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ARTICLE 2

THE SCIENCE OF BONDING:FROM FIRST TO SIXTH GENERATION

GERARD KUGEL, D.M.D., M.S.; MARCO FERRARI, M.D., D.D.S., PH.D.

Background. Adhesive dentistry has revolutionized restorative dental practice during the past
30 years. Improved adhesive materials have made
resin-based composite restorations more reliable and
long-standing.

As we enter the new millennium, it is important

for us to examine the past. The principles of adhesive dentistry date back to 1955 when Buonocore,
using techniques of industrial bonding, postulated
that acids could be used as a surface treatment
before application of the resins.1 He subsequently
found that etching enamel with phosphoric acid
increased the duration of adhesion under water.
In 1963, Buonocore demonstrated his insight into
adhesion dentistry when he discussed the difference in bonding to enamel and to dentin,2 particularly when he referred to Dr. Bowens attempts to
investigate substances that will displace water
from tooth surfaces3 with the idea that they could
be used as pretreatment for enamel or dentin.
Buonocore then stated that they could even be
incorporated into the adhesives.2
In the late 1960s, Buonocore suggested that it
was the formation of resin tags that caused the
principal adhesion of the resins to acid-etched
enamel.4 The idea that resin penetrates the
microporosities of etched enamel and results in a
micromechanical bond is well-accepted today.
As time went on, variations in duration of the
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Clinical Implications. This article

reviews the evolution of bonding from the first generation to current bonding materials. It discusses
the composition and effectiveness of the various iterations. Current products are highlighted to improve
clinical use and performance of the materials.

acid-etching procedure and concentration of the

phosphoric acid, along with alternative acids,
were tested for the etching of enamel.5-7 The current thinking is that a 30 to 40 percent phosphoric acid etch of 15 seconds is acceptable.
The ability to bond reliably to enamel is now
well-accepted, but as Buonocore suggested in
1963, adhesion of our restorative materials to
dentin has proved to be more elusive.2
Early attempts to bond to dentin resulted in
poor bond strengths.8 This is not surprising given
the fact that while enamel contains little protein,
dentin is 17 percent collagen by volume. This collagen is inaccessible due to surrounding hydroxyapatite crystals.9 The dentinal tubules are the
only pores available for micromechanical retention. These tubules contain fluid, which would be
an impediment to bonding. The number of
tubules available for bond also varies depending
on location, with deep dentin having more
tubules than superficial dentin.9 Other factors
such as age of teeth, direction of tubules and of
enamel prisms, presence of cementum and type
of dentin can affect dentin bonding.10,11

JADA, Vol. 131, June 2000

Copyright 1998-2001 American Dental Association. All rights reserved.

Early dentin bonding was

further complicated by the presence of the smear layer. (The
smear layer is the organic
debris that remains on the
dentin surface after the preparation of the dentin during
restoration of a tooth.) The
smear layer blocks the dentinal
tubules and acts as a diffusion
barrier. This was originally
thought of as an advantage in
that it protected the pulp by
decreasing the permeability of
dentin.12 As dentin bonding
improved, the removal of the
smear layer became necessary,
but not without controversy.
Several factors characterize
the change in bonding systems
from the Buonocore era to today:
detching enamel;
detching-conditioning dentin;
dsmear layer treatment;
dhandling properties.
This article reviews several
aspects of the different generations of bonding systems.
FIRST GENERATION

In 1956, Buonocore and colleagues demonstrated that use

of a glycerophosphoric acid
dimethacrylate-containing resin
would bond to acid-etched
dentin.13 This bond was
believed to be due to the interaction of this bifunctional resin
molecule with the calcium ions
of hydroxyapatite. Of course,
immersion in water would
greatly reduce this bond. Nine
years later Bowen14 tried to
address this issue using
N-phenylglycine and glycidyl
methacrylate, or NPG-GMA.
NPG-GMA is a bifunctional
molecule or coupling agent.
This means that one end of this
molecule bonds to dentin while
the other bonds (polymerizes) to
composite resin. The bond
strengths of these early systems

were only 1 to 3 megapascals.

The clinical results with these
systems were poor.
SECOND GENERATION

As improvements were made in

the adhesive coupling agents
for composites, the adhesion to
dentin increased. In the late
1970s, the second-generation
systems were introduced. The
majority of these incorporated
halophosphorous esters of
unfilled resins such as bisphenol-A glycidyl methacrylate, or
bis-GMA, or hydroxyethyl
methacrylate, or HEMA.15
The mechanism by which
these second-generation systems bonded to dentin were
postulated to be through an
ionic bond to calcium by
chlorophosphate groups. These
were weak bonds (in compari-

As dentin bonding
improved, removal
of the smear layer
became necessary,
but not without
controversy.
son to fifth- and sixth-generation systems) but they were a
significant improvement over
first-generation systems.
One major concern with
these systems was that the
phosphate bond to calcium in
the dentin was not strong
enough to resist the hydrolysis
resulting from water immersion. This hydrolysis, resulting
from either saliva exposure or
moisture from the dentin itself,
could result in composite resin
debonding from the dentin and
causing microleakage.
Since dentin was not etched
in these early bonding systems,

much of the adhesion was due

to bonding to the smear layer.
Some of the second-generation
systems were thought to soften
the smear layer and thus
improve resin penetration.
However, these systems resulted in bond strengths to dentin
that were weak and unreliable.
THIRD GENERATION

