Kuraray). The neck of the resin tag contains residual smear layer particles.
Ad, adhesive; D, dentin; RT, resin tag; SP, resin-impregnated smear plug.

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DENTAL ADHESION

Table 1
pHa of self-etch adhesives
Adhesive (manufacturer)

pH

AdheSE (Ivoclar Vivadent)

Adper Prompt L-Pop (3M ESPE)
Clearfil S3 Bond (Kuraray)
Clearfil SE Bond (Kuraray)
iBond (Heraeus Kulzer)
Xeno IV (Dentsply Caulk)

1.7
0.91.0
2.4
1.8
2.2
2.5

pH of 35% silica-thickened phosphoric-acid gel 00.4.

Data from Refs. [1922].

Because of their higher pH, two-step self-etch adhesives result in shallower

enamel demineralization compared with that of phosphoric acid [16,23].
Nevertheless, roughening of enamel to remove prismless enamel improves
the enamel-bonding ability of self-etch adhesives [24]. A separate phosphoric-acid enamel-etching step also enhances the efficacy of self-etch adhesives
[25]. Two-step self-etch adhesives bond at an acceptable level to normal dentin and to ground enamel in vitro [2628]. Conversely, two-step self-etch
materials may not bond as well to intact enamel and sclerotic dentin
[16,24,29,30].
All-in-one self-etch systems are not as acidic as the phosphoric acid used
with the etch-and-rinse adhesives [2]. This characteristic has raised concerns
about the performance of all-in-one self-etch systems on intact enamel
(Fig. 9). Several in vitro investigations have reported low resinenamel
bond strength of all-in-one self-etch materials [15,26,30,31]. Grinding the
enamel during a bevel or cavity preparation, for instance, makes the substrate more receptive for bonding with all-in-one self-etch systems [31,32].

Fig. 9. Backscattered field emission scanning electron micrograph of resinenamel interface

formed by Xeno IV (Dentsply). The restorative material used was Filtek Z250 (3M ESPE).
Intense silver deposits at the resinenamel interface (asterisks) denote intense enamel leakage.
Ad, adhesive; Comp, composite restoration.

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Despite the increased popularity of self-etch adhesives, etching with phosphoric acid is still considered the golden standard against which new materials are tested [27].
Dentin bonding with self-etch adhesives
In spite of their user-friendliness and low technique sensitivity, all-in-one
adhesives have resulted in low bonding effectiveness in vitro [15,26,30] while
their clinical reliability has often been questioned. Another drawback associated with all-in-one adhesives is their behavior as semipermeable membranes. These materials allow the movement of water across the bonded
interface, which potentially leads to hydrolytic degradation (Fig. 10) [31,32].
Consistent information regarding the durability of self-etch adhesives
when applied on dentin is available in the literature [28,33,34]. Although
high early resindentin bond-strength values may be achieved with selfetch adhesives, their bonding effectiveness over time is disappointing
[28,33,34]. Because of the high hydrophilic nature of the acidic monomers
and the high water concentration required for ionization of the acidic monomers in all-in-one self-etch solutions, these materials are likely to have resin
enamel bonds compromised over time. An inadequate resin penetration into
tooth substrates may result in accelerated degradation of the structure of the
bonding interface [30]. As polymerization shrinkage stresses the bonding interface, dentin adhesives that do not resist these stresses result in low bond
strengths, marginal gaps, recurrent caries, and pulpal irritation [33,35].
For some all-in-one adhesives, performance may depend on the application method, as the number of coats recommended by the manufacturer
may not suffice [30,36]. All-in-one adhesives have resulted in a wide range
of dentin bond strengths [30,36,37]. Application of the all-in-one adhesive
in multiple layers may result in higher bond strengths [37,38] and better

Fig. 10. Transmission electron micrograph of resindentin interface formed with Clearfil S3
Bond (Kuraray). Deposits of silver grains may correspond to areas of residual water. D, dentin;
H, hybrid layer.

