Copy of dentin bonding agents1/ rotary endodontic courses by indian dental academy

DENTIN BONDING AGENTS
1. INTRODUCTION
2. HISTORY
3. ENAMEL
4. DENTIN
5. ADHESION
6. REQUIREMENTS
7. PROBLEMS IN BONDING
8. CLASSIFICATION
9. SMEAR LAYER
10. HYBRID LAYER
11. CONDITIONING
12. PRIMERS
13. ADHESIVES
14. AMALGAM BONDING
15. BIOCOMPATIBILITY
16. CLINICAL FACTORS AFFECTING ADHESION
INTRODUCTION
DENTINE BONDING AGENTS Introduction: It has rightly been said, that the only thing that remains constant in
this world is change. Since the advent of time, and particularly since the dawn of the 20th century, man has been faced
with the opportunity to change and improve upon pre-existing ideas and inventions in order to progress and evolve.
The field of Dental Materials has not been exempt from this challenge, and this is best reflected by the evolution seen
in Dentine Bonding Agents. However, change for its own sake is unwise and unnecessary. Is it prudent to tamper with
a current system if it functions adequately? In order to answer this question, we must first have a sound understanding
of where we stand in the field of Dentine Bonding Agents today. How we determine improvement depends on our
perception of it. In today’s times, the objectives of restorative dentistry are vastly different from those of yesteryear and
we are called to challenge the pre-existing paradigm and make way for a new one. Earlier performance standards were
based on the concept of longevity: the longer the restoration lasts, the fewer the number of times the tooth will require
a change of restoration. Therefore, pursuing a material whose chief function is to effectively withstand the rigors of
the oral environment has long held our attention. The materials commonly used for restorative purpose in order to
achieve this end were amalgam, gold foil and cast restorations. However, changing times have also meant a change in
objective: Increasing public awareness of tooth-colored restorations has led to a rising demand for more esthetic,
biocompatible materials such as composites, glass ionomer cements and porcelain. Of all the innovative materials
available today, the direct placement of resin composites has assumed its place as the current technique of choice in
restorative dentistry. One of its principal advantages is its bondability to enamel and dentin, which has been made
possible by the use of Dentine Bonding Agents. The advent of Dentine Bonding Agents, with its property of adherence
to the tooth structure by both micro-mechanical and chemical means, has heralded a new era in the field of dentistry
owing to. The formulation of this path-breaking material has been attributed to momentous contributions by great
scientists like MICHAEL BUONOCORE, RAFEL BOWEN, NUBO NAKABAYASHI and FUSYAMA. Recent
improvements in adhesive systems have generated a revolution in dentistry, placing adhesive restorations on the front
stage. Clinicians have had to rise to the challenge of confronting this continuous and rapid change. There has also
been a surge in the development of more refined and diverse restorative materials. These materials along with the
new, improved bonding agents have left the clinician spoilt for choice and he is faced with the daunting aspect of
determining which offers the most advantages. This Library dissertation discusses Dentin Bonding Agents, with a
complete coverage of bonding systems with the hope that it will contribute to a better understanding of these systems
and thus empower dental professionals with the ability to make more effective treatment and material choices.
Acknowledgement: Several people have contributed towards the inception, compilation and final completion of this
library dissertation and I would like to take this opportunity to gratefully acknowledge them all. Firstly, I extend
heartfelt thanks to Dr. Baskar Rao, Principal of S.D.M. College of Dental Sciences and Hospital, for providing us not
only with excellent facilities but also with his help at all times. I am extremely grateful to Dr. Nageshwar Rao, Head of
Department of Conservative Dentistry, S.D.M. College of Dental Sciences and Hospital and my mentor for his
unwavering support, guidance and invaluable suggestions which have been instrumental in the successful completion
of this dissertation. I would also like to sincerely thank all the other members of the staff of the Department of
Conservative Dentistry for their timely help and advice. I am grateful to Mr. Javale, (Neha, put his college designation
here.. statistician, I think) for helping me with the monumental task of typing this manuscript. My sincere thanks to
my parents and my sister, for being a constant source of love and encouragement without which I would not be where I
am today. Lastly, but definitely not the least, I am grateful to my friends (Neha, their names come here) for their help,
support and inspiration.
As we more through time, we are continuously faced with the opportunity to change this is true for our restorative

materials, as it is for anything else. In order to know whether or not we should change, we must have an
understanding of where we are currently. If the change mill not precede improvement is it mice to presence.
