Prof.Dr.

Bilinç Bulucu (2022-23)

Development, Use and Classification of Dentin Adhesive Systems
Adhesive systems:
Enamel/dentin bonding systems used to perform adhesive bonding are today called
“adhesive systems”. Adhesive systems consist of; dentin conditioner, dentin primer, and dentin
adhesives applied at different stages. There are also systems where the primer and
conditioner are combined or primer and adhesive are combined.
They are solutions of resin monomers that make the resin - dental substrate interaction
achievable. The chemical composition of adhesives also includes curing initiators, inhibitors or
stabilizers, monomers of composite ( HEMA, MMA, MA, 4-MET, Phenyl –P…), solvents (water,
ethanol,acetone) and, in some cases, inorganic fillers, specific components (polykenoic
copolymer, glutaraldehyd, antibacterial componenets)
Many resin adhesive systems and types have been developed to achieve a durable bond to
dental tissues. Further complication are associated with the heterogeneity of tooth structure
and composition, the hydrophilicity of the exposed dentine surface, the features of the dental
substrate after cavity preparation and the characteristics of the adhesive itself, such as its
physicochemical properties and its strategy of interaction with enamel and dentin.
Classification of Contemporary Adhesives
Dentin bonding agent (adhesives) can be defined as “a thin layer of resin applied between
the conditioned dentin and resin matrix of composite”.

Over the years, there have been numerous classifications of dentin bonding agents that have
been advocated by many authorities. Researchers have made this classification based on the
stages of clinical practice and modern adhesive strategies, sometimes through generation.
Each generation has tried to minimize procedure steps, allowing clinicians to finish restorations
in less time with less technical precision. In addition, improved chemical structures of dentin
adhesives have resulted in better bonding.
Dentin adhesives can be classified in three main groups:
1. Historical classification:
- First generation
- Second generation
- Third generation
- 4th, 5th, 6 th, 7th generation
- Eight generation dentin adhesive systems

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 2. Classification according to their effect on smear layer *
- Applied over Smear layer
- Modifying the smear layer
- Completely removes the smear layer
- Dissolves the smear layer
* Smear layer: As a result of the tissue removal procedures performed during cavity
preparation by using milling tools, the dentine surface is covered by a smear layer consisting
of blood, saliva, bacteria, hydroxyapatite crystals and denatured collagen. The smear layer,
which protects the dentin and pulp tissue against irritation, is about 0.5-2 µm thick and is
porous and amorphous in appearance. The different thickness of the smear layer also causes
differences in the permeability of dentin tissue. Dentin tubule mouths are clogged with smear
plugs, which reach a depth of 1 to 10 µm of tubules. These smear plugs are a continuation of
the smear layer consisting of fragmented and denatured hydroxyapatite. There are various
opinions about the removal or modification of this layer, which is effective in adhesion
bonding. Some of the researchers have argued that the smear layer creates a barrier for
rnicroorganisms to reach the pulp, and have reported that with removal of this layer, dentin
permeability will increase 5-10 times. Another group of researchers have shown that the
smear layer is a shelter for bacteria to settle and multiply.

3. Current classification (according to clinical application types)

 Etch&rinse (ER) adhesives
-Three-stage etch & rinse (ER) adhesives (Fourth generation)
-Two-stage etch & rinse (ER) adhesives (Fifth generation)
 Self-etch adesives
- Two-component self-etch adhesives (Sixth generation)
-One-component and one-stage self-etch adhesives (Seventh generation) (All-in-one)
- Eighth generation
-Universal (Multi-mode)

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 According to Historical Classification;

First Generation Adhesive Systems (Adhesive Systems Applied on Smear Layer); -

The first generation bonding systems were published by Buonocore in 1956, who
demonstrated that use of glycerophosphoric acid dimethacrylate (NPG-GMA) containing resin
would bond to acid etched dentin.
- These bonding agents were designed for ionic bonding to hydroxyapatite or for covalent
bonding (hydrogen bonding) to collagen. However, immersion in water would greatly reduce
this bond. After nine years, Bowen used a coupling agent to overcome this problem. He
addressed this issue using that acted as NPG-GMA a primer or adhesion promoter between
enamel/dentin and resin materials by chelating with surface calcium, where one end would
bond to dentin, and other would polymerize with composite resin.
- Overall, this generation leads to very poor clinical results. Dentin bondings in this
generation had a hydrophobic structure, so their attachment strength to dental tissues was
low (2-6 MPa).

