1.

Introduction
2. Basic concepts of adhesion
3. Requirements for good adhesion
4. Applications of Adhesive restorative
techniques
5. Enamel adhesion
6. Mechanism of etching and etch patterns
7. Dentin adhesion
8. Challenges in dentin bonding
9. Generations of dentin bonding agents
10. Conclusion
11.Bibliography
• Adhesion is one of the ideal requirements of a restorative material.

• The obvious advantage of adhesion would be the absence

of marginal gap between the restoration and tooth structure

• This minimizes microleakage and the possibility of

secondary caries.
ADHESION The state in which two surfaces are held together by
: interfacial forces which may consist of valance forces
or interlocking forces or both.
(The American Society for Testing and Materials Sp. D 907)

• An adhesive is a material, frequently a viscous fluid, that joins two

substrates together and solidifies and is able to transfer load
from one surface to the other. (Sturdevant)
 ADHESIVE : this refers to the bonding agent that when
applied to the surfaces or substances, can join them
together, resist separation and transmit loads across
the bond.

 ADHEREND : this refers to the surface or substrate

that is adhered to.

MECHANISMS OF ADHESIONS :

1. Mechanical adhesion : interlocking of the adhesive with

irregularities in the surface of the substrate, or
adherent.

2. Adsorption adhesion : chemical bonding between the adhesive

and adherent

3. Diffusion adhesion : interlocking between mobile molecules, such

as the adhesion of two polymers through diffusion of polymer
chain ends across an interface,
• The surface of the substrate should be clean

• The adhesive should wet the substrate well, have a

low contact angle, and spread onto the surface.

• There should be intimate adaptation between the

adhesive and the adherent.

• The bond strength between the adhesive and the adherent

should be strong enough to resist debonding.

• The adhesive should be well cured.

• Buonocore in 1955 introduced the acid-etch technique for
the adhesion of resin to the tooth.

• He envisioned the use of acids to etch enamel for sealing pits

and fissures.

• Acid etching transforms the smooth enamel into an

irregular surface and increases its surface free energy.
• When a fluid resin-based material is applied to the irregular etched
surface, the resin penetrates into the surface, aided by capillary action.

• Monomers undergo polymerization and the material becomes

interlocked with the enamel surface.

• The formation of resin microtags within the enamel surface is

the
fundamental mechanism of resin-enamel adhesion
• Originally Buonocore suggested the use of 85% phosphoric acid for
2 minutes on the enamel surface to etch it.

• Silverstone et al found that the application of 30-40%

phosphoric acid resulted in retentive enamel surfaces.

• Presently a 37% concentration of phosphoric acid is preferred.

• An etching time of 60 seconds originally was recommended

for permanent enamel using 30-40% phosphoric acid.
• Acid may be available as a liquid or gel form.

• Gel etchants are preferred due to better control in placement

over the enamel surface.

• The acid may be applied by means of syringe or brush. Syringe

placement is easy and precise.
• After etching, the enamel surface should be thoroughly
rinsed with a continuous stream of water spray for 5-10
seconds so that the acid is completely washed off.

• This should be followed by proper drying which will produce

a frosty, white appearance.
ENAMEL BONDING AGENTS

• Originally enamel bonding agent consisted of Bis-GMA or UDMA

resins with a diluent like TEGDMA to lower their viscosity.

• These agents flow easily into the microporosities of the enamel

surface and when polymerized by light activation form ‘resin tags’
which lock them into the enamel surface.

• Bond strength of composite resins to etched enamel is in the

range
from 15 to 25 MPa.
• The classic concepts of operative dentistry were challenged in the
1980-90s by the introduction of new adhesive techniques to
dentin as well as to the enamel.

• Dentin adhesion primarily relies on the penetration of adhesive

monomers into the filigree of collagen fibers left exposed by
acid etching.
 CHALLENGES IN DENTIN BONDING

• Bonding to enamel is a relatively simple process. Adhesion to

dentin presents a much greater challenge

• Structurally dentin consist of a substantial proportion of water

and organic material as compared to the 90% mineral
composition of enamel.