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341

infiltration into the hybrid layer [38]. One manufacturer recommends rubbing the adhesive continuously for 15 seconds, followed by the application
of a second coat after gentle air-drying and curing the first coat. This second
coat prevents the formation of dry spots on the dentin surface and may
result in better impregnation of the monomers into the hybrid layer, as
observed in Figs. 11 and 12.
Low enamel and dentin bond strengths have been reported when acetonebased all-in-one adhesives are applied as per manufacturers directions
[33,37]. These adhesives result in severe enamel microleakage following thermal stresses [39,40]. When applied to one-surface occlusal preparations, one
of the most popular acetone-based all-in-one adhesives is not able to withstand polymerization shrinkage stresses nor thermocycling, resulting in
a high percentage of pretesting debonds [33]. Several mechanisms may account for this poor performance as compared with adhesives with different
solvents. The magnitude of dentin bond strengths depends on the degree
of infiltration of the resin monomers into the collagen pretreated with an
acidic conditioner or with phosphoric acid [41]. The authors electron microscopy analyses (Figs. 13 and 14) have demonstrated that acetone-based
all-in-one adhesives result in a hybrid layer 0.2 to 0.5 mm thick, interfacial
gaps, and limited resin penetration into the dentinal tubules. It is known
that hybrid layers are particularly susceptible to degradation when the
cavo-surface margins are not in enamel [42]. The degradation of the dentin
bonding interface is caused by the availability of exposed collagen fibrils at
the base of hybrid layer [43] or by hydrolytic degradation of resin components in the hybrid layer [28,4345]. Water can also infiltrate and plasticize

Fig. 11. Field emission scanning electron micrograph of the dentin hybridization formed upon
application of two coats of Adper Prompt L-Pop. Note the infiltration of the material into the
dentin tubules and the absence of interfacial gaps. When Adper Prompt L-Pop is applied in one
coat, a separation gap forms between the adhesive and the hybrid layer (not shown). Ad, adhesive; Comp, composite restoration; D, dentin; H, hybrid layer.

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Fig. 12. Transmission electron micrograph of the dentin hybridization formed upon application of two coats of Adper Prompt L-Pop (3M ESPE). Note the reticular morphology of
the hybrid layer corresponding to the resin embedding of the collagen fibers. Ad, adhesive;
C, composite particle; D, dentin; H, hybrid layer.

the resin matrix, which decreases the mechanical properties of the polymer
[46].
Other factors may play a role in the weak bonding performance of acetone-containing all-in-one adhesives. Porosities (or blisters) occur at the
enamel and dentin bonding interfaces because most all-in-one adhesives
behave as semipermeable membranes [31,33,4749]. These porosities may
be a result of water accumulation either caused by an osmotic gradient or
by monomersolvent phase separation upon evaporation of the acetone
[21,49]. The number and size of these blisters may also depend on the intensity of the air-drying step [47].
High hydrophilicity, and consequent higher water sorption, has been reported associated with another acetone-based all-in-one adhesive containing

Fig. 13. Field emission scanning electron micrograph of a resindentin interface formed with
G-Bond (GC America). Ad, adhesive; Comp, composite restoration; D, dentin.

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343

Fig. 14. Transmission electron micrograph of a resindentin interface formed with G-Bond
(GC America) Asterisks indicate residual smear particles. Ad, adhesive; D, dentin; H, hybrid
layer; SP, smear plug; T, resin tag.

a poly-phosphate molecule, dipentaerythritol penta-acrylate phosphate [50].