With the third-generation systems, the acid etching of the

dentin partially removes and/or
modifies the smear layer.16 This
effect is due to the pK of the
primer solution. The acid opens
dentinal tubules partially and
increases their permeability.
The acid must be rinsed completely before the primer is
applied. The primer contains
hydrophilic resin monomers
which include hydroxyethyl
trimellitate anhydride, or
4-META, and biphenyl
dimethacrylate, or BPDM. The
primers contain a hydrophilic
group that infiltrates the smear
layer, modifying it and promoting adhesion to dentin, and the
hydrophilic group of the primer
creates adhesion to the resin.
Following primer application,
an unfilled resin is placed on
dentin and enamel. These
third-generation adhesion systems usually use a hydrophilic
dentin-resin primer. Dentin
primers may be 6 percent phosphate penta-acrylate, or
PENTA; 30 percent HEMA; and
64 percent ethanol. Following
etching and primer application,
the unfilled resin adhesive is
applied to dentin and enamel.
In most of these systems, the
phosphate primer modifies the
smear layer by softening it;
after penetration, it cures,
forming a hard surface. The
adhesive is then applied,
attaching the cured primer to

JADA, Vol. 131, June 2000

Copyright 1998-2001 American Dental Association. All rights reserved.

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Figure 1. Collagen fibers exposed after etching

dentin (scanning electron microscopy X5000;
reprinted with permission of P.N. Mason).

the composite resin. Bonding to

smear-layercovered dentin was
not very successful before 1990,
however, because the resins did
not penetrate through the
smear layer and the smear
layer was very weak.17
FOURTH GENERATION

The complete removal of the

smear layer is achieved with
fourth-generation bonding systems. Fusayama and colleagues
tried to simplify bonding to
enamel and dentin by etching
the preparation with 40 percent
phosphoric acid.18 Unfortunately, it was not understood
that this procedure overetched
dentin and resulted in the collapse of exposed collagen fibers.
In 1982, Nakabayashi and
colleagues reported the formation of a hybrid layer resulting
from the polymerized methacrylate and dentin.9 The hybrid
layer is defined as the structure formed in dental hard tissues (enamel, dentin, cementum) by demineralization of the
surface and subsurface, followed by infiltration of
monomers and subsequent polymerization.9
The use of the total-etch
technique is one of the main
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Figure 2. Hybrid layer formed between etched

dentin and a one-bottle system (scanning electron
microscopy 1,550).

characteristics
of fourth-generation bonding
systems.19,20 The
total-etch technique permits
the etching of
enamel and
dentin simultaneously using
phosphoric acid
for 15 to 20 seconds. The surface must be
Figure 3. Resin tags and adhesive lateral branches
left moist (wet contribute to micromechanical bonding formation
bonding), how- (scanning electron microscopy 2,000).
ever, in order to
avoid collagen collapse (Figure
dissolved by the acidic action;
1); the application of a
the initial surface penetration
hydrophilic primer solution can
exposes the collagen fibers. In
infiltrate the exposed collagen
this area, for a depth of 2 to 4
network forming the hybrid
micrometers, hybridization
layer (Figure 2).21,22 Unfortakes place, and resin tags can
seal the tubule orifices
tunately, moist dentin is not
firmly.16,26
easily defined clinically and
may lead to less-than-ideal
FIFTH GENERATION
bonds if the dentin is excessively wet23 or dried.16
To simplify the clinical proceThe formation of resin tags
dure by reducing the bonding
and adhesive lateral branches
steps and thus, the working
complete the bonding mechatime, a better system was neednism between the adhesive
ed. Also, clinicians needed a
material and etched dentin sub- better way to prevent collagen
strate (Figure 3).22,24,25 The mincollapse of demineralized
eralized tissues of the peritubudentin. The fifth generation of
lar and intertubular dentin are
bonding systems was developed

JADA, Vol. 131, June 2000

Copyright 1998-2001 American Dental Association. All rights reserved.

Figure 4. Enamel surface after etching with a selfetching primer solution; the enamel surface is less
retentive than that obtained with phosphoric acid
(scanning electron microscopy 1,500).

to make the use of adhesive

materials more reliable for
practitioners.
The fifth generation consists
of two different types of adhesive materials: the so-called
one-bottle systems and the
self-etching primer bonding
systems.
One-bottle systems. To
facilitate clinical use, one-bottle systems combined the
primer and adhesives into one
solution to be applied after
etching enamel and dentin
simultaneously (the total-etch
wet-bonding technique) with 35
to 37 percent phosphoric acid
for 15 to 20 seconds.27 These
bonding systems create a
mechanical interlocking with
etched dentin by means of resin
tags, adhesive lateral branches
and hybrid layer formation and
show high bond-strength values
both to the etched enamel and
dentin.28,29
Self-etching primer.
Watanabe and Nakabayashi
developed a self-etching primer
that was an aqueous solution
of 20 percent phenyl-P in 30
percent HEMA for bonding to
enamel and dentin simultaneously.30

Figure 5. Laminate veneers of maxillary central incisors; the porcelain restorations are luted thanks to
the adhesive technique.

