ADHESION AND BONDING FOR

COMPOSITE RESINS
- Namrata Jajoo
1st Year PGT
Department of Conservative Dentistry and Endodontics
CONTENT
• INTRODUCTION
• COMMONLY USED TERMINOLOIES
• PRINCIPES OF ADHESION
• MECHANISM OF ACTION
• FACTORS AFFECTING ADHESION
• ADVANTAGES OF ADHESIVE TECHNIQUE
• HISTORY OF BONDING IN COMPOSITE RESIN
• IDEAL REQUIRMENTS OF BONDING AGENTS
• COMPONENT OF BONDING SYSTEM OF COMPOSITE RESIN
• MECHANISM OF BONDING
• ENAMEL BONDING
• DENTIN BONDING
 INTRODUCTION
• One of the major requirement in restorative dentistry is the proper b0nding
between the restorative material and the tooth surface. The inventions over a
period of time have led to the development of various techniques and modalities,
which help in adhesion thereby reducing the tooth restoration gaps. Certain
materials have also been developed which possess the property of bonding TO
the tooth surfaces which may be physical, mechanical or chemical and such
restorations are known as bonded restorations or adhesive restorations.
• However , the continuous search to minimize the restoration—tooth interface has
not been able to achieve complete success because of many inherent weakness of
restorative materials. Composite resin is one of the most commonly used tooth
coloured restorative material in the field of adhesive dentistry. Composite resin do
not show an intimate microscopic contact with dentin when placed directly into
the cavity. In order to overcome this, an intervening layer of fluid is used, which
fills in the microscopic space, polymerizes and combines with the composite resin
and components of dentin and thereby reducing microleakage.
 COMMONLY USED TERMINOLOGY
• The American Society for
Testing and Materials (ASTM)
Sp no D 907
• ADHESION: The state in which
two surfaces are held together
by interfacial forces which may
consist of valence forces or
interlocking forces or both.
• ADHESIVE: This refers to the
bonding agent that when
applied to the surfaces of
substances, can join them
together, resist separation and
transmit loads across the bond.
• ADHEREND: Surface or
substrate that is adhered to.
 PRINCIPLES OF ADHESION

The phenomenon of adhesion is dependent upon certain factors. The

main factors are
• Characteristics of the substrate
• Wettability of the substrate by the adhesive
• Viscosity of the adhesive
• Morphology or surface roughness of the substrate
• SUBSTRATE : knowledge of surface chemistry and physics of the substrate is
essential to understand the basic principles of adhesion
• WETTABILITY : it is the relative affinity of the liquid for
the surface of the solid
• Wetting – the degree of spreading of a liquid drop on a
solid surface is called wetting
• The degree of wetting can be measured by the contact
angle formed by the liquid surface and the interface
separating the liquid and the solid.
• Good wetting results in better capillary penetration and
the adhesion, indicating stronger attraction between the
solid and liquid.
• the contact angles are directly proportional to the
viscosity
• The factors governing the interaction between the substrate and the adhesive are
as follows :
1. Driving force (surface energy) that tends to spread the adhesive over the
substrate
2. resistance to spreading that depends on the viscosity of the adhesive
3. Surface irregularities on the substrate
4. Presence of contaminants on the substrate
• Surface energy : Inside the lattice arrangement of a
solid, all the atoms are equally attracted to each
other. The interatomic distances are equal and the
energy is minimal. The outermost atoms at the
surface of the lattice are not equally attracted in all
directions, resulting in a surface energy
• The increase in energy per unit area of surface –
surface energy
• In liquids, this is known as the surface tension.
Expressed in joules x square meter
• For effective spreading of the liquid on the substrate,
the surface energy of the substrate should be greater
than that of the cohesive forces of within the
molecules of the liquid
• more the surface irregulartities – better is the
adhesion
MECHANISM OF ACTION
 FACTORS AFFECTING ADHESION
1. Clinical factors :
• Contamination – saliva, blood, moisture contamination from hand pieces, oil
contamination from hand pieces or air water syringes
• Surface roughness / mechanical undercuts
• Fluoride content of the tooth
2. Factors effecting adhesion to mineralized tissues :
Structural aspect of enamel and dentin and cementum
changes in dentin with age
Smear layer
Composition and structural aspect of enamel and dentin
• Composition and structure of enamel and dentin are substantially
different- thus affecting adhesion
• Enamel is almost homogenous in structure and composition
except some aprismatic enamel at the outer surface.
• Unlike enamel the constituents of dentin are unevenly
distributed in intertubular and peritubular dentin which makes it
heterogeneous.
• Dentin is a dynamic and vital tissue and able to develop defence
mechanism.
• Diameter of dentinal tubules decrease from 2.5µm on pulpal side
to 0.8µm towards the DEJ.
• Similarly the number of dentinal tubules decrease in number
from pulp (45,000/mm²) to the surface(20,000/mm²).
• The dentinal tubules are occupied by fluid i.e. 1% in the
superficial tubules and 22% in the deeper tubules.
• Hence, dentin is an intrinsically wet tissue and the fluid present in
tubules is under constant outward pressure from pulp.
Intrapulpal fluid pressure is estimated to be 25-30mmHg or 34-
40cm water.
• Bond strength of deeper dentin is lesser than superficial dentin -
remaining dentin thickness affects adhesion.

• Therefore , bonding to dentin has been more problematic than

bonding to enamel.
Cementum bonding

• It is a hard calcified tissue containing 45-50% inorganic

material and the balance is organic material and water.
• Thickness- increases from CEJ to apex being thickest at
the apex.
• Calcium component – decreases from cervical third to
apical third.
- increases from outer to inner third
in the cervical and middle third with
no change in the apical third.
• The aspect of cementum bonding may be termed as ‘not pure
bonding to cementum’ because it rather bonds to underlying
dentin with only a margin lying on cementum.
• Cementum plays an important role when restoring class V or deep
proximal lesions or root caries or attempting to rebond split teeth.
• Thus the presence of a cementum layer of 16-60µm at the cervical
margins of cavities can be a major deterrent for good bonding.
Changes in the dentin structure
• Dentin is a dynamic substrate.
• It undergoes physiological dentinal sclerosis and reactive sclerosis.
• Tertiary or reparative dentin is deposited in response to insult.
• Dentin sclerosis or formation of transparent dentin generally occur at
cervical area of tooth.
• Sclerotic dentin is characterized by apposition of peritubular dentin and
precipitation of rhomboidal mineral crystal.
• Low permeability.
• It is an area of complete hyper mineralization without tubule exposure even
when etched with an acid.
• All these morphologic and structural transformations by physiologic and
pathologic process result in dentinal surface less receptive to adhesive
treatments than in normal dentin.
DENTIN BONDING: effect of degree of
mineralization and acid etching time

According to study done by GC Lopes, LCC Vieira, S

Monteiro
Hardness of sclerotic dentin is approx. 30% higher
than normal dentin.
Thickness of the hybrid layer less than normal dentin.
Bond strength less.
To obtain bond strength similar to normal dentin, the
etching time ( with 35% phosphoric acid ) needs to be
doubled.
For normal occlusal dentin no difference exists in
bond strength.
Smear layer

• Any debris , calcific in nature, produced by

reduction or instrumentation of dentin,
enamel or cementum or as a contaminant
that precludes interaction with underlying
pure tooth tissue.

Porous smear layer with water filled channels between

the smear particles
• Great influence on any adhesive bond formed between cut tooth
and restorative material.

• Thickness - 0.5µ to 5µm.

• Factors determining thickness of smear layer :-

- Type of instrument used

- Method of irrigation used
- Site of dentin at which it is formed
• Occlude the dentinal tubules with formation of smear plug.