The adhesive may undergo a substantial reduction in elastic modulus after
water sorption, due to the plasticizing effect of water [50]. If the adhesive
has been plasticized by water, the restoration will likely fail when a load
is applied on the surface because the stresses cannot be transferred across
the adhesive joint. Another factor that may lead to lower bond strengths
is the adhesives low degree of conversion, which has been demonstrated
for specific adhesive compositions [51].
Clearfil SE Bond (Kuraray) (Table 2), a two-step self-etch adhesive based
on 10-methacryloyloxy decyl dihydrogen phosphate (10-MDP), is a reference for all other self-etch adhesives when it comes to dentin bond strengths
[15,28]. In the authors laboratory, Clearfil S3 Bond, the all-in-one successor
of Clearfil SE Bond, shows lower dentin bond strengths than its predecessor.
The pH of Clearfil S3 Bond is less acidic than that of Clearfil SE Bond
primer (2.4 versus 1.8, respectively). In spite of its relatively high pH, the
bond strengths of Clearfil S3 Bond on unground enamel are statistically similar to those of a more aggressive self-etch adhesive, Adper Prompt L-Pop
(pH 0.91.0) when tested in the authors laboratory. The manufacturer
of Clearfil S3 Bond claims that the difference between the two 10-MDP
based adhesives may lie on the molecular dispersion technology that
keeps the homogeneity of Clearfil S3 Bond adhesive and prevents phase separation that occurs with acetone-based all-in-one adhesives [21]. A recent
study showed that Clearfil S3 Bond is more resistant to mechanical stress
than its two-bottle predecessor [52], which is surprising taking into consideration the excellent retention rates (above 90%) of Clearfil SE Bond
in class-V clinical studies at 2 to 3 years [53,54]. This clinical behavior
of both Clearfil adhesives denotes a good resistance to clinical fatigue of
adhesives containing 10-MDP.

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Table 2
Recent dentin adhesives
Adhesives and
manufacturers

Instructions for use

Type

1. Apply self-etch primer. Once the

cavity is thoroughly coated, brush
for 15s. Total reaction time should
not be shorter than 30s.
2. Dry with mild airflow.
3. Apply self-etch bonding.
4. Dry with mild airflow.
5. Light cure for 10s.
1. Activate the L-Pop Unit Dose
Dispenser to mix the adhesive.
2. Apply mixed adhesive to entire
surface, rubbing in the solution
with moderate finger pressure for
15s.
3. Use a gentle stream of air to
thoroughly dry the adhesive into
a thin film.
4. Rewet the brush tip with adhesive
and apply a second coat of adhesive
to the tooth surface. The second
coat does not require rubbing.
5. Use a gentle stream of air to
thoroughly dry the adhesive into
a thin film.
6. Light cure for 10s.

Two-step self-etch

AdheSE

Ivoclar
Vivadent

Primer: phosphoric acid acrylate,

bis-acrylic acid amide, water,
initiators, and stabilizers
Bonding component: dimethacrylate,
hydroxy ethyl methacrylate,
highly dispersed silicon dioxide,
initiators and stabilizers

Adper Prompt
L-Pop

3M ESPE

HEMA phosphates, HEMA,

bis-GMA, modified
polyalkenoic acid, water,
photo-initiator

All-in-one self-etch,
but requires mixing

PERDIGAO

Composition

3M ESPE

HEMA, bis-GMA, DMAs,

methacrylate functional copolymer
of polyacrylic and polyitaconic
acids, water, ethanol, nanofiller,
photo-initiator

Clearfil S3 Bond

Kuraray America

10-MDP, HEMA, bis-GMA, water,

ethanol, silanated colloidal silica,
camphorquinone

1. Apply Scotchbond Etchant (35%

silica-thickened phosphoric acid
gel) to tooth surface for 15s.
2. Rinse thoroughly for 10s.
3. Blot excess water using a cotton
pellet or mini-sponge. Do not air
dry.
4. Apply 23 consecutive coats of
adhesive for 15s with gentle
agitation using a fully saturated
applicator.
5. Gently air-thin for 5s to evaporate
solvent.
6. Light cure for 10s.
1. Thoroughly wet brush tip with
Bond. Apply Bond to the tooth
surface and leave in place for 20s.
2. Dry the entire surface sufficiently by
blowing high-pressure air for more
than 5s while spreading the bond
layer thinly.
3. Light cure for 10s.