• Type I collagen is the principal organic content of dentin.

• Dentin is an intrinsically hydrated tissue, penetrated by a maze of

1-
2.5µm-diameter- fluid filled dentinal tubules.
• Dentinal tubule connects pulp with the DEJ. The constant
pressure from the pulp causes the fluid to move towards the DEJ.

• Dentin is a dynamic tissue that shows changes due to ageing,

caries, or restorative procedures.

• Diameter of dentinal tubules reduces as we move from the

periphery towards the pulpal side. Inversely the relative
area occupied by the tubules increase.

• Cut dentinal surface form an unique structure called as the

‘smear layer’. It is composed of debris of hydroxyappatite
crystals and denatured collagen.
• The smear layer fills the orifices of dentin tubules, forming ‘smear
plugs’ and decreases dentin permeability by 85%.

• Submicron porosity of the smear layer still allows for diffusion

of dentinal fluid.

• The removal of smear layer and smear plugs with acidic

solutions
will result in an increase of fluid flow onto the exposed dentin.
CHANGES IN DENTIN STRUCTURE AFTER
ETCHING

Changes in intertubular dentin :

•Exposes longitudinally/obliquely oriented collagen fibres

Interfibrillar spaces : 15-20nm

Changes in peritubular dentin :

•Opens tubule orifices in typical funnel shape
configuration
•Exposes circularly oriented collagen fibril arrangement
•Decrease surface energy
•Increase surface roughness
 HYBRIDIZATION

The structure formed in dental hard tissues by demineralization of the

surface and subsurface, followed by infiltration of monomers and
subsequent polymerization.
 CHEMISTRY

 Bonding to the organic part of dentin

 Interaction with
 Amino (–NH), Present in dentinal
collagen.
 Hydroxyl (–OH),
 Carboxylate (–COOH),
 Amide (–CONH) groups
 Dentin bonding agents have
 isocyanates, which extract hydrogen from the
above mentioned groups and
 aldehydes, bond chemically.
 carboxylic acid
 anhydrides and
 carboxylic acid chlorides
BEGINNING
• During 1950s, it was reported that a resin containing
glycerophosphoric acid dimethacrylate (GPDM) could bond to a
hydrochloric acid-etched dentin surface.

• A few years before that report, another researcher had used the
same monomer chemically activated with sulfinic acid.

• The bond strength of these primitive adhesion techniques

were severely reduced by immersion in water
FIRST GENERATION

• NPG-GMA(N-phenyl glycine glycidyl methacrylate), a surface active

comonomer is considered as the first generation dentin bonding
system.
• Bond strength - 1 to 3 MPa.
• Both Invitro and invivo clinical study results were discouraging.
• Example : Cervident
SECOND GENERATION
• They are phosphate ester material (phenyl-P and hydroxyethyl
methacrylate in ethanol)

• Mechanism of action is based on polar interaction

between phosphate group and calcium in the smear layer.

• The smear layer was the weakest link in the system

because of its
loose attachment with dentin.

• Bond strength was also poor (1-5 MPa).

• They show less wettability and penetration into the dentin
crossing the smear layer.

• Example :Clearfil Bond, Scotchbond, Bondlite

THIRD GENERATION
• The third generation dentinal adhesives attempted to deal smear
layer in Two way system.

• Either by modification of the smear layer to improve its properties

or by the removal of the smear layer by keeping the smear plugs
intact.

• Treatment of smear layer using acid primers were also attempted.

2.5% maleic acid, 55% HEMA, and traces of methacrylic acid were
used for this.
• Bond Strength : 3-8 Mpa
• Example : Scotch bond 2
FOURTH GENERATION
• They are; three step, total etch adhesive systems.

• Although smear layer acts as a ‘diffusion barrier’ that reduces the

permeability of dentin, it also can be considered as an obstacle
to the bonding.

• Based on this this consideration a fourth generation

dentin adhesives was introduced for use on acid etched
dentin.

• This method is commonly known as the total-etch

technique or the
etch and rinse technique.