How we determine improvement depends on our paradigm, our new of the objectives of restorative dentistry
traditionally, dentists have as much as possible is the ideal permit we have in the time that challenges that paradigm.
The earlier performance standard is rendered on the concept of longevity. The longer the restoration lasts,
the fever the number of times a tooth mill require restoration in a lifetime. Therefore, pursuing a material that will
withstand the rigors of oral environment has long held our attention.
The materials commonly used for restorative purpose are amalgam, gold foil and cast restorations in ‘colour’.
Increasing environmental consumes and public awareness for tooth colored materials have heralded patients to
demand more esthetic, biocompatible materials such as rempasites glass inomer cements and porcelain.
Of all the innovative esthetic materials available today, the direct placement of rein composite has assumed
the cement thrust in restorative dentistry one of the principle advantages in the use of these resin composites is the
hondalility to the enamel and dentin; which has been possible due to mostly improved bonding systems.
Dentin bonding agents have created a new in the field of dentistry, owing to its property of adherence to the
tooth structure by both micromechanical and chemical means. This momentous change like Michal Buroocore, Rafel
Bomen, Nubo Nakahayashi, Fusyama.
Recent improvement in adhesive systems have generated a revolution in dentistry, placing adhesive
restorations on the front stage clinicians have been confornt4d with this continuous and rapid turnover is adhesive
materials. These has been an angering process in developing more refined and diversified restorative materials along
with the production of steadily improving bonding agents creating confusion as to which and is letter.
This library dissertation discuses dentin bonding agents, with complete coverage of the bonding systems,
hoping that this would help dental professionals better in understanding bonding systems.
HISTORY
Dentin Bonding Agents have developed over several decades. The various historical events, with took place
have led to our present day DBA.
1938 -Development of epoxy molecule by Castan
1951 -Development of glyecrophosphoric acid dimethacrylate molecule by Dr.Oscar Hagger. This molecule
permitted resin adhesion to dentin.
1952 -Usage of glyrerophosphoric acid dimethacrylate by Kramer and Mclean (earliest description of hybrid layer)
1955 -Buonocore introduces etching of teeth any phosphoric acid; he found that an acrylic resin; bonds well with
etched enamel.
1956 -Buonocore pioneers the work on adhesion to dentin. Initial dentin bonding agent’s developed were lased on
the glycerophosphoric acid dimethacrylate molecule and bonds to hydrochloric acid etched dentinal surfaces, but bond
strength diminishes greatly on immersion in mater.
1957 -Bowen starts work on bio-phenol glycidyl methacrylate (BIS-GMA) resin systems.
1962 -Bowen conducts first workshop dental materials.
1965 -Causton describes how primers work.
1982 -Bowen, Cobb, Rapson develops the multilayer adhesive system.
1982 -Nakabayashi reports the presence of hybrid layer.
1987 -Fusayama described the concept of total etching and boning.
1997 -Ferrari et al established the bonding mechanism of one bottle adhesive system to conditioned dentin.
2000 -Evaluation of bonding ability of the sixth generation bonding systems done by Ferrari et al.
2003 -Seventh generation by Ferrari et al.

ENAMEL
Enamel is the hardest of the mineralized tissues of the body. It coves the anatomical crown of the tooth. This
tissue is very brittle in nature but protects the underlying structure, i.e. dentin and pulp.
The inorganic component of enamel is principally appetite it its, hydroxy, fluoro carbonate forms. Calcium and
phosphate are the two major inorganic elements (Brudevold, Steadman and Smith 1960). Minor variations occurs is
composition in which aluminum, barium, magnesium, strontium, radium and vanadium among others can be found in
the lattice.
Crystallites are embedded is an organic matrix with comprises less than 1% of the volume of mature enamel (Estoe,
1963). Less than one half of the organic component contains protein; high glutamic acid with significant amount of
proliferation and glucose (Deutch&Pe’er,1982). During mineralization of the crown, a significant shift occurs in the
value of organic material. The ameloblasts produce large amounts of organic matrix among early phases of enamel
development, then as crown saturation proceeds, the volume of organic matrix decreases while the volume of
inorganic material increases. A mineralization gradient (Crabb and Darling 1960) exists in mature enamel, thus the
outer portion of enamel is relatively more mineralized than the inner portions.
Water exists in enamel in a significantly larger amount (up to 4% by value). About 25% of water is loosely bound to
the crystallites.
A dynamic gradient involving fluid exists between the pulp and oral environment (Bergman 1963) in which enamel
participates through its porous permeable structures,but enamel is selectively permeable (Darling and Others, 1961)
allowing the passage of water and ions but excluding large molecules (Poole, Tachy and Berry, 1963).