Two-step etch and rinse

All-in-one self-etch

DENTAL ADHESION

Adper Single Bond Plus

(continued on next page)

345

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Table 2 (continued )
Adhesives and
manufacturers

Instructions for use

Type

1. Thoroughly wet brush tip with

primer. Apply primer to the tooth
surface and leave in place for 20s.
2. Dry with a mild air stream to
evaporate the volatile ingredients.
3. Dispense the necessary amount of
Bond into second mix well.
4. Apply Bond to the tooth surface.
5. After applying Bond, create
a uniform film using a gentle air
stream.
6. Light cure for 10s.
1. Before dispensing, shake the bottle
of G-Bond thoroughly. Replace
bottle cap immediately after use.
2. Immediately apply to the prepared
enamel and dentin surfaces using
the microtip applicator.
3. Leave undisturbed for 10s.
4. After application, dry thoroughly
using oil free air under maximum
air pressure for 5s, in the presence
of vacuum suction to prevent
splatter of the adhesive.
5. Light cure 10s.

Two-step self-etch

Clearfil SE Bond

Kuraray America

Primer: 10-MDP, HEMA, hydrophilic

DMA, tertiary amine, water,
photo-initiator
Bonding: 10-MDP, HEMA,
bis-GMA, hydrophilic DMA,
tertiary amine, silanated colloidal
silica, photo-initiator

G-Bond

GC America

4-MET, UDMA, phosphate

monomer, DMA component, fumed
silica filler, acetone, water,
photo-initiator

PERDIGAO

Composition

All-in-one self-etch

iBond

Heraeus Kulzer

UDMA, 4-MET, glutaraldehyde,

acetone, water, stabilizer,
photo-initiator

Xeno IV

Dentsply Caulk

UDMA, PENTA, acetone,

polymerizeable trimethacrylate
resin, and two polymerizeable DMA
resins, photo-initiator.

All-in-one self-etch

All-in-one self-etch

DENTAL ADHESION

1. iBond is applied in three

consecutive layers and massaged
into the prepared hard-tooth
structure for 30s.
2. Following that, the solution is
blown away with a gentle air
stream.
3. Polymerize for 20s.
1. Using the supplied disposable
microbrush applicator tip,
immediately apply and scrub
surfaces with generous amounts of
Xeno IV adhesive to thoroughly
wet all the tooth surfaces for 15s.
2. Apply a second application of Xeno
IV adhesive with the microbrush as
above, scrubbing for 15s (20s for
larger restorations).
3. Remove excess solvent by gently
drying with clean, dry air from
a dental syringe for at least 5s.
4. Cure Xeno IV adhesive for 10s.

(continued on next page)

347

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Table 2 (continued )
Adhesives and
manufacturers
XP Bond

Dentsply DeTrey

Instructions for use

Type

1. Etch enamel for at least 15s and

dentine for 15s or less with 36%
phosphoric acid.
2. Wet all cavity surfaces uniformly
with XP Bond in a disposable
brush. Avoid pooling.
3. Leave the surface undisturbed for
20s.
4. Evaporate solvent by thoroughly
blowing with air from an air syringe
for at least 5s. The cavity surface
should have a uniform, glossy
appearance. Otherwise repeat steps
2 and 4.
5. Light-cure for a minimum of 10s.
Ensure uniform exposure of all
cavity surfaces.
6. Immediately place the restorative
material over cured XP Bond.

Two-step etch and

rinse

Abbreviations: bis-GMA, bisphenol glycidyl methacrylate; DMA, dimethacrylate; HEMA, 2-hydroxyethyl methacrylate; 10-MDP, 10-methacryloyloxy
decyl dihydrogenphosphate; 4-MET, 4-methacryloxyethyl trimellitic acid; PENTA, dipentaerythritol penta-acrylate phosphate; TEGDMA, triethyleneglycol
dimethacrylate; UDMA, urethane dimethacrylate.