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Second Generation Adhesive Systems (Adhesive Systems Applied on Smear Layer):
- They were developed in the early 1980s.
- These systems, which are halophosphate esters of resin monomers such as Bis-GMA (
bisphenol A and glycidyl methacrylate) or HEMA( hydroxyethly methacrylate).
- The second generation adhesive systems did not have sufficient binding strength to resist
the polymerization shrinkage of composite resin (1-10 MPa).
- The smear layer was still not removed, and this contributed to the relatively weak and
unreliable bond strengths of this second generation. The smear layer is really a smooth layer
of inorganic debris that remains on the prepared dentin surface as a result of tooth
preparation with rotary instruments (the drill).
-This generation of bonding agents is no longer used, due mainly to failed attempts to bond
with a loosely bond smear layer.

Although the first and second generation adhesive systems were developed to bind to the
inorganic structure of the dentin, the desired clinical success was not achieved.

Third Generation Adhesive Systems (Adhesive Systems that Modify the Smear
Layer):
- The third generation bonding systems introduced a very important change: the acid etching
of the dentin in an effort to modify or partially remove the smear layer.
- This opened the dentin tubules and allowed a primer to be placed after the acid was
completely rinsed away. ( It was considered controversial in dentistry as the feeling existed
that dentin ought not to be etched).
-After the primer was added, an unfilled resin was placed on both dentin and enamel.
However, due to the hydrophobic nature of the bonding agent, the desired success in terms of
binding strength was not achieved again.
The weak link with this generation was the unfilled resins that simply did not penetrate the
smear layer effectively.

Fourth Generation Adhesive Systems (Adhesive

Systems that Completely Eliminate the Smear Layer): ( Etch and Rinse adhesive
systems, ER)
- In 1980s and 1990s, fourth generation dentin bonding agents were introduced.
- The fourth generation materials was the first to achieved complete removal of smear layer
and still considered as the golden standard in dentin bonding.
- In this generation, the three primary components (etchant, primer and bonding) are typically
packaged in separate containers and applied sequentially.

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 - In these systems, which reduce dentin permeability and eliminate the smear layer, which is
considered to be a diffusion barrier, orthophosphoric acid is applied to both enamel and dentin
tissue at the same time (Total-etch) at a concentration of 30-40% ( ( %37)) for a period of
15–20 s. However, the surface must be left moist “wet bonding”, in order to avoid collagen
collapse. The application of a hydrophilic primer solution can infiltrate the exposed collagen
network forming the hybrid layer. The hybrid layer is formed by the resin infiltrated surface
layer on dentin and enamel.

- The goal of ideal hybridization is to give high bond strengths and a dentin seal. Bond
strengths for these adhesives were in the low- to mid-20 MPa range and significantly reduced
margin leakage compared to earlier systems. This system was very technique sensitive and
required an exacting technique of controlled etching with acid on enamel and dentin, followed
by two or more components on both enamel and dentin. These systems are very effective
when used correctly, have good long-term clinical track record, and are the most versatile of
all the adhesive categories, because they can be used for virtually any bonding protocol
(direct, indirect, self-cure, dual-cure or light-cure).

Etch & rinse adhesive systems can be either three-stage or two-stage.

i- Three-stage Etch&Rinse Adhesive Systems: These adhesive systems with proven
binding strength values to enamel (20-50 MPa) and dentin (13-80 MPa) are applied in three
stages following each other.
1st Stage: Changing the surface conditions of enamel and dentin (roughening with acid),

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 2nd Stage: Application of adhesion enhancing agents (application of primer),
3rd Stage: Infiltration of bonding agent to demineralized enamel/ dentin surface.
1st Stage: Change of Enamel/Dentin Surface Conditions: The reason for changing the
enamel/dentin surface conditions is to create a suitable enamel/dentin surface that can provide
chemical and micro-mechanical bonding of bonding agents. At this stage, %37 phosphoric
acid is applied to the enamel and dentin tissue (Total-etch) for a certain period of time
(minimum=15 sec, maximum=30 sec) and then the acid is washed away from the tooth
surface as far as the duration in which acid is applied. As a result of acid roughening process,
the smear layer in the enamel is removed.

- By acidification, a large number of microscopic indentations and protrusions are created at

a depth of approximately 5-50 µm, increasing the surface area and increasing the critical
surface tension value (CST) of the enamel tissue to 72 dynes/cm. All these factors provide an
alignment between composite resin and cavity wall, increasing the retention of restoration and
greatly reducing edge leaks.
-Generally, 37% orthophosphoric acid is used for roughening with acid. The purpose of the
primer applied in the second phase of adhesive systems is to increase critical surface tension
value.