Histochemical studies have shown the complex nature of the surface integument. This fully reacted low energy
surface confers significance in the bonding equations, as does the traumatically or operatively imposed tissue. An
understanding of the micro-morphological properties have been significant is remaining interactions between enamel
and bonding agents.
DENTIN
Dentin forms the largest portion of the tooth structure. It is covered by the enamel and cementum on the
outer surface andinternally it forms the walls of the pulp cavity.
The dentin comprises of dentinal tubulle that are small canals that extend across the entire width of dentin, from
dentinoenamel junction(DEJ) or dentinocemental junction(DCJ) to the pulp. Each tubule contains cytoplasmic cell
process (Tomes Fiber) of an odontoblast. Each dentinal tubule is lined with a layer of peri tubular dentin that is much
more mineralized than the surrounding intertubular dentin. The number of tubules increases from DEJ (15000-
20000/mm2) to the pulp (45000-65000/mm2). The dentinal tubules are fiiled with dentinal fluid which makes it
difficult to bond.
The chemical composition of dentin comprises of 75% inorganic, 20% , 5% H2O and other minerals. It is less
mineralized than enamel but more mineralized than cementum or bone. As age advances there is a structural change
in dentin. The mineral content of dentin increases with age. This mineral phase is composed primarily of
hydroxyapetite crystallites. The organic phase is primarily collagen (Type I with traces of type IV collagen).
They consist of carboxy, amino, hydroxyl surface groups. The other non-collagenus constituents that can be found are
dentin phospho-protein, sialoproteins and osteocalcins.
Dentin permeability is highly variable. Variation in permeability may arise from tubular irregularities

associated with mineral deposits, organic components of the odontoblastsic pocesses. An outward flow of dentinal
fluid occurs because of a small but positive pulpal pressure (10-15 mm Hg).The permeability characteristics of dentin
are of crucial importance in dentin bonding because most of the current bonding systems rely on resin penetration or
infiltration into dentin(Transdentinal Permeation).Resin penetrates into tubules to form tags that can contribute to
resin adhesion.More important factor is permeation of resin into intertubular dentin (Intradentinal permeation).
Dentinal permeability is reduced with age and also in caries affected dentin as the lumina becomes narrow/may get
obliterated by deposition of intratubular crystals and apposition of irregular sclerotic or reparative dentin.
Adhesion
Adhesion is defined by the “American society for testing and materials as “A substrate capable of holding material
together”. The word adhesion is derived from the Latin word adherer, which means ad-to and hearer- to stick.
Adhesion refers to the attraction between the atoms and molecules at the contacting surface of different materials (De
Brayer et al 1951, Wake 1982).
In adhesive terminology adhesion or bonding is the attachment of one substrate to another. The surface of the
substrate that is adhered to is termed as adherent. The adhesive or bonding agent may be defined as the material that
when applied to the surface of the substrate can join them together, resist separation and transmit loads across the
bond.
An important requirement for any of these interphase phenomenons to take place is that two materials being
joined must be sufficiently in close and intimate contact and besides this sufficient wetting only occurs if its surface
energy of adhesive is less than the surface energy of the adherent. If the adhesive had a high surface tension, then it
would roll up into a droplet and which will prevent adhesion.
Based on this theory of wetting and surface free energies, adhesion to enamel is much easier to achieve than adhesion
to dentin. This is because enamel is primarily made up of hydroxyapetite which has a high surface free energy
whereas dentin has a low surface free energy because it is compared of two distinct material hydroxyapetite and
collagen.Hence,wetting is easy for enamel than for dentin.
In the oral cavity, the tooth surface is normally covered by a pellicle. This salivary pellicle is organic in nature and
has a low critical surface tension that impairs adequate adhesion. Moreover,instrumentation of the tooth substrate
during tooth preparation produces a smear layer which has a low surface free energy. Hence, the natural tooth surface
should be thoroughly cleaned and penetrated prior to bonding procedures to increase the surface free energy.