PERDIGAO

Composition
Carboxylic acid modified
dimethacrylate (TCB resin),
PENTA, UDMA, TEGDMA,
HEMA, butylated
benzenediol (stabilizer),
ethyl-4-dimethylaminobenzoate,
camphorquinone, functionalized
amorphous silica, t-butanol

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349

Clinical performance of all-in-one adhesives

Some manufacturers of all-in-one self-etch adhesives do not recommend
enamel pre-etching, while other manufacturers recommend phosphoric-acid
etching of unground enamel. One would argue that additional enamel bond
strength is always required to prevent marginal gaps and leakage. In a clinical setting, the adhesive is extended past the boundaries of the preparation,
forming composite flashes. Bonding to this uninstrumented surface is
needed to resist potential staining. The manufacturer of Xeno IV (Dentsply)
recommends beveling the enamel margins for all procedures, which may be
difficult to achieve in the cervical margin of class-II preparations. The manufacturers of Adper Prompt L-Pop (3M ESPE) and iBond (Heraeus Kulzer)
do not recommend a separate enamel-etching step. The manufacturer
of Clearfil S3 Bond (Kuraray) recommends phosphoric-acid etching of
unground enamel. Pre-etching may improve bonding to uninstrumented
surfaces for all mild all-in-one adhesives, especially in areas where an adhesive flash formed during insertion. When enamel is etched separately, bond
strengths increase significantly for self-etch adhesives [52,55]. However, if
etching is extended to dentin, bonding may be compromised [52].
The enamel bond strengths of aggressive self-etch adhesives are usually
higher than those of other self-etch adhesives [55], which may have to do
with the relatively low pH compared with other less acidic adhesives (see
Table 1). A recent morphological scanning electron microscopy study reported that the etching pattern on Adper Prompt, the bottle version of Adper
Prompt L-Pop, is similar to that of phosphoric acid [56]. Other all-in-one
adhesives, such as G-Bond (GC America) and iBond (Heraeus Kulzer), do
not result in any discernible etching pattern or minimal exposure of crystallites
in sporadic areas of unground enamel. On ground enamel, these adhesives result in islands of superficially dissolved enamel within areas without any sign
of enamel dissolution (Fig. 15). One of the first clinical signs that a composite

Fig. 15. (A) Field emission scanning electron micrograph of enamel treated with iBond (Heraeus Kulzer) after roughening the enamel with a diamond bur for 5 seconds. The adhesive
was removed with acetone. (B) Enamel etched with 38% phosphoric acid (Pulpdent) for 15
seconds.

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restoration is prone to failure is its early marginal staining. In fact, iBond is

unable to penetrate the enamel smear layer [34], which explains why it is not
very effective when applied on ground enamel. The almost inexistent etching
pattern of iBond (an adhesive based on 4-methacryloxyethyl trimellitic acid
(4-MET)) may have been responsible for massive marginal failure in a posterior composite clinical study at 1 year [57]. The all-in-one adhesive iBond resulted in statistically worse marginal staining than any of the other adhesives
used in this study. Two other adhesives, a 10-MDPbased all-in-one adhesive
(Clearfil S3 Bond) and a self-etch adhesive based on polyalkenoic acid copolymer and hydroxyethyl-methacrylate (Adper Prompt L-Pop) resulted in
a slightly lower percentage of excellent margins than the etch-and-rinse adhesive One-Step Plus, but these differences were not significant. At 1 year, the restorations inserted with iBond showed a dark orange aspect in most of the
restorations, which was already evident at 6 months (Figs. 16 and 17). The
change in color of the restoration might have been a result of the degradation
of the adhesive itself, not that of the composite material, as the other adhesives
did not result in such catastrophic results. This color change of the 4-MET
based all-in-one adhesive may be a result of its rapid hydrolysis, which is temperature-dependent and occurs as early as at 1 month, when specimens are
stored at 25" C to 37" C [58].
Marginal adaptation is another parameter for which some self-etch adhesives result in unacceptable clinical results, which means they have a deficient
enamel bonding ability. This bonding inability has been observed in laboratory studies as some all-in-one self-etch adhesives fail prematurely, with pretesting failures in the range of 50% [59]. Another study found 50% to 66%
of pretesting failures with iBond with and without 20,000 cycles of thermal
fatigue [33]. When the prevailing failure mode is adhesive, the bond
strengths are generally low, while cohesive failures are more often associated
with high bond strengths [60]. Several investigators have reported very low
bond strengths with iBond when applied as per manufacturers directions
[37,6163]. Clinically, iBond has resulted in more marginal staining than
an etch-and-rinse adhesive in a class-V study [64], which corroborates the