2nd Stage: Use of Adhesion Enhancing Agents

- The primer containing the HEMA monomer is applied to the surface of the enamel/dentin,
where the surface conditions have been changed, in order to increase the surface energy due
to its wettability. Instead of HEMA, many monomers are also used as primers.
- The primer molecules are bipolar and contain two different functional groups. Of these, the
hydrophilic one interacts with moist dentin, while the hydrophobic one interacts with adhesives.

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 Hydophobic and hydrophilic molecule in primer.

- Primers are binding-enhancing materials that dissolve in solvents such as water, ethanol, or
acetone. ( The primer is applied to the dentin surface with a microbrush until a bright surface is
obtained in two or more layers according to the case after the roughening stage with acid, and
dried with air for 5-10 seconds. During the drying process, care is taken to fully vaporize the
solvents (acetone, ethanol) in the adhesive content. The primer prepares the surface for
adhesive bonding by altering the sequences of collagen fibrils, and then helps make the
penetration of the monomer more effective. The primer, which passes through the residual
smear base in the acidified dentin tissue, is replaced by water on the dentin surface due to the
volatile property of acetone and/or ethanol and fills the nano-cavities left by hydroxyapatite
crystals that melt between the collagen fibrils.
3rd Stage: Infiltration of Bonding Agent to Demineralized Enamel/Dentin Surface
- Bonding agents attached to enamel/dentin and resin are applied to enamel/dentin surfaces
where surface conditions have been changed by acidification and then primer has been
applied. Resin tags formed between the outer surfaces of enamel prisms as a result of
penetration of bonding agents into interprismatic spaces are called “macrotag”, while many
resin tags formed in the form of network by penetration into intraprismatic spaces are called
“mikrotag”. Macro and microtags are responsible for micromechanical bonding in enamel
tissue. Due to having large number and width of the fields of touch, the contribution of
microtags to bonding is greater than that of macrotags. As a result of the studies, acceptable
tag length is determined as 10-30 µm and it is shown that longer tags can break from the neck
regions and tag length does not have an important role in bonding. After the primer applied,
bonding agent is applied to the surface with a microbrush, a thin film layer is created by gently
squeezing air and then it is polymerized. Thus, the hybrid layer formed after the primer
application is polymerized with the binding agent.

Three-stage etch&rinse (ER) adhesive systems (fourth generation) are still recognized as the
gold standard. However, these systems can be very confusing and time consuming with so
many bottles and application steps. Because of the complexity of multiple bottles and steps,
dentists began requesting a simplified adhesive system. These systems are still the standards
by which the newer systems are judged.

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 Fifth Generation: Two-stage Etch&Rinse Adhesive Systems
In the 1990s and in the ongoing decade, the fifth generation bonding systems sought to
simplified the process of fourth generation adhesion by reducing the clinical steps which
results in reduced working time ( By switching from three-stage systems to two-stage
systems, the practice was simplified and began to be widely used by clinicians). . These are
distinguished by being “one step” or “one bottle” system.
In two-stage ER adhesive systems; following the stage of changing surface conditions of:
- enamel/dentin (1. stage),
- the primer and bonding agent (adhesive resin) application stages (2. and 3. stage) are
combined, hydrophilic and hydrophobic monomers are collected in the same bottle (2. stage).
Excessive etching and drying procedure can cause collagen collapse in dentin structure. This
will cause deficient in adhesion and also postoperative sensitivty. An improved way was
needed to prevent collagen collapse of demineralized dentin and to minimize if not totally
eliminate, postoperative sensitivity. So the most common method of simplification is “one
bottle system” combined the primer and adhesive into one solution to be applied on enamel
and dentin simultaneously with 35 to 37% phosphoric acid for 15–20 s.
This single bottle, etch-and-rinse adhesive type shows the same mechanical interlocking with
etched dentin occurs by means of resin tags, adhesive lateral branches and hybrid layer
formation and shows high bond strength values to dentin with marginal seal in enamel. These
kinds of adhesives systems may be more susceptible to water degradation over time than the
fourth generation. This is because the polymerized primer of the “one bottle system” tends to
be hydrophilic in nature. However, when using the fourth generation, the hydrophilic primer is
covered by a more hydrophobic resin, making it less susceptible to water sorption. Several
long term studies indicate that 5th generation dental adhesive achieve high clinical bond
strengths.
In addition, the resin-dentin bond is prone to water degradation, 5th generation adhesives
are more prone to water degradation than 4th generation dental adhesive. The binding
strength values of enamel tissue (35-45 MPa) are the same as the three stage adhesive
systems, but the binding strength values of dentin tissue (30-35 Mpa) are found to be lower
than enamel.