• Porous and penetrated by submicron channel which allow small

amount of dentinal fluid to pass through.

• Reduce dentin permeability about 86%[Bart Van Meerbeek et al].

• Acidic conditioner in order of increasing potential to remove the
smear layer.:-
-citric acid<polyacrylic acid<lactic acid<maleic acid< phosphoric acid.

• Cavity cleanser such as tubulicid and hydrogen peroxide have slight

effect
 Mandibular vs maxillary arch

• Clinically dentin adhesion more effective in maxillary arch.

• Greater difficulty in moisture control and the potentially higher tooth flexure in
lower jaw.

• Consistent use of rubber dam most effectively reduces this tooth arch
discrepancy.
ADVANTAGES OF ADHESIVE TECHNIQUES
• Minimal invasive or minimal intervention care. [Derange and Roulet
1997]
• Reduces microleakage -reduces clinical problems such as
postoperative sensitivity, recurrent caries.
• Better transmits and distributes functional stresses.
• Potential to reinforce weak tooth structure.
• Allows deteriorating restoration to be repaired and debonded
restoration to be replaced.
• Expands possibility for esthetic restorative dentistry.
 EXPANDING INDICATION FOR ADHESIVE
DENTISTRY
• Adhesive techniques with resin composites initially were used for the replacement
of carious and fractured tooth structure or for the filling of erosive and abrasive
defects.
• The modern adhesive techniques enables restorative material to be added to
tooth for correction of unaesthetic shapes, position and dimensions or shades.
• Other uses include :-
 Bonding anterior and posterior ceramic restorations such as
veneers, inlay and onlays with adhesive resins.
 Bond silver amalgam restorations
 Retain metal framework
 Bond orthodontic brackets
 Periodontal or orthodontic splints
 Treat dentin hypersensitivity
 Repair fractured amalgam, porcelain and resin
restorations
 Pit and fissure sealants
 Core build up foundation
 Bond fractured segment of anterior teeth
 Bond prefabricated and cast post
 Reinforce fragile roots internally
 Seal apical restorations used during
endodontic surgery
 HISTORY OF BONDING IN
COMPOSITE RESIN
• Experiments on bonding of acrylic resins to enamel and dentin was
started in the early 1950s in England with Dr. Osker Hagger. He
developed a monomer based on GPA-DMA (glycerophosphoric acid
dimethacrylate)(Sevriton) that was chemically cured with sulphinic
acid. This was shown in a swiss patent to bond to tooth structure.
• In the, US, Dr. Michael
Buonocore (1955)made the
second, and more important,
advance in adhesive dentistry,
by demonstrating that acid
etching of enamel led to
improve resin-enamel bond. He
knew that concentrated (85
wt%) phosphoric acid was used
in industry to pre-treat metal
surfaces prior to painting or
resin coating, thus, it was
logical for him to use 85 %
phosphoric acid for 30 s to etch
enamel followed by water
rinsing. The result of his work
was very controversial.
• Prior to the introduction of enamel acid etching, restorative
materials were placed directly on the smear layer of the
prepared tooth. It is evident that the apparent bond strength
is the cohesive strength (5-10 Mpa) of the smear layer.
• After enamel bonding proved to be a successful attempt in
clinical practice, it did not take long for the investigators to
direct their attention towards dentin as a possible substrate
for improving adhesion.
• Dentin etching did not gain wide
acceptance until Takao Fusayama
introduced the total-etch concept in
1979. For this method both enamel
and dentin are etched
simultaneously.
• In 1984 Nakabayashi describes resin infiltration of
dentin collagen to form a “hybrid “layer having
good bond strength.
• Kanka introduced dentin
wet bonding techniques - 1992
• Gradually bonding system advanced into self-etch
“all-in-one” system by the early 2000’s
 IDEAL REQUIRMENTS OF BONDING
AGENTS
• Should be biocompatible.
• Should bond effectively to both enamel and dentin .
• Should have sufficient strength to resist failure as a result of masticatory forces .
• should have mechanical properties close to tooth structure.
• Should be resistant to degradation in oral environment.
• Should be easy to use.
 COMPONENT OF BONDING SYSTEM OF
COMPOSITE RESIN
1. Etchants or conditioner
2. Primers
3. Adhesives
4. Initiators and accelerators
5. Fillers
6. Other ingredients
Etchants or conditioner
• Etchant are chemicals used to Etch enamel and dentin to make their
surface more reactive.
• Enamel and Dentin both can be etched.
• Definition of enamel conditioning: The procedure that leads to the
removal of inorganic layer, making the enamel surface more
reactive.
• Defintion of etching : the procedure that leads to demineralization
of superficial calcium ions
• Acid etching removes about 10 um of the enamel surface and
creates a microporous layer from 5-50um deep.
 Enamel Etching—
• Enamel etching transforms the smooth enamel surface into an
irregular surface with a high surface free energy(72 dynes/cm), more
than twice that of unetched enamel.
• Phosphoric acid is used in concentration of 37%.
• The etching time is 15 seconds.
• Placement done by a syringe or brush.
• Rinsing is done for 5-10 seconds with continuous water spray.
• On drying the enamel surface appears frosty and white.
• Amongst the various agents that have been used as an etchant,
phosphoric acid is the most commonly used acid at concentrations
between 30 to 50 %, with 37 % concentration being the most accepted.
Higher and lower concentration of acid is not effective.
• At concentration greater than 50% there occurs formation of a layer of
monocalcium phosphate monohydrate on etched surface which prevents
any further dissolution.
• whereas below 30% there forms a precipitate of dicalcium phosphate
dihydrate that can not be easily removed.
• Higher concentration of acid produces deeper tags , which being brittle
give way leaving 5-10 micrometer similar to as obtained with the lower
concentration of the acid.
• It is accepted that 30-40% concentration of the acid is the most effective.
• Three patterns of enamel
etching have been described:
TYPE 1
TYPE 1: removal of enamel
prism cores with prism
peripheries remaining relatively
intact
TYPE 2
TYPE 2:peripheries are
removed leaving the core intact
TYPE 3: combination of type1
and type2
TYPE 3
• Definition of dentin conditioning: Alteration of dentin surface including smear
layer with the objective of producing a substrate capable of micromechanical and
possibly chemical bonding to dental adhesives .
Physical changes after conditioning:
Removal or modification of smear layer.
Opening of dentinal tubule orifices
Chemical changes after conditioning:
Modifications in organic matter
Decalcification of inorganic portion
• Conditioning of the dentin
1. Chemicals
• Acids
• Calcium chelators
2. Thermal
Lasers
3. Mechanical:
Abrasion
The various acid etchants used are:
• Organic
Maliec acid
Tartaric acid
Citric acid
EDTA
Acidic monomers
• Polymeric
Polyacrylic acid
• Mineral acids
Phosphoric acid
Hydrochloric acid
Nitric acid
Hydrofluoric acid
• Calcium chelators:
Remove smear layer without decalcification or significant
physical changes in the underlying dentin substrate. No funnel
shaped changes are seen.
• EDTA ---pH of 7.4
• Tublicid
0.1% EDTA
0.15% Benzalkonium chloride
• Scrubbed on the surface for a few seconds, then left passively for
another 60 seconds followed by additional scrubbing.
• Smear layer removal, smear plug intact.
• Lasers:
Nd: YAG lasers used at 10-30 pulses per second. Laser etching is
the process of continuous vaporization of water trapped within the
Hydroxyapatite matrix . The lased surface is desensitized by
occlusion of open and permeable dentinal tubules.
• Air abrasion:
Aluminium oxide particles are used for air abrasion of a particle
size of 0.5 Microns
Primers
• Primers are solutions containing amphiphilic bifunctional adhesive monomer
molecules dissolved in a solvent having surface tension less than the surface
energy of the acid etched dentin.
• Monomers used are
a) HEMA (2-hydroxyethyl methacrylate)
b) NPG-GMA (N-phenyl-glycin-glycidyl methacrylate)
c) PMDM (pyromellitic dianhydride)
d) PENTA (Dipentaerythritol penta acrylate monophosphate)
e) 4-MET (4-methacryloyloxyethyl trimellitic acid)
g) 4-AETA(4-acryloyloxyethyl trimellitic anhydride )
h) MAC-10 (11-methacryloyloxy-1,1’-undecanedicarboxylic acid)
i) 10-MDP (10-methacryloyloxydecyl dihydrogen phosphate)
j) Phenyl-P