Types of Adhesion
Van Noort in 1994 suggested that one or more of the following of mechanism can create an adhesive bond:
1. Mechanical Adhesion
Here, retention is by the interlocking of one phase into surface of another. This type of adhesion can be due to
a. Geometrical effects
These are caused by microscopic porosity or roughness of the surface, i.e. mechanical locking provided by undercuts,
grooves etc.
b. Rheological effects
This is caused by flow of materials in both liquid and semisolid phase
Mechanical adhesion also referred to as micro-mechanical adhesion results from the presence of surface
irregularities that give rise to microscopic undercuts. The liquid adhesive can penetrate these undercuts and once set
is locked in them. A prerequisite for this form of adhesion is that the adhesive can readily adapt to the surface of the
substrate.The adaptation is determined by the wettability of the adhesive on the substrate, the ideal situation being that
of perfect wetting when the adhesive spreads spontaneously over the surface. The degree of penetration of the
adhesive may also depend on the pressure used during application of the adhesive that helps to force the adhesive into
surface irregularities.
II. Physical Adhesion
When the two surfaces come in close proximity to one another, secondary forces of attraction can be generated through

dipole-dipole interactions. The polar reaction occurs as a result of attractive forces between the positive and negative
charges on the molecules. The magnitude of the interaction energy is dependant on the mutual alignment of the
dipoles.
This type of bonding is a rapid and reversible process because the molecules remain chemically intact on the surface.
Therefore, this weak physical adsorption is also easily overcome by thermal energy and is not suitable if a permanent
bond is desired. It follows that non-polar liquids will not readily bond to polar solids and vice-verse,because there is
no interaction between the two substances at the molecular level even if there is good adaptation. A familiar example
of this problem is the inability of hydrophobic silicone rubber impression materials to adapt to the hydrophilic moist
surfaces of the soft tissue (This problem is overcome by the use of surfactant).
III. Chemical Adhesion
If an absorbed molecule dissociates on contact with a surface and constituents alone rearranges themselves in
such a way that as for covalent, a strong adhesive bond can result. This form of adhesion is called as chemisorption.
The feature that distinguishes the chemical bond from the physical type of interaction described previously is that a
chemical reaction takes place between the molecules and the surface molecules of the substrate. Adhesives must be
strongly attracted chemically to the surface of application to form strong bond and require identical reactive groups on
both surface.
IV Adhesion through molecular entanglement
So far it has been assumed that there is a distant surface between the adhesive and the substrate. In effect, the
adhesive as adsorbed on the surface and can the be considered surface active. If the substrate is permissive the
adhesive is able to penetrate through the surface of the substrate and absorb into rather than adsorb onto the substrate.
If the absorbing molecule is a long chain molecule or better still forms polymers in the pretreated layer, the resultant
enlargement between the adhesive and the substrate is capable of producing very high bond strength.
This approach is being adopted for resin bonding system.
CHEMISTRY OF ADHESIVE SYSTEMS
Dentin bonding systems contain monomers that have hydrophilic and hydrophobic groups these provide a
stable link with the dentin and the restoration.
The chemistry of adhesive agents can be explained as.
Adhesion based on ionic polymers
Adhesion by coupling agents
Adhesion by grafting reaction
TYPES OF Chemical adhesion
There are two types of chemical adhesion
Primary Valence Forces
Covalent Bonds
Co-ordinative Bonds
Ionic Bonds
Secondary Valence Forces
Intermolecular adhesion (Vander Waal’s Forces)
Hydrogen Bonds.
Adhesion by coupling agents
Coupling agents utilizing the concept of hydrophobic and hydrophilic groups are the monomers based on
phosphate or phosphonate.
The hydrophilic PO4 group interacts with Ca+ ions in dentin. This type of adhesion is seen to occur with the non-
electrolyte adhesion. Bonding can be accomplished with the inorganic part of the dentin,hydroxyapetite, or to the
organic part. Use of coupling agents for bonding leads to only minor improvement in the bond strength. One coupling
agent ; 3-methacryloyloxy propyl trimethoxysilane. Another coupling agent ; butylacrylate acrylic acid copolymer
with free carboxylic acid groups. NPG-GMA is another coupling agent used.
The coupling agent utilizes the concept of hydrophilic and hydrophobic groups i.e. it consists of a bi-functional
molecule ,where the outer partinto a chemically unites with the tooth surface whilst the other attaches to resin.
The coupling agents have basically the formula.
M-R-X
M- Methacrylate group, which eventually becomes bound to the resin by copolymers.
R- is the clearing and spacing group spacing group must be able to provide the necessary flexibility to the
coupling agent to enhance the potential for bonding of the reactive group. If the molecule is excessively rigid, the
ability of the reactive group to find a satisfactory conformational arrangement is jeopardized ,such as hydrocarbon
chains.
X- represents a reactive or functional group with interacts with the tooth surface. The reactive

groups are end groups.