• The acid will result in complete or partial removal of smear layer

with demineralization of underlying dentin. They also exposes
the collagen.
• The fourth generation dentin bonding system consist of three
essential components.
1. Phosphoric acid etching gel that is rinsed off
2. A primer containing reactive hydrophilic monomers in
ethanol, acetone, or water
3. An unfilled or filled resin bonding agent

• Acid treatment not only alters the mineral content of the

dentin substrate but also alters the surface free energy.

• When primer and bonding resins are applied to etched dentin,

they penetrate the intertubular dentin, forming a resin-dentin
interdiffusion zone, or ‘hybrid layer’.

• Examples : Scotch Bond Multi Purpose(3M), All Bond 2, Panavia

21
FIFTH GENERATION

• These adhesives are a simplified version of the fourth generation

adhesives. Also known as ‘one bottle’ system.

• The primer and adhesive is combined in one bottle. A

separate etching step is still required.

• Though they require fewer steps to achieve dentin bonding,

these agents are inferior to the fourth generation bonding agents
in terms of bond strength.

• Example : Single Bond(3M), One-Step, Gluma Comfort Bond.

SIXTH GENERATION
• Sixth generation dentin boding systems try to further simplify
the process of dentin adhesion by minimizing the clinical steps.

• Acids of lower concentration are generally used :10%

Phosphoric, 2.5%nitric, 10% citric, 10% maleic acids.

• They are also known as SEP – Self Etching Primers.

• Commercially they are available in two forms :

1. Self etching primers : etchant and primer is

in one bottle while adhesive is in a
separate bottle. First the etchant and
primer are applied on the tooth surface
which is then followed by application of
adhesive agent.
example : Clearfil SE bond, Xeno
2. Self etching adhesives : in these, the etchant, primer and
adhesive are all in one package but require mixing
before application on the tooth surface
example : Prompt-L-Pop(3M)
SEVENTH GENERATION
• Also known as All-in-one adhesive system.

• These are the most recent generation of dentin bonding agents.

• They combine etchant, primer, and adhesive in one bottle. They do

not require any mixing prior to application.

• Primarily these agents are intricate mixes of hydrophilic and

hydrophobic components in one bottle.

• Their bond strength is less than fourth and fifth

generation adhesives.

• Example : Adper easy bond , Cleaefil S3 Bond,

G-Bond, Xeno IV
 History
3-step
Etch&Rinse
N-Phenyl-Glycin-Glycidyl-Methacrylate
Bowen 1965
1th / 2th Generation 2-step
No etching, pH-neutral Etch&Rinse

1960 1970 1980 1990 2000 2010

3th Gen. 2-step

pH < 7 Self-etch

1-step
Self-etch

1989: Hybridlayer
FRQ
 Perfect Unperfected No Weak
Impregnation Impregnation Impregnation Hybridization

No Sensitivity Nanoleakage Sensitivity Microleakage

An Issue with Total Etch Adhesives…
Right Surface Moisture

WE DR
T Y
MOIS
T

FRQ
What happens if the tooth surface is overdried?

Dull dentin appearance indicates dehydration

The collapsed collagen decreases porosity and reduces

adhesive absorption : Increases chance for sensitivity
FRQ
The tooth surface needs to be moist!

Expanded collagen is porous and will absorb adhesive:

minimizes post-op sensitivity.

FRQ
 Over Dryness
There will be collapse of collagen fibres and demineralised dentin.

Inaffective penetration due to the collapsed collagen has been obs

ultramorphologically as the formation of “HYBRIDOID ZONE”.
 “OVER WET” PHENOMENA

•In the total-etch, wet bonding technique,

there is the danger that some regions in
complex cavity preparations (such as
proximal boxes) may be too wet.

•When single bottle primer/adhesives are

applied, the solvent may diffuse into the water,
instead of vice versa, forcing adhesive
monomers to undergo phase changes, forming
blisters, resin globules
Low POS with Self-Etch Adhesives Adper Easy
Bond Application test 3M ESPE internal data

Total number of dentists 100

Number of dentists encountering

7
post-operative sensitivity

Total number
of post-operative sensitivities 26

Total number of restorations

placed 5572

Percentage of restorations
with post-operative sensitivity 0.5%

FRQ
Why do Self-Etch Adhesives reduce
Post-Operative Sensitivity?