Priming is necessary to maintain an expanded collagen network

while removing residual water to allow for the infiltration of
the hydrophobic adhesive monomer.
• Such monomers exhibit hydrophilic properties through phosphate,
carboxylic acid, alcohol, or ester functional groups.
• HEMA is a widely used primer monomer because of its high
hydrophilicity and solvent like nature. It has 6.79 cps(Centiposes )
viscosity at 20°C.
• Primer mixtures have a wide PH range .
• The rank of functional groups in their acidity is as follows:
Sulphonic acid> phosphonic acid>phosphoric > carboxylic>alcohol
• Acidic primers containing carboxylic acid groups are used in self
etching bonding agents
MECHANISM OF BONDING - M-R-X concept
• M represents an unsaturated methacrylate group or groups capable of
copolymerizing with the other monomers of a resin cements or composite.
• X represents a group capable of chemically reacting with siliceous materials such
as glass and silicate filler particles in composites, and porcelain crowns and
veneers, and/or the calcium ions (Ca++) in dental hard tissues.
• R is a spacer group that provides flexibility and mobility, and thus enhanced
reactivity, for the M group after the X group has been immobilized by reaction at
a surface.
• Bonding to Inorganic part of Dentin ( M-R-X concept)
• X group may be phosphate ( in
NPG-GMA) , may be
polymerizable phosphate (e.g..
Phenyl P ,10-MDP), carboxylate
compounds (e.g.. 4-MET ,
MAC-10, 4-META)

Different types of X-group

• However in spite of theoretical evidence that chemical
bonding to tooth structure is possible, minimum
convincing experimental evidence has yet been
validated to prove that significant chemical bonding
occurs between dentin adhesives and tooth structure
under intra-oral conditions.
Solvents
• Primers and/or adhesive resins tends to have a low viscosity, which
is partly due to the dissolution of the monomers in a solvent which
improves their diffusion ability in the micro-retentive tooth surface.
• Most commonly used solvents are :
1. Ethanol
2. Water
3. Acetone
 Acetone has a high vapor pressure (184mmHg at 200 C), which is
about four times as high as that of ethanol (43.9mmHg at 200
C), is a main advantage.
However, it’s high volatility may also lead to reduce shelf-life of
acetone-containing adhesives, by rapid evaporation of the
solvent.
• Ethanol and acetone have better miscibility with relatively
hydrophobic monomers, and their “water-chasing” ability
facilitates water removal.
Adhesives
• Adhesives need to be hydrophobic so that fluid will not be allowed
to permeate through the intermediate layer.
• At the same time adhesives require a certain hydrophilicity to
defuse into the hydrophilic , primer –wetted dentin.
• Generally, adhesive resins are composed mainly of hydrophobic
dimethacrylates e.g. Bis-GMA, TEGDMA, UDMA, and a small
amount of a hydrophilic monomer such as HEMA.
• Although dimethacrylate adhesives yield strong bond strengths,
the polar ester bond inevitably absorbs water and gradually
hydrolyses.
• Since Carbamides are more hydrolytically stable than ester
groups, methacrylamides have recently been adopted to replace
methacrylates.
Initiators
• Polymerization can be initiated either through a photo initiator system consisting
of a
1. Photosensitizer ( e.g. camphoroquinone) in light cure system
2. Chemical initiator (e.g. benzoyl peroxide, acetyl peroxide, lauroyl peroxide) in
self cure system. Initiators may be about 2 wt% or less and more preferable
about 1 wt% or less
3. Dual cure initiator system.
Fillers
• The aim of filler addition to dentin adhesives are to increase the
mechanical properties and elastic modulus of adhesive, to improve
the distribution of the stresses induced by resin composite
polymerization shrinkage and occlusal loading .

• Incorporation of nanofiller particles to experimental adhesive

system increased the micro tensile bond strength to dentin layer.
• Incorporation of fillers with larger dimensions than the interfiblliar
space (15-20 nm) of the etched dentin not only increases viscosity of
the adhesive, but also might cause filler accumulation over the top
of etched dentin surface. Therefore, it might reduce the adhesive
penetration into the etched dentin and produce a defective hybrid
layer. Even in situation that nanofillers are smaller than the
interfiblliar spaces, there is some controversy as whether or not the
extremely small nanofillers used in adhesive system can penetrate
into the hybrid layer.
• According to Davidson's elastic cavity wall concept, it is expected
that the filled adhesive layer act as a shock absorber between
composite resin and dentin, and result in an increase in bond
strength of bonding system to dentin . Other studies have indicated
that no significant difference exists between filled and unfilled
bonding system.

• Marketed nanofilled DBA’s. E.g.-

Prime and bond NT (7nm fillers)
Excite (12nm fillers)
Other Ingredients
• Sometimes additional ingredients are used with dentin bonding agents for a
variety of purposes
• Glutaraldehyde –desensitizer
• 12-methacryloyloxydodecylpyridinium bromide ( MDPB) and paraben—
antimicrobials
• Fluorides—prevent secondary caries
• Benzalkonium chloride– prevent collagen degradation by prevent the action of
matrix metalloproteinase enzymes which is responsible for denaturation of hybrid
layer collagen.
Bonding to Enamel
Enamel etching transforms
the smooth enamel surface
into an irregular surface with
a high surface free energy(72
dynes/cm), more than twice
that of unetched enamel.
 An unfilled or filled liquid
acrylic(hydrophobic) resin
with low viscosity wets the
high energy surface and is
drawn into the
microporosities by capillary
attraction.
 After light curing, the bond between enamel and the restorative material is
established by polymerization of monomers inside the microporosities and by
copolymerization of remaining carbon – carbon double bonds with the matrix
phase of the resin composite, producing strong chemical bonds.
 In addition, the potential for chemical interaction between specific monomers
and the etched enamel surface cannot be excluded.
The bond strength is 15-25Mpa.
Bonding to Dentin
• Dentin Bonding Agents --
• Difunctional or multifunctional organic molecules that contain reactive group
which interacts with dentin and the monomer of the restorative resin.