Fig. 16. Tooth #30 (left) preoperatively and (right) 1 year after being restored with the etchand-rinse adhesive One-Step Plus (Bisco Inc.).

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351

Fig. 17. Tooth #19 (left) preoperatively and (right) 1 year after being restored with the all-inone self-etch adhesive iBond (Heraeus Kulzer) (same patient as in Fig. 15).

poor marginal staining observed in the 1-year posterior composite clinical

study [57]. In that class-V study [64], iBond was compared with Gluma Solid
Bond (Heraeus Kulzer), an etch-and-rinse adhesive, at 18 months. Other
studies have also reported severe enamel microleakage in vitro, especially
with thermal stresses with iBond [39,40], which explains the high percentage
of marginal openings found clinically. Only 2 out of 27 iBond restorations
were rated Alfa for marginal adaptation at 1 year [57].
According to the American Dental Association (ADA) guidelines for
enamel and dentin adhesives, the cumulative incidence of clinical failures in
each of two independent studies must be less than 10% to obtain full acceptance at 18 months [65]. While the enamel bonding ability of mild all-in-one
adhesives may be jeopardized by thermal and mechanical fatigue, more aggressive all-in-one adhesives have resulted in acceptable clinical behavior
[57,66]. At 18-months, 7% of the class-V restorations placed with Adper
Prompt were lost versus none of the restorations inserted with Single Bond
(3M ESPE), an etch-and-rinse adhesive [66]. The restorations bonded with
Single Bond had slightly better marginal adaptation and marginal discoloration, but not statistically better. In spite of a slightly poorer clinical behavior
at 18 months in class-V noncarious lesions, all-in-one adhesives like Adper
Prompt have demonstrated lower bond strength to both enamel and dentin
than one-bottle etch-and-rinse systems, such as Single-Bond [15,28,67].
In a posterior composite clinical study [57], marginal staining with Adper
Prompt L-Pop at 1 year was not significantly different from baseline, but the
P value was close to significance (P .06). Marginal adaptation at 1 year
was significantly worse than at baseline (P!.0001), as 18 out of 29 restorations were rated Bravo and 2 restorations were rated Charlie. Postoperative
sensitivity to air at 1 year improved significantly for Adper Prompt L-Pop as
compared with the preoperative values (P!.016). All 7 restorations that
were sensitive to air preoperatively were not sensitive at 1 year.
While the aggressiveness (acidity) of the self-etch solution is important to
determine the interaction depth of the restorative material with enamel, the
chemical attributes of all-in-one adhesive are also important. Clinical studies

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with Prompt L-Pop, the predecessor of Adper Prompt, in cervical lesions resulted in a high failure rate [68,69]. The most crucial difference between the
two versions is the presence of the polyalkenoic-acid copolymer in the latest
versions (Adper Prompt and Adper Prompt L-Pop). This polyalkenoatebased component was first introduced in a resin-modified glass ionomer material (Vitrebond, 3M ESPE) and subsequently used in other formulations,
including the adhesive systems (Scotchbond Multi-Purpose Primer and Single Bond). The polyalkenoate salt has been claimed to provide water stability to the adhesive system by a dynamic potential of breaking and renewing
the bonding between the carboxyl groups and calcium, forming a stressrelaxation zone at the bonded interface [70].