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Sixth and seventh generation adhesive systems: SE (self etch) adhesive systems
(Adhesive systems that solve the smear layer)

Sixth Generation: Two-stage Self-etch Adhesive Systems

The sixth generation bonding systems introduced in the latter part of the 1990s and the early
2000s also known as the “self-etching primers”, were a dramatic leap forward in technology.
The sixth generation bonding systems sought to eliminate the etching step, or to include it
chemically in one of the other steps: (self-etching primer + adhesive) acidic primer applied to
tooth first, followed by adhesive or (self-etching adhesive) two bottles or unit dose containing
acidic primer and adhesive; a drop of each liquid is mixed and applied to the tooth. It is
recommended that the components are mixed together immediately before use. The mixture
of hydrophilic and hydrophobic resin components is then applied to the tooth substrate.
Evidently, these bonding systems are characterized by the possibility of achieving a proper
bond to enamel and dentin using only one solution. The biggest advantage of the sixth
generation is that their efficacy appears to be less dependent on the hydration state of the
dentin than the total-etch systems.
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 pH that is not enough to properly etch
enamel. In order to overcome this problem, it is recommended to etch enamel first with the
traditional phosphoric acid prior to using it. However, those utilizing this technique should take
care to confine the phosphoric acid solely to the enamel. Additional etching of the dentin with
phosphoric acid could create an “over-etch” situation where the demineralization zone is too
deep for subsequently placed primers to completely penetrate.
While data indicates that 6th generation adhesives will adhere well to dentin (41 MPa at 24
hours), the bond to enamel is at least 25% weak to enamel then both the 4th and
5th generation adhesives in pooled data studies. Several respected clinicians have utilized
6th generation adhesives for bonding to dentin after selectively etching the enamel.

Mechanism;
In this system, adhesive and acidic primer are applied in two separate stages.
* In the first stage, after weakly acidic primer is applied in two layers to dentin covered with
smear layer, it is waited for the solute smear layer to join the binding and for adequate
penetration of the primer into the intercollogenous cavities. After making it spread into the
cavity by squeezing mild air, it is polymerized with a light source. If necessary, this process
can be repeated several times in accordance with the recommendations of the manufacturer.

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 * In the second stage, the primer is polymerized with light by applying adhesives to the
applied surfaces.
SE (self etch) adhesive systems have been developed to protect the dentin and pulp tissue of
the smear layer against bacterial irritation, to reduce fluid movements in the tubules and
dentin permeability. Therefore, the working principle of SE adhesive systems is based not on
removing the smear layer but on solving this layer. In these systems, the absence of
roughening with separate acid, washing and drying processes found in ER adhesive systems
reduces the stages of clinical application and saves clinicians’ time.
Weakly acidic primers used in SE adhesive systems are classified as;
- ultra-light (pH >2.5),
- light (pH ≥2),
- medium (pH~1.5) and
-strong (pH ≥1) SE adhesives according to their pH.
They cause minimal dissolution of the smear tags without eliminating the smear layer and
partially demineralize the dentin tissue, allowing the monomer to infiltrate the dentine. SE
adhesive systems do not produce as effective roughening of enamel as ER adhesives. For this
reason, it is recommended to apply acid to enamel to increase the binding with enamel.

Seventh Generation: Single Stage Self-etch Adhesive Systems

Self etch adhesive materials that combine acid, primary and bonding steps in a solution,
without washing and with reduced clinical application stages are gaining increasing popularity.
The reduction of stages has made this system an easier system for physicians. The seventh
generation bonding systems was introduced in late 1999 and early 2005. The seventh
generation or one-bottle self-etching system represents the latest simplification of adhesive
systems. With these systems, all the ingredients required for bonding are placed in and
delivered from a single bottle. This greatly simplifies the bonding protocol as the claim was
that could be achieved consistent bond strengths while completely eliminating the errors that
could normally be introduced by the dentist or dental assistant who had to mix the separate
components with other more complicated systems. However, incorporating and placing all of
the chemistry required for a viable adhesive system into a single bottle, and having it remain
stable over a reasonable period of time, poses a significant challenge. These inherently acidic
systems tend to have a significant amount of water in their formulations and may be prone to
hydrolysis and chemical breakdown. Furthermore, once placed and polymerized, they are
generally more hydrophilic than two-step self-etching systems; this condition makes them
more prone to water sorption, limits the depth of resin infiltration into the tooth and creates

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some voids. The advantage of this generation was not any mixing required and the bond
strengths were consistent. However, the seventh generation adhesives have proven to have
the lowest initial and long term bond strengths of any adhesive on the market today that may
be considers as disadvantage. Seventh generation adhesives involve the application of etch,
primer, and adhesive which have already been mixed, followed by light curing the tooth.
Seventh generation adhesives are “all-in-one” if there has ever been such a thing. The clinical
and scientific data on these adhesives proves that they are hydrophilic and degrade more
rapidly. In addition, the chemistry mast be acidic, as etch is involved in this liquid, and this has
been shown to adversely react with the composite initiator systems.