CLINICAL FACTORS AFFECTING ADHESION
Salivary or blood contamination
. Although dentin is a wet substance, the constituents of saliva and blood create an environment that can
destroy dentin bonding. These contaminants act in a negative manner for adhesion
. Rubber dam and other dry field aids should be used to prevent contamination.
Moisture and Oil contamination from Handpiece
During cavity preperation ,there may be water or oil contamination.This should be prevented by using a three
way syringe and maintaing the air compressors well.
Surface Roughness of tooth structure
Increased surface area created by surface roughness results in better bonds with dentin. Mechanical retention
may be increased by the microscopic roughness produced on dentin or enamel by rotary cutting instrument.
Mechanical undercuts in tooth preparation
The mechanical undercuts placed in the tooth structure hold the restorative material from bodily displacement
from the preparationand by microscopic movement caused by thermal or polymerization influences. This type of
retention is further augumented with the current generation dentin bonding agents.
Flouride content of teeth
Increased flouride content in enamel is considered to be resistant to acid etching but it was found that if the
etching time was made double ,the same effect would be produced.
Dentinal canal characteristics
Dentinal canals at the external surface of tooth roots or near the dentinoenamel junction have small diameters.
As dentinal canals are observed closer to the dentinal pulp, they become larger. Older dentin has small dentinal
canals, while younger dentin has larger dentinal canals. Superficial abraded dentin may have occluded canals. If the
canals are small, attachment is less and vice versa.Bonding agents use mechanical attachment into dentinal canala as
well as chemical bond.If canals are small ,attachment would be less whereas if canals are large,attachment is
enhanced.
Presence of plaque, calculus, extrinsic stains or debris
Any enamel or dentin surface that requires bonding must be scrupulously cleaned before the bonding
procedure begins. Plaque present on the tooth surface prevents etching . Penetration of plaque by the acids used in
DBA’s is not possible and will result in a clinical adhesive failure. Tooth surface stains and dental calculus if not
removed will not permit bonding.
Presence of bases or liners
The presence of varnish eliminates the potential to bond restorative material to the tooth surface. Liners may
result in creating moderate bonds with dentin but the bond strength is significantly lower than that created by placing
resin on acid etched enamel surfaces.
Tooth dehydration
Overdrying the tooth preparation before placing bonding agents should be considered to be a negative factor. Drying
only till the obvious shine of moisture remains is a good clinical guide.
Constituents of temporary cements
If a temporary cement is present since a long time in the tooth,the liquid portion of the cement is rendered
inert.Etching is done above the cement,which results in better adhesion.
DENTIN BONDING AGENTS
The dentin bonding agents are di or multifunctional organic molecules that contain reactive group, which interacts
with dentin and the monomer of the restorative resin.
Components of DBA Conditioner
Primer
Adhesive
Requirements of DBA
Ideally, dentin-bonding system should have

Sufficient bond strength, optimum 17-20 Mpa
Be compatible with dental tissues
Provide an immediate permanent high strength bond to dentin
Minimize microleakage at the margins of the restoration
Prevent recurrent caries and marginal staining
Easy to use and less technique sensitive
Reasonable shelf life
Compatible with all resins
No reduction in bond strength when applied to moist surface
No potential for sensitization of patient on operator
Problems in Bonding to dentin
The developments of adhesives that adhere to dentin have still been and still remain a challenge to
researchers.
Dentin consists of 50% inorganic hydroxyapetite, 30% organic material and 20% of fluid
Dentinal hydroxyapetite is randomly arranged in an organic matrix
The high fluid content of dentin places certain requirements on restorative dental material (resin are
hydrophobic)
The tubular nature of dentin provides a variable area through which the dentinal fluid might flow to surface
and adversely affect adhesion.
Sclerosed dentin if present is difficult to penetrate (results from aging or mild irritation and causes a change
in the structure of primary dentin, i.e. the peritubular dentin becomes wider, gradually filling the tubular with calcified
material. The areas are harder, denser, less sensitive).
Presence of intertubular and peritubular dentin,(each tubule is surrounded by a collar of hyper-mineralized
dentin called peritubular dentin. The less mineralized dentin between the tubules is called intertubular dentin).
The presence of smear layer complicates dentin bonding. The smear layer is present on cut dentin surface
and is of limited strength so it must be either removed or penetrated by the resin.
Permeability of dentin differs at different sites.Variation in permeability may arise due to tubular
irregularities associated with mineral deposits. It also increases near the pulp and pulp horns than the adjacent areas.