The combination of etching

and priming steps reduce the
working time, eliminate the
washing out of the acidic gel
and also eliminate the risk of
collagen collapse. However, the
self-etching primer solution also
has some disadvantages. For
example, the solution must be
refreshed continuously because
its liquid formulation cannot be
controlled where it is placed,31
and often a residual smear
layer remained in between
adhesive material and dentin.16
Also the effectiveness of selfetching primer systems on
properly etching the enamel
was less predictable than the
result obtained with phosphoric
acid gel (Figure 4).31 Toida32
advised that removal of the
smear layer by a separate etching step before bonding would
produce a more reliable and
durable bond to dentin.
Bond strength tests made
under laboratory conditions
often did not demonstrate statistically significant differences
between one-bottle systems and
self-etching primer bonding systems.33 Leakage tests conducted
under laboratory and clinical
conditions showed that the seal

achieved at the enamel margins

with one-bottle systems is superior to that resulting from selfetching primer.31
SIXTH GENERATION

Recently, several bonding systems were developed and proposed as the sixth generation of
adhesive materials. These bonding systems are characterized
by the possibility to achieve a
proper bond to enamel and
dentin using only one solution.
These materials should really
be a one-step bonding system.
Unfortunately, the first evaluations of these new systems
showed a sufficient bond to conditioned dentin while the bond
with enamel was less effective.
This may be due to the fact that
the sixth-generation systems
are composed of an acidic solution that cannot be kept in
place, must be refreshed continuously and have a pK that is
not enough to properly etch
enamel.34
However, any improvement
in the direction of clinical simplification of bonding procedures can bring us closer to
achieving an ideal bonding
system.

JADA, Vol. 131, June 2000

Copyright 1998-2001 American Dental Association. All rights reserved.

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DISCUSSION

Bonding to etched enamel was

considered a safe and reliable
procedure for many years.
Because of the inorganic composition of the enamel, the acid
attack produces interprismatic
and prismatic dissolution, creating irregularities into which
the resin can flow and, after
polymerization, create a
mechanical interlocking. The
demineralization of the enamel
depends on the low pH of the
acid and on the etching time.
The pH and the etching time
must be sufficient to provide
adequate enamel retention
without the need for additional
steps. The morphological studies made on the first five generations of bonding systems, in
which phosphoric acid was used
to etch enamel, showed a uniform etch pattern. When phosphoric acid was not used or
when self-etching primers (fifth
and sixth generations) were
applied, the bonding mechanism of adhesives to enamel
was less effective.
The bonding mechanism to
dentin was effective and predictable when the smear layer
was completely dissolved, intertubular and peritubular dentin
were dissolved, collagen fibers
exposed and, after infiltration
of resin monomers, a hybrid
layer formed. This bonding
mechanism was evident from
fourth to sixth generations of
enamel dentin bonding systems.
A wide range of clinical indications for bonding systems are
commonly followed by practitioners. Bonding systems can be
used as coupling resin sealants
to enamel in young patients.35
Also, the sealing effect of bonding systems can be used on protecting dentinal surfaces after
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preparation36 or beneath amalgam restorations.37,38

Desensitization of root exposure is another clinical indication for bonding systems.39-41
Also, bonding systems are indicated in any direct esthetic
restorations. In fact, the
mechanical properties of the
bonding mechanism achieved
with hybrid layer and resin tag
formation can be greater than
the forces of polymerization
contraction.16 Finally, bonding
systems are essential for a
proper bonding-luting procedure of any indirect restorations (Figure 5).42
CONCLUSIONS

To satisfy the growing esthetic

demands of todays dental
patients, improvements in
materials and procedures have
been made to make it possible

The mechanical
properties of the
bonding mechanism
achieved with
hybrid layer and
resin tag formation
can be greater than
the forces of
polymerization
contraction.
to reproduce the natural
appearance of natural teeth
with direct and/or indirect
esthetic restorations. Esthetic
techniques involve a bonding
step to ensure durability and
reliability. Thus, the ideal bonding system should be biocompatible, bond indifferently to enamel and dentin, have sufficient
strength to resist failure as a
result of masticatory forces,

have mechanical properties

close to those of tooth structures, be resistant to degradation in the oral environment
and easy to use for the clinician.
Although important improvements in bonding have been
made in the last 30 years, note
that the requirements of an
ideal bonding system are quite
similar to those indicated by
Buonocore.2 Apparently, the
future has a sound background
in the past.
Dr. Kugel is professor and assistant dean
for research, Tufts University School of
Dental Medicine, Boston, Mass. 02111
Address reprint requests to Dr. Kugel.
Dr. Ferrari is a research professor at Tufts
University School of Dental Medicine, Boston,
and professor, University of Siena, Italy.
The authors dedicate this paper to the
memory of Gaia Gotti. They also express
their appreciation to Jennifer Towers for her
help in the preparation of this manuscript.
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