The Dentin bonding agents are classified as follows:

1. Based on generations
2.Based on etching pattern
3.Based on the treatment of smear layer
ADHESION AND BONDING FOR
COMPOSITE RESINS
- Namrata Jajoo
1st Year PGT
Department of Conservative Dentistry and Endodontics
 CONTENT
• INTRODUCTION

• COMMONLY USED TERMINOLOIES

• PRINCIPES OF ADHESION

• MECHANISM OF ACTION

• FACTORS AFFECTING ADHESION

• ADVANTAGES OF ADHESIVE TECHNIQUE

• HISTORY OF BONDING IN COMPOSITE RESIN

• IDEAL REQUIRMENTS OF BONDING AGENTS

• COMPONENT OF BONDING SYSTEM OF COMPOSITE RESIN

• MECHANISM OF BONDING

• ENAMEL BONDING

• DENTIN BONDING

• BONDING AGENTS
• ON GOING RESEARCH AND ADVANCEMENT
• CONCLUSION
• CLASSIFICATION-BASED ON GENERATION ---
1. First-Generation Dentin bonding agents ( DBA)(1960)
2. Second-Generation DBA(Late 1970s)
3. Third-Generation DBA(1980s)
4. Fourth-Generation DBA(Early 1990s)
5. Fifth-Generation DBA
6. Sixth-Generation DBA
7. Seventh-Generation DBA
8. Eighth-Generation DBA
 FIRST GENERATION DENTIN BONDING AGENTS

Developed in 1960 s
The development of NPG-
GMA (N-phenyl glycin-
glycidyl methacrylate), a
surface active comonomer
was the basis of the first
commercially available
dentin bonding agent,
Cervident(SS White).
Theoretically, NPG-GMA was
supposed to chelate with the
calcium in dentin to form a
water resistant chemical bond
to dentin.
But the bond strengths
produced by this agent were
very low, only 2-3Mpa.
Carbon 13 NMR (nuclear
magnetic resonance) analysis,
shows that no ionic bonding
actually occurs. Bonding of NPG portion
Clinically, this agent did not
To Ca++ ions by chelation
successfully bond composite
resins to dentin.
 SECOND GENERATION DENTIN BONDING
AGENTS
• Developed in 1970s.
• Did not recommend dentin etching.
• Low bond strength (4–6 MPa).
• Most of these agents were phenyl phosphorus, phosphorus,
chlorophosphorus esters of unfilled resins such as BisGMA or HEMA.
• The bonding mechanism involved improved wetting of surface and
ionic interaction between the phosphate group and calcium of the
tooth.
• Examples : Clearfil bond
Scotchbond
Bondlite
Prisma Universal bond
• Clearfil is composed of an ethyl
alcohol solution containing
tertiary amine as the activator .
The catalyst liquid was BisGMA
monomer containing a phenyl
phosphate ester, benzoyl
peroxide and methyl
methacrylate.
• The interfacial bond was
established through attraction
between the negative charges
of the oxygen on the
phosphate group and the
Bonding mechanism in clearfil
positively charged calcium ions
in the dentine surface .
• Scotch bond , a halo phosphorus ester of BisGMA was introduced in
1983. This type of compound is formed by reaction between
BisGMA and phosphorus oxychloride (POCl3). Bonding to tooth
calcium occurs through chlorines having a negative charge. It may
be that the chlorophosphate group becomes rapidly hydrolyzed on
contact with moisture at dentin surface producing a reactive group
and liberating hydrochloric acid . This acid plays a part in bond
formation by altering the structure of surface dentin including the
smear layer.

Bonding mechanism in Scotchbond

Drawbacks in the first and second generation DBA

1. Lack of adequate bond strength that could overcome

contraction stresses during polymerization.
2. Being hydrophobic in nature, close adaptation to the hydrophilic
dentin could not be achieved.
3. Biocompatibility was not appropriate.
4. Lack of sufficient knowledge about the presence and nature of
smear layer. Moreover, the adhesive bonded to the smear layer
rather than the dentin . As a result the bond achieved was limited
by cohesive failure in the smear layer or a break at the smear
layer-dentin interface.
Scanning electron micrograph of the fractured edge
of smear layer-covered human dentin. Note the
presence of smear plugs occluding the orifices of
the tubules. B. Adhesive resin (blue) bonded to
smear layer (no-etch bonding systems). When
stressed to failure, the smear layer split (black gap)
indicating that it was a weakest link in teeth bonded
using the no-etch technique
 SMEAR LAYER
• According to American
Association of Endodontics
(AAE): It is defined as a surface
film of debris retained on
dentin or other tooth surface
like enamel, cementum after
instrumentation with either
rotary instruments or
endodontic files.
• It is revealed by SEM to be 0.5-
2um thick layer of debris with a
mainly granular substructure
that entirely covers the dentin.
• Early studies of dentinal walls after cavity preparation performed by
Brännström and Johnson (1974) showed the presence of a thin layer
of debris that was 2 to 5 micrometres thick.
• In 1975 McComb and Smith first described the smear layer. They
observed an amorphous layer of debris, with an irregular and
granular surface, on instrumented dentinal walls using a scanning
electron microscope.
• In 1984 Pashely described the smear layer as being composed of
two phases; an organic phase, composed of collagen residues and
glycosaminoglycans and an inorganic phase.
The burnishing action of the cutting instrument generates
frictional heat and shear forces, so that the smear layer
becomes attached to the underlying surface in a way that it is
prevented from being removed.
The orifices of dentinal tubules are obstructed by debris tags,
called as smear plugs that may enter tubule upto a depth of 1-
10um.
It is reported to reduce dentin permeability upto 86%.

Due to its small and varying dimensions and its irregular and
weak structure, studying the smear layer is rather
complicated.
It can be a detriment to effective bonding. It has an inherently
weak attachment to the underlying dentin and brittle in
nature.
• To obtain satisfactory bonding, the tooth surface should be treated
to obtain a clean bonding substrate.
Two strategies used to overcome low attachment strength of smear
layer:
1. Removal of smear layer prior to bonding.
2. Use of bonding agents that can penetrate it and incorporate it
into bonding layer.
 Removal of smear layer greatly increases the permeability of
dentinal tubules.
 After removal of smear layer with an acid, dentinal permeability
through the tubules increases more than 90%.
 Treatment of tooth surfaces to remove smear layer can induce
tooth sensitivity.
• Olgart et al. (1974) examined the penetration of bacteria into
dentinal tubules of ground, fractured and acid treated dentin
surfaces. Olgart came to a conclusion that acid produced
by microorganisms may dissolve the smear layer allowing bacteria
to pass into dentinal tubules.
• However when Pashley et al. (1981) studied the scanning electron
microscope (SEM) appearance of dentin before and after removing
successive layers of the smear layer they came to a different
conclusion. Pashley concluded that the maintenance of the smear
layer established a protective diffusion barrier.
 THIRD GENERATION DENTIN BONDING
AGENTS
• As it became evident that the smear layer had a negative influence
on the performance of adhesive systems, to overcome this , third
generation dentin bonding agents were introduced in the United
States during the late 1980s.
• These systems either modified or removed the smear layer to allow
resin penetration into the underlying dentin.
• The bond strength to dentin with these agents were usually higher
(9-15MPa) and more durable thereby reducing microleakage.

• Examples:
Scotchbond 2 (3M),
Gluma (Heraeus Kulcer Dental Products, South Bend, IN)
Tenure (Den-Mat Corporation, Santa Maria, CA)
Prisma Universal Bond 3 (Dentsply Caulk, Milford, DE)
Syntac (Ivoclar Vivadent, Amherst, NY), and
XR-Bond (Kerr)
• Shear dentin bond strengths these agents were typically greater
than those of the second-generation agents. However, their
performance was still unpredictable, even in laboratory studies.
Although these dentin adhesives were more effective than their
predecessors in reducing microleakage at dentin margins they
certainly did not eliminate marginal leakage. Clinically, these
systems provided better retention rates and marginal integrity than
earlier adhesives.
• First system of third generation was known as the oxalate bonding
system or the FNP system.
• The initial system utilized a solution of acidic ferric oxalate (2.5%
nitric acid + ferric oxalate) as a conditioner. The ferric ions are
absorbed onto the dentin to increase the number of positive ions on
the surface. This is followed by the application of an acetone
solution of NTG-GMA ( reaction product of N p-toluidine glycine
and glycidyl dimethacrylate) and then another acetone solution of
PMDM (Pyromellitic dianhydride)+ 2 HEMA. This technique gave
bond strengths of about 15MPa.
• Later researchers replaced ferric oxalate with aluminium oxalate to
eliminate the possible risk of discoloration due to ferric ions.
• Tenure was the first commercial oxalate bonding system, which
utilized phosphoric acid in conjunction with aluminium oxalate and
nitric acid as a dental conditioner.

