THE SCIENCE OF BONDING: FROM

FIRST TO SIXTH GENERATION

GERARD KUGEL and MARCO FERRARI
J Am Dent Assoc 2000;131;20S-25S

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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.
A B S T R A C T
Background. Adhesive dentistry has revo-
lutionized 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 adhe-
sive 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 differ-
ence in bonding to enamel and to dentin,2 particu-
larly 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
20S JADA, Vol. 131, June 2000
Copyright 1998-2001 American Dental Association. All rights reserved.
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Clinical Implications. This article
reviews the evolution of bonding from the first gen-
eration to current bonding materials. It discusses
the composition and effectiveness of the various iter-
ations. 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 cur-
rent thinking is that a 30 to 40 percent phos-
phoric 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 col-
lagen is inaccessible due to surrounding hydroxy-
apatite crystals.9 The dentinal tubules are the
only pores available for micromechanical reten-
tion. 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
 Early dentin bonding was
further complicated by the pres-
ence of the smear layer. (The
smear layer is the organic
debris that remains on the
dentin surface after the prepa-
ration 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 genera-
tions of bonding systems.
FIRST GENERATION
In 1956, Buonocore and col-
leagues 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 inter-
action 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
Copyright 1998-2001 American Dental Association. All rights reserved.
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 bisphe-
nol-A glycidyl methacrylate, or
bis-GMA, or hydroxyethyl
methacrylate, or HEMA.15
The mechanism by which
these second-generation sys-
tems 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-genera-
tion 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 immer-
sion. 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 result-
ed in bond strengths to dentin
that were weak and unreliable.
THIRD GENERATION
With the third-generation sys-
tems, 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
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dentinal tubules partially and
increases their permeability.
The acid must be rinsed com-
pletely 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 promot-
ing 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 sys-
tems usually use a hydrophilic
dentin-resin primer. Dentin
primers may be 6 percent phos-
phate 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 21S
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 sys-
tems. Fusayama and colleagues
tried to simplify bonding to
enamel and dentin by etching
the preparation with 40 percent
phosphoric acid.18 Unfortu-
nately, it was not understood
that this procedure overetched
dentin and resulted in the col-
lapse of exposed collagen fibers.
In 1982, Nakabayashi and
colleagues reported the forma-
tion of a hybrid layer resulting
from the polymerized methacry-
late and dentin.9 The hybrid
layer is defined as the struc-
ture formed in dental hard tis-
sues (enamel, dentin, cemen-
tum) by demineralization of the
surface and subsurface, fol-
lowed by infiltration of
monomers and subsequent poly-
merization.9
The use of the total-etch
technique is one of the main
22S JADA, Vol. 131, June 2000
Copyright 1998-2001 American Dental Association. All rights reserved.
Figure 2. Hybrid layer formed between etched
dentin and a one-bottle system (scanning electron
microscopy 1,550).
Downloaded from jada.ada.org on June 9, 2009
characteristics
of fourth-gener-
ation bonding
systems.19,20 The
total-etch tech-
nique permits
the etching of
enamel and
dentin simulta-
neously using
phosphoric acid
for 15 to 20 sec-
onds. The sur-
face 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 Unfor- takes place, and resin tags can
tunately, moist dentin is not seal the tubule orifices
easily defined clinically and firmly.16,26
may lead to less-than-ideal
FIFTH GENERATION
bonds if the dentin is excessive-
ly wet23 or dried.16 To simplify the clinical proce-
The formation of resin tags dure by reducing the bonding
and adhesive lateral branches steps and thus, the working
complete the bonding mecha- time, a better system was need-
nism 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 min- collapse of demineralized
eralized tissues of the peritubu- dentin. The fifth generation of
lar and intertubular dentin are bonding systems was developed
Figure 4. Enamel surface after etching with a self- Figure 5. Laminate veneers of maxillary central inci-
etching primer solution; the enamel surface is less sors; the porcelain restorations are luted thanks to
retentive than that obtained with phosphoric acid the adhesive technique.
(scanning electron microscopy 1,500).

Downloaded from jada.ada.org on June 9, 2009

to make the use of adhesive
materials more reliable for
practitioners.
The fifth generation consists
of two different types of adhe-
sive materials: the so-called
one-bottle systems and the
self-etching primer bonding
systems.
One-bottle systems. To
facilitate clinical use, one-bot-
tle 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 simultane-
ously.30
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 self-
etching 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 etch-
ing step before bonding would
produce a more reliable and
durable bond to dentin.
Bond strength tests made
under laboratory conditions
often did not demonstrate sta-
tistically significant differences
between one-bottle systems and
self-etching primer bonding sys-
tems.33 Leakage tests conducted
under laboratory and clinical
conditions showed that the seal
achieved at the enamel margins
with one-bottle systems is supe-
rior to that resulting from self-
etching primer.31
SIXTH GENERATION
Recently, several bonding sys-
tems were developed and pro-
posed as the sixth generation of
adhesive materials. These bond-
ing 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 evalua-
tions of these new systems
showed a sufficient bond to con-
ditioned 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 solu-
tion that cannot be kept in
place, must be refreshed contin-
uously and have a pK that is
not enough to properly etch
enamel.34
However, any improvement
in the direction of clinical sim-
plification of bonding proce-
dures can bring us closer to
achieving an ideal bonding
system.

JADA, Vol. 131, June 2000 23S

Copyright 1998-2001 American Dental Association. All rights reserved.
DISCUSSION
Bonding to etched enamel was
considered a safe and reliable
procedure for many years.
Because of the inorganic compo-
sition of the enamel, the acid
attack produces interprismatic
and prismatic dissolution, cre-
ating 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 stud-
ies made on the first five gener-
ations of bonding systems, in
which phosphoric acid was used
to etch enamel, showed a uni-
form etch pattern. When phos-
phoric acid was not used or
when self-etching primers (fifth
and sixth generations) were
applied, the bonding mecha-
nism of adhesives to enamel
was less effective.
The bonding mechanism to
dentin was effective and pre-
dictable when the smear layer
was completely dissolved, inter-
tubular 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 indi-
cations for bonding systems are
commonly followed by practi-
tioners. Bonding systems can be
used as coupling resin sealants
to enamel in young patients.35
Also, the sealing effect of bond-
ing systems can be used on pro-
tecting dentinal surfaces after
24S JADA, Vol. 131, June 2000
Copyright 1998-2001 American Dental Association. All rights reserved.
preparation36 or beneath amal-
gam restorations.37,38
Desensitization of root expo-
sure is another clinical indica-
tion for bonding systems.39-41
Also, bonding systems are indi-
cated 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 proce-
dure of any indirect restora-
tions (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 bond-
ing system should be biocompat-
ible, bond indifferently to enam-
el and dentin, have sufficient
strength to resist failure as a
result of masticatory forces,
have mechanical properties
close to those of tooth struc-
tures, be resistant to degrada-
tion in the oral environment
and easy to use for the clinician.
Although important improve-
ments 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
Downloaded from jada.ada.org on June 9, 2009
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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