Etch-and-rinse adhesives: Are they the benchmark for other adhesives?

Etch-and-rinse adhesives result in high enamel and dentin bond strengths.
The enamel-etching pattern and the penetration into the dentinal substrate reinforce the idea that etch-and-rinse adhesives are still the benchmark for other
adhesives when it comes to laboratory performance [26,27,47]. However, there
are still concerns regarding the degree of infiltration of the etched dentin by
some etch-and-rinse adhesives, such the ethanol- and water-based Single
Bond, the unfilled version of Adper Single Bond Plus [7173]. In spite of the
high retention rate in clinical studies, reports have indicated that the bonds
formed with Single Bond may undergo degradation in vivo at 1 year [73].
Acetone-based etch-and-rinse adhesives are more technique-sensitive
than adhesives containing ethanol or water [74,75]. The clinical behavior
of acetone-based etch-and-rinse adhesives may be determined by variations
in the respective application technique, namely the amount of moisture left
after rinsing the etchant and the amount of adhesive applied in the preparation [76]. One-Step Plus is the filled version of the acetone-based etch-andrinse adhesive One-Step. Dentin bond strengths do not improve when the
filled version is used [52,75]. Clinical studies using One-Step in class-V lesions have resulted in a wide variety of retention rates. One study found a retention rate of 75% at 3 years, while another study reported a 56% retention
rate at 18 months [77,78]. Van Dijken [79] reported a 51% retention rate at
3 years, with higher failure rates in cervical lesions with sclerotic dentin. This
low retention rate reported in some studies is not in agreement with the high
dentin and enamel bond strengths found in other studies [80,81].
For multi-bottle etch-and-rinse adhesives, 5 full papers and 11 abstracts
were published from 1998 to 2004 [82]. In 81% of the studies, multi-bottle
etch-and-rinse adhesives fulfilled the full acceptance ADA guidelines (18
months), with an average annual failure rate of 4.8% [82]. With regard to
one-bottle etch-and-rinse adhesives, 15 full papers and 17 abstracts appeared in the literature in the same period [82]. The clinical performance
of multibottle etch-and-rinse adhesives was better than that of one-bottle

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353

etch-and-rinse adhesives, as only 51% fulfilled the full acceptance ADA

guidelines (18 months) [81]. Even though dental adhesives have been available over several generations with an array of new materials being launched
every year, clinical studies are not abundant in the literature. Several reasons
may account for the discrepancy: first, the time constraints associated with
setting up and running a clinical study with the respective periodic recalls;
second, a generalized scarcity of industrial and independent funding for
this type of applied research; and third, the frequent practice among manufacturers to launch a new version of a specific adhesive even before the
previous one has been fully tested. As a result of all these limitations, researchers and clinicians still rely on data from laboratory studies to predict
the behavior of adhesive materials.
Summary
Numerous simplified adhesives have been introduced to the dental market within the last few years, sometimes without comprehensive testing to
validate the performance claimed by the respective manufacturers. Mild
self-etch adhesives are unable to etch enamel to provide adequate retention
for bonded restorations. Although high early resindentin bond strength
values can be achieved with some self-etch adhesives, their resistance to thermal and mechanical stresses over time is disappointing. In light of the current drawbacks attributed to all-in-one self-etch adhesives, etch-and-rinse
adhesives are still the benchmark for dental adhesion in routine clinical use.
Acknowledgments
The author gives special thanks to Drs. S. Duarte, G. Gomes, and
M. Lopes for help preparing the scanning electron microscopy and transmission electron microscopy specimens.
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