• Mirage bond utilized conditioner of NPG (N-Phenyl glycine)+ 2.5%

nitric acid followed by application of PMDM. Dentin bond strength
achieved was 10.9 Mpa.
• In 1984 , a new bonding agent called Gluma was developed. It
utilizes o.5 M EDTA at an approximately neutral pH to remove the
smear layer and free the collagen from embedding apatite, The
second step is treatment with an aqueous solution of HEMA and
glutaraldehyde. The bonding reaction involves attack of the
aldehyde on the amino group of the collagen. The resulting complex
is able to react with the hydroxy group of methacrylate monomer
which then bond to resin.

Gluma bonding system

• Scotchbond 2 was the first to utilize a self-etching primer for conditioning the
dentin surface.
primer -- aqueous solution of 2.5% maleic acid and 58.5% HEMA.
Bonding agent—HEMA(32.5%), Bis-GMA (62.5%)
And photoinitiator
Fourth Generation DBA

• Fourth generation of dentin bonding systems appeared in the early

1990s and is still widely used. Most of these systems are based on
the "total-etch" technique, or simultaneous etching of enamel and
dentin, typically with phosphoric acid.
• Total etching and moist dentin bonding, concepts developed by
Fusayama and Nakabayashi in Japan in the 1980s, introduced to
North America by Bertollotti, and popularized by Kanca, are
innovative hallmarks of the fourth generation adhesives.
• The bonding mechanism of the fourth-generation adhesive systems
is a three-step process: (1) condition, (2) prime, and (3) bond.
Conditioning (or etching) removes the smear layer, opens the
dentinal tubules, increases dentin permeability, and decalcifies the
intertubular and peritubular dentin. Removal of hydroxyapatite
crystals leaves a collagen meshwork that can collapse and shrink
due to the loss of inorganic support.
• This generation is characterized by the process of hybridization at
the interface of the dentin and the composite. Hybridization is the
replacement of the hydroxyapatite and water in the surface dentin
with resin. This resin, in combination with the remaining collagen
fibers, constitutes the hybrid layer. Hybridization dramatically
improving bond strength to dentin.
• HYBRID LAYER ---
When primer and bonding resins are applied to etched dentin, they
penetrate the intertubular dentin, forming a resin-dentin interdiffusion
zone, or “hybrid layer”.

The ultrastructure of dentin hybrid layers was first described by Van

Meerbeek et al. and by Tay et al.. They showed that the collagen fibrils
exhibited 67 nm periodicity, took up heavy metal TEM stains and had 20 nm
interfibrillar spaces between the collagen fibrils, presumably filled with
infiltrated resin.
• This concept was given by Nakabayashi
in 1982.
 The adhesive system must have a high
surface free energy for adequate
interfacial contact. Dentin consists of
two distinct substrates, one of high-
surface energy(hydroxyapatite) and
one of low surface energy (collagen).
 Thus, after acid etching with acidic
agents, the dense web of exposed
collagen is a low-energy substrate.
 An increase in the critical surface
tension of dentin surface-active
components (such as primers) is
therefore highly desirable in such case.
• When a bonding agent is
applied, part of it penetrates
into the collagen network,
known as intertubular
penetration and the rest of it
penetrates into dentinal
tubules called intratubular
penetration.
• In intertubular penetration, it
polymerizes with primer
monomers forming a hybrid
layer/resin reinforced layer.
• Intratubular penetration causes
resin tags.
• ZONES OF HYBRID LAYER ---
1. Top layer: Consists of loosely arranged collagen
fibrils and interfibrillar spaces filled with resin.

1. Middle layer: Consists of interfibrillar spaces in

which hydroxyapatite crystals have been replaced
by resin monomer because of the hybridization
process.

1. Bottom layer: Consists of almost unaffected dentin

with a partly demineralized zone of dentin.
• Several major dental product manufacturers market fourth-
generation bonding systems that etch dentin with phosphoric or
other acids.
• Examples include
1. All-Bond 2 (Bisco, Inc., Schaumburg, IL),
2. Amalgambond (Parkell, Farmingdale, NY),
3. Clearfil Liner Bond (Kuraray/J. Morita USA, Inc., Tustin, CA),
4. EBS (ESPE America, Norristown, PA),
5. OptiBond (Kerr),
6. ProBond (Dentsply Caulk),
7. Scotchbond Multi-Purpose Plus (3M).
Fourth Generation DBA
Advantages of Fourth Generation DBA
1. Many investigators have reported shear bond strengths for these materials that
approach or exceed the typical enamel bond strength of 20 Mpa.
2. In addition, microleakage studies indicate that they provide a better marginal
seal than earlier generations of adhesives.
Drawbacks in the Fourth generation DBA

Technique sensitive , requires post conditioning rinse.

Risk of over-wetting and over-drying.

The materials in this group are distinguished by their components; there are two
or more ingredients that must be mixed, preferably in precise ratios. This is easy
enough to accomplish in the research laboratory, but rather more complicated in
chair side.
Fifth Generation Dentin Bonding Agents
• The number of mixing steps involved in Fourth Generation DBA ,the requirement for exact
component measurements tend to confuse the process and reduce the bonding strengths
to dentin. This led to the development and the great popularity of the fifth-generation
dental adhesive.
 Developed in mid 1990s.

 Uses two steps, i.e. Total etching + Application of primer and bonding agent.

 Primer + Bonding agent are available in single bottle.

 High bond strength.

 Easy to use.

 Reduced postoperative sensitivity.

• Bond strength is 20 to 25 Mpa.

• Examples are :
1. Prime & Bond
2. Opti Bond Solo
3. Single Bond
Advantages--
1. Bond strength is sufficient.
2. Post operative sensitivity is much less.
3. Some agents have incorporate fluoride and elastomeric components to
improve marginal integrity.
4. Time saving and simple to use.
Disadvantages –
Technique sensitive , requires post conditioning rinse.
Risk of over-wetting and over-drying.
Solution must be refreshed continuously and a residual smear layer
remained.
 SIXTH GENERATION DENTIN BONDING
AGENT
• Researchers have sought to eliminate the etching step, or to include it chemically
in one of the other steps. The sixth-generation adhesives require no etching, at
least at the dentinal surface.
Self-etching primer + adhesive:
• Available in two bottles:
• Primer
• Adhesive
Sixth generation dentin bonding agents are of two types
1. Type 1
2. Type 2
 Type 1–
First liquid 1( primer) applied to tooth surface followed by liquid2
( Adhesives).
Examples:
Clearfil SE Bond
AdheSE (Ivoclar Vivadent)
Type 2--
Here both the liquid mixed first then that mixture will apply to the
tooth surface.
Examples:
Xeno III
Prompt L PoP (3M)
Brush and Bond F (Parkell)
• Bond strength of sixth generation DBA is 18-23 Mpa.
• Unprepared enamel may require etching with phosphoric acid.
• solvent is water.
• Advantages –
1. No need to acid etch with phosphoric acid.
2. No post conditioning rinsing required.
3. Reduced post operative sensitivity
4. Less sensitive to degree of wetness and dryness.
5. Low technique sensitivity.
• Disadvantages –
1. Less effective bonding of enamel.
2. Initial bond might deteriorates with aging, which could lead to
premature failure.
 SEVENTH GENERATION DENTIN BONDING
AGENT
Developed in late 2000s.