No separate etching step – minimized danger of overetching

and desiccation of dentin

Resin penetrates as far as demineralization of dentin –

minimized danger of unimpregnated collagen layer under
adhesive

FRQ
Self etch
2 steps Adper Easy One

Demineralization
+
Resin resin penetration
Demineralization
penetration

Risk of
nanovoids

- 2 consecutive steps - 1 single step

- risk of nanovoids, if penetration depth - no risk of nanoleakage, since
of etchant and resin are not equal penetration depths are equal
- higher risk of post-op sensitivity - lower risk of post-op
sensitivity

FRQ
 Why do Self-Etch Adhesives reduce
Post-Operative Sensitivity?
No separate etching step – minimized danger of overetching and
desiccation of dentin
Resin penetrates as far as demineralization of dentin – minimized
danger of unimpregnated collagen layer under adhesive
Adhesive is neutralized by basic hydroxyapatite during
application
Mild self-etch adhesives do not dissolve smear layer completely –
most tubules remain protected by smear plugs

FRQ
7th Generation adhesive on dentin

Clearfil Protect Liner

particle-filled adhesive

smear plug

dentin tubule acid-resistant submicron hybrid

layer

lab-demineralized dentin

FRQ of Prof. van Meerbeek, Univ. Leuven, Belgium

TEM image courtesy
Van Meerbeek et al.
2009, Dental Materials

FRQ
Van Meerbeek et al.
2009 Conclusions

“3-step etch&rinse adhesives and (mild) 2-step self-etch adhesives are still
the benchmarks

When bonding to enamel, an etch&rinse approach is definitely preferred

When bonding to dentin, a mild self-etch approach is superior, as it involves

(like with glass-ionomers) additional ionic bonding

Altogether, … selective etching of enamel followed by the application of

the 2-step self-etch adhesive to both enamel and dentin currently
appears the best choice“

FRQ
Bond Strengths
Reality check

FRQ
Bond Strengths
Bart van Meerbeek et al

„Relationship between Bond-strength tests and Clinical Outcomes“

Dent Materials, 2009, 11, 148ff.
“A good correlation (…) was found between the annual failure
rates
reported in the systematic review of Peumans et al and the “Battle of the Bonds”
shear-bond strength data from Degrange et al.”

„The significantly highest bond strength was measured

for OptiBond FL (Kerr) that somewhat surprisingly
performed not significantly better than the relatively
new 1-step adhesive Easy Bond (3M ESPE).“

FRQ
Adper Easy Bond 3M
ESPE

Development Objectives
 A new self-etch formulation
 Fast and easy to use
 Robust application
 Moisture tolerant

+
++++

FRQ
 Adper™ Easy One Self Etch
Application

FRQ
Adper™ Easy One Self Etch
Application

FRQ
 Adper™ Easy One
Self Etch Application

Apply adhesive to tooth surface

for a total of 20 sec

FRQ
 Adper™ Easy One
Self Etch Application

Gentle agitation of adhesive maximizes penetration into etched

dentin and enhances integrity of hybrid layer leading to
better bonds and less sensitivity.
FRQ
 Adper™ Easy One
Self Etch Application

Dry for 5 sec

FRQ
 Adper™ Easy One
Self Etch Application

Light cure for 10 sec

FRQ
 Adper™ Easy One Self Etch
Application

FRQ
TEM-Interface Analysis
Dentin (self-etch) - Prof. van Meerbeek

FRQ
TEM-Interface Analysis
Cut Enamel (self-etch) - Prof. van Meerbeek

FRQ
 The Formulation
Meeting of the Generations

Adper Single Bond 2 Adper Easy Bond

HEMA Bis- HEMA Bis-GMA
GMA Dimethacrylate Vitrebond™
Dimethacrylate Vitrebond™ Copolymer Filler
Copolymer Filler Ethanol Water
Ethanol Initiators
Water Methacrylated
Initiators phosphoric esters

pH = 4.7 p
H

=
FRQ