Eighth Generation Adhesive Systems

Eighth generation adhesive systems containing nanoscale particles were first introduced in
2010 ( voco America introduced voco futurabond DC as 8th generation bonding agent ). These
systems have single component and have nano fillers with an average particle size of 12 nm in
their structure. These nano fillers increase the thickness of the hybrid layer which improves
the penetration of resin monomers and the mechanical properties of adhesive systems. (Based
on the manufacturer, nano-particles acting as crosslinks, will reduced the dimensional
changes. The type of nano-fillers and the method that these particles are incorporated affect
the adhesive viscosity and penetration ability of the resin monomers into collagen fibers
spaces. Nano-fillers, with dimensions larger than 15–20 nm or a content of more than 1.0
percent by weight, both can increase the viscosity of the adhesives, and may cause
accumulation of the fillers over the top of the moistured surface. These clusters can act as
flaws which may induce cracks and cause a decrease in the bond strength).
Nano-bonding agents are nano-filling solutions with a longer shelf life, which demonstrate
better enamel and dentin bonding strength and stress absorption. Acidic hydrophilic
monomers are involved in the structure of eighth generation adhesive systems. The main
advantages of these systems are that they can be easily applied to acidified enamel surface
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even if they are subsequently contaminated with saliva or moisture. It has been observed that
filled bonding agents produced higher in vitro bond strength.
Universal (Multi-mode) Adhesive Systems
Universal adhesives have been used in clinics since 2011. These systems are also known as
multi-mode or multi-purpose adhesives. Because these adhesive systems can be used as SE
adhesives, the ER adhesives or SE adhesives in dentin tissue and ER adhesives on enamel
tissue (a technique known as selective acidification of enamel). These systems, enabling the
implementation of the total-etch or selective-etch approaches, have been developed to
improve weakness of the previous generation single-step SE adhesives and to obtain a strong
bonding in enamel tissue. As a result of the studies, it was revealed that good results were
obtained regarding the bonding strengths of universal adhesives. The majority of universal
adhesives are designed based on the all-in-one concept of existing single-stage SE adhesives.
Water is needed to ionize hydrophilic acidic monomers in formulations of these new adhesive
systems. The pH value of current universal adhesives varies between 2.2 and 3.2, although it
varies by product. There is a concern that universal adhesives in this pH range may be very
effective when evaluated for attachment with dentin tissue, but they may not be effective when
it comes to attachment to enamel tissue, especially to prepared enamel.
Universal adhesives have, in fact, similar content with conventional single-stage SE
adhesives and contain carboxylate or phosphate monomer that bonds to calcium in
hydroxyapatite. Monomers such as methacryloyloxydecyl dihydrogen phosphate (10-MDP),
silane, polyacrylic acid are often added to their structures. 10-MDP monomer is included in
universal adhesive systems due to its chemical binding to hydroxyapatite, which exists in both
enamel and dentin tissue. Additionally, these systems include BPDM, PENTA and
polyalkenoic acid copolymers which can increase attachment to dental tissues.
Furthermore, the matrix structure of universal adhesive systems consists of a combination of
hydrophilic HEMA, hydrophobic UDMA and Bis-GMA monomers. As a result of the
combination of these properties, universal adhesives provide a bridge between hydrophilic
dental tissue and hydrophobic composite resin under various surface conditions.
The multifaceted uses of these systems primarily include the advantages of the traditional ER
technique. In addition, clinicians using this bonding system have the opportunity to apply both
selective etch and SE techniques. Therefore, universal adhesives have a much wider
application area than 7th generation dentin bonding systems. In addition, the manufacturer
states that universal adhesives can be used for the application of both direct and indirect
restorations, and they are also compatible with self-cure, light-cure and dual-cure resin based
simans, metal, zirconia, porcelain and composites. However, the main disadvantage of
universal adhesives is that they contain water like other single stage SE adhesives, resulting in
hydrolytic destruction. Therefore, it is recommended to apply hydrophobic resin on the
polymerized universal adhesive. Since the presence of water is a problem for all single-stage
adhesives, ethanol is being studied.

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