All in one concept, i.e.

components available as single
component.
Uses self etch primer.

Good bond strength.

They achieve the same

objective as the sixth
generation systems except that
they simplified the multiple
sixth generation materials into
a single component, single
bottle one-step self-etch
adhesive, thus avoiding any
mistakes in mixing.
Both the sixth and seventh generation adhesives are
self etching, self priming adhesives which are
minimum technique sensitive.
The seventh generation DBAs have shown very little
or no postoperative sensitivity.
Examples are :
I-Bond
G-Bond
Xeno IV etc.
• Bond strength –
Ground Enamel-20Mpa
Deeper Dentin-18 Mpa
Surface Dentin-25 Mpa
• Advantages –
1. One-step procedure, no
mixing or rinsing the tooth
2. Less postoperative
sensitivity
3. Tolerant to moist or dry
environments
• Disadvantages –
1. Some need refrigeration
2. Decreased shelf life due to
acidic formulation
Classification of contemporary adhesive into three-step total etch, two-step total-
etch, two-step self-etch and the single-step self-etch systems. The two-step total-
etch and the single-step self-etch adhesives may be considered as simplified
adhesives in which hydrophilic resins are employed without an additional coating of
comparatively more hydrophobic resins
EIGHT GENERATION DENTIN BONDING
AGENTS
• The number of parts in adhesive systems has been reduced over the years but
performance has suffered as well. It was decided that a new system would be
developed that had the best attributes of the fourth generation and the ease of
the sixth-generation bonding systems, and that system is Eight Generation
Dentin Bonding System.
• It is also Dual cure system.
• It is very different from other generations. It consists of three
bottles: an etchant/conditioner, a primer, and a separate
hydrophobic bonding resin. In that regard, it resembles fourth-
generation materials but the etchant/conditioner is not rinsed from
the tooth. Thus, it also has characteristics of the sixth generation—
the ease of a no-rinse system but the performance of a fourth-
generation system.
• Example :
Surpass
• Eight Generation Dentin Bonding system shows a dentin bond
strength near about mid-50 MPa range according to University of
North Carolina, Tufts University, and other testing institutions.
• Classification based on the treatment of
smear layer –

1. Smear layer modifying DBA

2. Smear layer removing DBA
3. Smear layer dissolving DBA
• Smear layer modifying dentin bonding
agents ---These agents aim to modify the smear layer
and incorporate it in the bonding process. They are based
on the concept that the smear layer is a natural barrier to
the pulp, preventing bacterial penetration and reducing
the outflow of dentinal fluid that can affect bonding.
• Clinically, they require a separate step
selectively etch the enamel using 37% phosphoric acid,
taking care not to flow the etchant onto dentin. This is
washed away and dried after which a one step
primer/adhesive combination or a separate primer and
adhesive are applied. The primers are weakly acidic
causing only weak interaction with superficial dentin
without removing the smear plugs. The adhesives consist
of monomers that exhibit good wetting and infiltration
into the smear layer. On polymerization, they form a
micromechanical bonding between the modified smear
layer and the underlying dentin. E.g.. Pro bond, Prime
and Bond 2.1. etc.
• Smear layer removing dentin bonding
agents –
• These agents are used after the smear layer is completely removed using the
total etch technique. They bond to dentin micromechanically by formation of
resin tags and hybrid layer. Here, the enamel and dentin are simultaneously
etched using either 37% phosphoric acid or other acids. Following this step, the
etchant is washed away and the tooth surface is gently dried to keep the
dentin surface moist. Next, the primer and adhesive resin are applied either as
two separate steps or as one step when they are combined in one bottle.
• Accordingly these agents are sub classified as:
 3 step dentin bonding agents:
Etching.
Priming.
Bonding.
e.g.: Scotch bond Multipurpose, All Bond 2,Amalgam Bond Plus
 2 step dentin bonding agents:
Etching.
Priming and bonding.
e.g. Prime & Bond , Opti Bond Solo , Single Bond
• Smear layer dissolving dentin bonding
agents --
• These agents partially demineralize the smear layer and
superficial dentin without removing the dissolved smear
layer or smear plugs. They simultaneously penetrate to
the depth of the demineralized dentin with monomers
that polymerize in situ.
• They are also known as “self etching
primers” and “self etching adhesives”. Here, both the
enamel and dentin are simultaneously etched and primed
by acidic primers. Following this, there is no washing
step; rather the primer is air thinned. Next the adhesive is
applied and cured.
e.g.– Clearfil SE Bond, Adper Prompt, Prompt – L- Pop.
• Classification based on etching pattern –
1. No etch adhesive
2. Total etch adhesive( etch & rinse adhesive)
3. Self etch adhesive

1) No etch adhesive—
First and second generation Dentin bonding system are called No-
etch system as etching step is absent.
Lack of adequate bond strength that could overcome shrinkage
stresses during polymerization.
Being hydrophobic in nature, close adaptation to the hydrophilic
dentin could not be achieved.
2) Total-etch Adhesive (etch-rinse Adhesive) –
• Total etching is the simultaneous etching of
enamel and dentin.
• Advocated by Fusayama in Japan (1979).
• 3 step Total etching –
Example Fourth generation DBA
2 Step Total etching –
Example: Fifth generation DBA
• Advantages of Total–etch system –
1. Bonding to enamel is good
2. There is possibility of particle filled adhesives.
3. Most efficient and consistent results.

• Disadvantages of Total–etch system –

1. Technique sensitive , requires post conditioning rinse.
2. Risk of over-wetting and over-drying.
3. Over etching phenomenon leading to nanoleakage.
4. High degree of post operative sensitivity.
• over-drying and over-wetting --
• Over-drying---
If the residual water in between collagen fibril is
evaporated by air-drying, the collagen fibril
network collapses into a relatively impermeable
organic film that interferes with resin-
infiltration1. Resin tags could still be formed, and
gave some resin retention, but hybridization of
the dentin between tubules (i.e. intertubular
dentin) could not occur. This left much naked
collagen fibrils in the acid-etched layer that could
slowly hydrolyze and lead to gap formation
between resin and dentin.
Schematic showing that smear layers are made up of microscopic cutting debris
burnished on dentin (left side). Total-etching not only removes the smear layer, it also
removes all of the mineral from around collagen fibrils in the matrix. After rinsing, the
spaghetti-like collagen fibrils are suspended in water. If the surface is dried, the fibrils
collapse upon themselves decreasing the size of interfibrillar spaces that are necessary for
resin uptake (modified from Pashley et al.5). The water used in wet bonding or in primers
re-expands the collapsed matrix when the total-etch techniques is coupled with wet
bonding preparing it for resin uptake courtesy of Dr. Franklin Tay, University of Hong
Kong, with permission.
• Ineffective penetration
due to collagen collapse
has been observed ultra
morphologically as a
formation of a so called
Hybridoid zone . These
hybridoid zone inside
the hybrid layer do not
appear electron dense
on demineralized TEM
sections. surface (Hs) and a basal (Hb) hybrid layer
sandwiching a middle, collapsed
"hybridoid region' (H)
• Over- wetting --
• Kanca discovered that if one left some residual
water in acid-etched dentin, bond strengths
could be doubled. Similar observations were
made independently in Japan by Sugizaki.
• Careful scanning electron microscopy by
Gwinnett1 revealed that wet bonding created
thicker hybrid layers (i.e. more resin uptake
into etched surfaces) than did dry bonding.
• However, the ability of acetone or ethanol to
“chase” water out of the wet collagen fibril
meshwork is often incomplete. The water
often diffuses into the organic solvents so fast
that the monomers can no longer remain
dissolved in the solvents. They undergo phase
changes that can lead to low bond strengths
due to the formation of resin globules and
poor resin tag formation, often permitting
postoperative sensitivity.
• There are no simple answers to the question of how much is “too
wet” or “too dry”. Thus, total-etch products have become known as
“technique-sensitive” products. When used in the laboratory on flat
dentin surfaces, one can obtain a relatively uniform surface
“wetness.” Clinically, however, there is a tendency to over-dry the
pulpal or axial wall of complex cavities and to pool too much water
at axio-gingival line angles, leaving the dentin surface with very
non-uniform degree of wetness and non-uniform resin infiltration.
The gingival floor of proximal boxes is often too wet to achieve
perfect bonding, leading to microleakage and sensitivity in those
areas.
• This is one of the major disadvantage of Total-etch system.
• Self-etching Adhesive-
• Based on the use of non rinse acidic monomers that simultaneously
condition and prime dentin and enamel.
• Concentration of acidic monomers from 5-10% wt to 30-40% wt
• Acidic monomers were dissolved in 30-40% wt HEMA.
• 2 step self adhesives-
e.g. Sixth generation DBA
• 1 step self adhesives DBA
e.g. Seventh generation DBA
• Depending on etching aggressiveness, the self-etch
systems are divided into
• “strong” (pH<1)
• “intermediately strong” (pH≈1.5),
• “mild” (pH≈2) and
• “ultra-mild” (pH≥2.5)
• At enamel, “strong” self-etching shows good
bonding performance , while the bonding
effectiveness of “mild” self-etching on enamel is not
efficient and can be improved by prior phosphoric
acid etching .
• On the other hand, at dentin,
• “strong self-etching” dissolves nearly all smear layer,
but does not remove the dissolved calcium
phosphates. These embedded calcium phosphates
seem to have low hydrolytic stability, with non-stable
chemical interaction with the exposed collagen,
thereby weakening the interfacial integrity,
especially in a long-term .

• “Intermediately strong” self-etching shows a

transition between “strong” and “mild” etching
characteristics of the hybrid layer formation. It has
typically a hybrid layer with demineralized top layer
and partially demineralized base.
• “Mild” self-etching partially removes the
smear layer, forming a thin hybrid layer . It has
the great advantage of leaving substantial
amount of hydroxyapatite-crystals around
collagen fibrils, which may establish chemical
bond with specific carboxylic or phosphate
groups of functional monomers .
• The ‘ultramild’ self-etching can only expose
superficially dentin collagen, producing a
nanometer interaction zone.
• Advantages –
1. Fast and easy to use
2. Acid Base Resistance Zone (ABRZ)formation

• Disadvantages –
1. Water tree phenomenon.
2. Lack of polymerization
3. May not bond durably to enamel.
4. Can increase MMP-2 (Matrix Metalo-protienase) synthesis in human
odontoblasts, possibly increasing MMP-2 penetration into the
hybrid layer via dentinal fluid.
•Water -tree phenomenon –
• The one of the problem with all-in-one
adhesives is that even if they are thick enough
to polymerize, their composition is very acidic
and very hydrophilic. That is, they attract and
absorb water, leading to leaching of
unpolymerized monomers or hydrolytic
degradation products through water-filled
channels called water-trees .
• The presence of water-filled voids and
channels are disclosed by soaking bonded
specimens in silver nitrate solutions. The filler
diffuses into the waterfilled spaces. Once
reduced, it forms black silver deposits. These
channels pass from the hybrid layers, through
the adhesives to the adhesive-composites
interface. Adhesive systems that form water-
trees tend to have lower bond strengths to
dental hard tissues, and are less durable.
Transmission electron micrographs of dentin bonded with an all-in-one adhesive, then
placed in 37ºC water for 24 hrs prior to soaking in silver nitrate to demonstrate the
presence of water-filled (now silver-filled) channels called “water trees” (finger-pointers)
extending from the hybrid layer (H) and passing through the cured adhesive layer. The
black silver deposits indicate where there were water-filled channels. Such water trees
do not form in self-etching primer adhesives23. Courtesy of Dr. Franklin Tay, University of
Hong Kong, with permission
Bonding to Cementum
• Very limited information exists on cementum-bonded restorations. Ferrari et al.
reported that cementum treated with dentin bonding systems is infiltrated by the
resin, but the predictability of the bond is unclear. Van Dijken et al. found excellent
adaptation in the cervical margins located below the cemento-enamel junction
with the directed shrinkage technique; however, in vitro measurements evaluating
similar restorative techniques have shown moderate to severe leakage in
cementum, with almost no leakage in enamel.
• the arrangement of collagen fibers in cementum is much more
irregular than dentin which restrict the proper infiltration of
monomer into etched cementum, which compromises the bond
strength.
• Bond strength to cementum is 0-35 Mpa
• According to Okada H et al (2009) – the Micro shear bond strength
to cementum are :
26.7 Mpa – Clearfil Tri S Bond
22.4 Mpa – G-Bond
35 Mpa – Clearfil AL
32.5 Mpa – Adper Single Bond
why resin-dentin bond strengths fell over time ?

According to modern concept it is mainly due to

Nanoleakage
• There are three main reasons for nanoleakage
1. Hydrolysis of monomer
2. Gap between collagen fibril and monomer
3. Collagen degradation by proteolytic enzymes

1) Hydrolysis of monomer --Most of the monomers used in primer

are hydrolytically unstable , thereby producing nanoleakage.
2) Gap between collagen fibril and monomer --
• Hydration of collagen prior to the monomer
penetration
• The inter-molecular distance in the lateral packing of collagen
molecules within a collagen fibril (the space supposed to be
occupied by monomer molecules) is within range of 1.26 nm to 1.33
nm. Since even the adhesive monomers (such as TEGDMA) units are
approximately 2 nm in diameter, the complete infiltration of the
adhesive material even at single monomer molecular level is
restricted by the space available within a collagen fibril .
• According to Spencer and Wang et al ,as adhesive comonomers
diffuse into the water around collagen fibrils, their relatively high
chemical concentrations (2–4 moles/L) lower the vapor pressure of
water (Raoult’s law) making it more difficult to evaporate residual
water using a dental air syringe .
• Toroian et al. found that molecules less than 6 kDa easily diffuse
between collagen molecules and entered “collagen water”, while
molecules larger than 40 kDa were excluded from “collagen water”.
• Toroian et al. conclude that hydrated collagen molecules function
as if their intermolecular size is significantly larger than 1.8 nm due
molecular vibration/rotation. The results support the hypothesis
“that individual collagen molecules have substantial freedom to
move in the lateral plane of the fibril”.
• Complete coverage of the nanoscale irregularities on the collagen
fibrils surface via passive monomer penetration may be difficult to
achieve. These irregularities are caused by the 4 to 6 nm height
difference between the fibril gap and overlap zones, and
nanometer-scale microfibrils at the surface of dentin collagen fibrils
. Microfibrils, detected with X-ray diffraction, are discontinuous 5-
mer repeats of collagen molecules with 4 to5 nm diameters.
3) Collagen degradation by proteolytic enzymes-
• In 2003, Hashimoto and co-workers demonstrated
the degradation of acid-etched dentin collagen in
water storage for 500 days in vitro.
• Pashley and co-workers demonstrated that dentin
demineralized by acid etching slowly degrades in the
absence of bacteria . Collagen matrices incubated in
artificial saliva were almost completely degraded
within 250 days..
• Dayan et al. also supports enzymatic degradation of
dentin collagen.
• Pashley et al. clearly demonstrated the time-related collagen
destruction with TEM , quantitative techniques which include
measuring the release of hydroxyproline (HYP) in the media or C-
terminal telopeptides into incubation medium.
• Armstrong and co-workers were the first to carefully examine such
hybrid layers in resin-bonded dentin that had been stored in water
for 5 years. Their TEMs revealed that almost 70% of the collagen
fibrils had disappeared. They had a “ghost-like” appearance(called
Ghost Hybrid Layer). The other 30% of the hybrid layers appeared
to be normal in TEM appearance with 67 nm cross-striations that
stained well with heavy metals.
• Many experimental setup clearly revealed a specific gelatinolytic
activities of the dentin bonding system/dentin powder mixtures, but
they did not clarify which type of endogenous enzymes (MMPs,
cathepsins or others) were involved in the degradation process.
• The intense enzymatic activity reported along the dentinal tubules
also supports the hypothesis shown by Lehmann et al. that a SE
adhesive can increase MMP-2 synthesis in human odontoblasts,
possibly increasing MMP-2 penetration into the hybrid layer via
dentinal fluid.
• Similarly Orsini et al. showed that unreacted monomers eluted
from polymerized adhesives are capable of inducing human pulp
fibroblasts to overexpress MMP-2.
Still today, nanoleakge can
not be prevented
On going research and advancement
1) Prevention of collagen degradation in
Hybrid layer -- Matrix metalloproteinases and cysteine
cathepsins in mineralized dentin and dentinal fluid have been
shown to contribute the enzymatic degradation of the composite
adhesive hybrid layer collagenous matrix.
• This, in turn, has already led to several experimental strategies
that aim to improve the durability of the resin-dentin bond
strength by inhibiting the enzymatic degradation of collagen in
the hybrid layer. Even though work remains to be done.
2)Removal of collagen in demineralized dentin ---
Modification of intact dentin/cementum surfaces to improve
adhesion may include a deproteination step, prior to any adhesive
treatment, in order to remove the high organic content and expose
the inorganic substrate, like conditioning with aqueous solutions of
sodium hypochlorite (NaOCl).
• NaOCl is a well-known, non-specific proteolytic agent that
demonstrates effective removal of organic constituents from
biological materials at room temperature.
• According to Xiong et al. Int Chin J Dent -- The proteolytic action of
NaOCl involves extensive fragmentation of long peptide chains and
formation of n-chloramines with terminal amine groups that may
form other byproducts, including inter- and intramolecular
crosslinks via Schiff base formation. NaOCl has been advocated as
an intermediate conditioning treatment of acid- demineralized
dentin, in order to remove exposed collagen and produce protein-
depleted channels into subsurface intact dentin for resin diffusion,
thus creating the so-called reverse hybrid layer.
• But as NaOCl having toxicity to
tissues, it is controversial to use
NaOCl. Scanning electron micrograph of the
acid-etched dentin surface after
• Research is going on to invent new treatment with 10% sodium
proteolytic agents that can improve hypochlorite
the bond strength. (e.g. : Bromelain
enzyme)

Scanning electron micrograph of

the acid-etched dentin surface after
treatment with bromelain enzyme
3)Increase the Hydrophilicity of collagen
It was found that a short plasma treatment
could change the chemical structure of the
exposed collagen fibrils and increase the
dentin surface hydrophilicity, which allowed
better adhesive penetration into dental
collagen fibrils and enhance the bonding
strength at adhesive/dentin interface.
• According to Dong et al.01 August
2014 The treatment of dentin using
non-thermal plasma brush has
provided about 60 % stronger
adhesive/dentin interface bonding
than their untreated control.
• The active species in argon plasmas can react with
the treated surface and thus modify the surface
chemistry and properties without affecting the bulk
material properties . It has been reported that, after
treated with argon plasma,
1. the water contact angle of collagen surface was
significantly decreased.
2. the hydrophilicity of the dentin surface was
increased due to an increased number of
carbonyl groups, that were found on the surface.
• After argon plasma treatment, Surface hydrophilicity increase will
improve the penetration of hydrophilic monomer components (e.g.
HEMA) of dental adhesive.

• Another reason for enhancing the adhesive/dentin bonding

strength is that plasma treatment could introduce activated sites,
such as free radicals or peroxides, to the dentin surface, which
would initiate polymerization (in between collagen fibrils and dentin
tubules) of adhesive monomers and graft resin onto the collagen
fibrils through covalent chemical bonding.
CONCLUSION
• To satisfy the growing esthetic demands of today’s dental patients, improvements
in materials and procedures have been made to make it possible 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. 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. Apparently, the future has a sound
background in the past.
References
• Phillip’s Science of DENTAL MATERIALS
• “Textbook of Operative Dentistry" - Dr. Vimal K Sikri
• Craig's Restorative Dental Materials
• The evolution of Dentin Bonding from no etch to total etch to self etch---
David H. Pashley
• Self-Etch Adhesive Systems:
• A Literature Review-- Marcelo Giannini1, Patricia Makishi2, Ana Paula
Almeida Ayres2--- Brazilian Dental Journal (2015) 26(1): 3-10
• The dynamic behavior of a liquid ethanol–water mixture: a perspective
from quantum chemical topology Sol M. Mejía,a Matthew J. L.
Mills,bc Majeed S. Shaik,bc Fanor Mondragona and Paul L. A. Popelier
bc Show Affiliations Phys. Chem. Chem. Phys., 2011,13, 7821-7833.
• ORIGINAL ARTICLEYear : 2013 | Volume : 4 | Issue : 4 | Page : 421-426 A
new concept in hybridization: Bromelain enzyme for deproteinizing
dentin before application of adhesive system- Raad Niama
Dayem, Mona Adnan Tameesh
• Dental Hard Tissues and Bonding– Interfacial Phenomena and
Related Properties---G. Eliades , D.C. Watts , T. Eliades Eds.
• Effect of Operator-specific Handling on Tooth-composite
Interface and Microleakage Formation -- H Schneider • I Busch •
M Busch H Jentsch • M Häfer -- Operative Dentistry, 2009, 34-2,
200-210
• Bonding to Dentin: Smear Layer and the Process of
Hybridization --K.Van Landuyt, J.De Munck, E. Coutinho, M.
Peumans,P. Lambrechts, B.Van Meerbeek.
• Enamel and Dentin Adhesion – dr.dong @ tmu. Edu. tw
• Bonding to enamel and Dentin: A brief history and state of art ,1995
– Edward. J. Swift. Jr. / Jorge Perdigao / Harald O. Heymann.
• Resin Permeation into Acid-conditioned, Moist, and Dry Dentin: A
Paradigm using Water-free Adhesive Primers-- F.R. Tay, A.J.
Gwinnett2*, K.M. Pang', and S.H.Y. Wei
• Its All About Bonding--Annil Dhingra, Amteshwar Singh -10.5005/jp-
journals-10039-1048
• “Bonding”: Foundation of Dentistry--Gupta N., Kathuria N., Gulati
M., Mehta L. K.
• Optimizing dentin bond durability: control of collagen degradation
by matrix metalloproteinases and cysteine cathepsins --- Leo
Tjäderhane,*, Fabio D. Nascimento, Lorenzo Breschi, Annalisa
Mazzoni, Ivarne L.S. Tersariol, Saulo Geraldeli, Arzu Tezvergil-
Mutluay, Marcela R. Carrilho, Ricardo M. Carvalho, Franklin R. Tay,
and David H. Pashley
• Micro shear bond strength of current one step adhesives to cementum and dentin
– Okada H , Sod r A, Shimada Y, Togani J.– Am J. Dent –2009 Oct 22(5):259-63
THANK YOU