CLASSIFICATION OF DBA
1. According to generation
2. According to their adhesion strategy towards enamel,dentin or on the basis of number of clinical application
3. Depending on chemical composition
4. According to treatment of smear layer
5. According to chronology, chemistry and shear bond strength
6. According to mode of curing
7. According to type of solvent
1. On the basis of Generations:
1. First Generation Dentin Bonding Agents
Developed by Bowen - 1965.
Agents used in this generation are:
a. Glycerophosphoric acid dimethacrylate,
b. Cyanoacrvlates
c. NPG - GMA
d. Polyurethanes
Buonocore four decades ago found that a resin containing GPA-DMA could bond to Hcl etched dentin surfaces.
However, the bond strength was by water. To overcome this problem Bowen synthesized NPG-GMA a surface-active
comonomer that theoretically produced water resistant bonds. NPG-GMA acted as an adhesion promoter between the
tooth structure and resin material by chelating with surface calcium.
Disadvantages:
Poor clinical results
Hydrolysis of GPA-DMA in oral environment
Difficulty - in bulk polymerization of cyanoacrylates
Instability of NPG-GMA in solution
Hydrophobic resin
Low bond strength (2.1 - 2.8 Mpa)
Ex: Cervident (S.S.White Co.)
First commercially available dentin bonding agent.
Cosmic bond (Amalgamated Dental)
Palakav (Kulzer, USA)
2. II Generation Dentin Bonding Agents:
In general, the second-generation dentin bonding agent was much improved compared with the first generation.
These were developed during the early 1980's.
Most of the agents were primarily - (polylmerizable phosphates in BIS-GMA) resin
1. Halophosphorous esters of BIS-GMA. Hence they were called as phosphate-bonding systems.

2. Polyurethane based compounds were also used.
The bonding mechanism involves a surface wetting
Phenomenon as well as ionic interaction b/n phosphate groups and dentinal calcium.
The II-generation systems had the smear layer intact. This was to create a Ca+ rich layer where the phosphate can
combine with Ca+.
Disadvantages:
1. Low bond strength (1-3 Mpa) (studies by Relief and others 1986 and Solomon & Beech)
2. Hydrolysis of phosphate Ca+ bond.
A major reason for the poor performance of these bonding agents is the fact. that these bond to the smear laver rather
than to the dentin itself.
Ex: Scotch bond dual cure ('OM Dental)
Bond Lite, (Kerr)
Dentin Bonding Agent (Johnson &. Johnson) Prima Universal
Creation Dentin Bonding Agent
Clearfil (Kuraray)
3. III generation Dentin Bonding Agents
Developed in mid 1980s.
The third generation dentin adhesives showed increased bond strength and improved clinical performance.
These systems resulted either total or partial removal of the dentinal smear laver.
In addition they required a surface-conditioning step. They used a solution or a series of solutions to increase the
wettability of dentin (i.e. priming solution).
Their mechanism of bonding to dentin was by penetration of smear layer i.e. they used micro mechanical means of
adhesion rather than the unreliable chemical bonding of previous material.
Disadvantages:
Time consuming (More of number of steps)
Technique sensitive
Ex:
Gluma (Bayer Dental)
Conditioner: EDTA 17%
Primer: 35% 1-iEMA (Adhesion Promoter)
5% Glutaraldehyde
Adhesive: 55% BISGMA 45% TEGDMA
Bonding was achieved by
Glutaraldehyde bonds to amino groups in collagen
Charge compounds
Reacts with
OH group of HEMA
And causes mechanical interlocking in the opened ends of dentinal tubules
2. Tenure:
Oxalate was the first available dentin-bonding agent developed by Bowen.
Conditioner: 2.5% nitric acid + ferric oxalate (stains the teeth).
SYSTEM CONDITIONER ADHESION PROMOTERBA
1 Gluma 17% ED'FA 35% HEMA 5% GA 55% BISGMA TEGDMA
2 Scotchbond 55% HEMA 2.5% Maleic acid BIS-GMA HEMA
3 TENURE (10.2-18.2 Mpa) 1% Nitric acid 2% Phos. Acid 2.5% Aloxalate 5% NTG- GMA
PMDM BIS-GMA TEG- DMA
4 4. Prisma Univ. Bond 2 30% HEMA 6% PENTA 50% UDMA 25%TEG- DMA 4.5% PENTA
0.5% GA
4. Fourth Generation Dentin Bonding agent:
In these systems there was complete removal of smear layer.
These bonding systems involved the "Total etch" technique that is simultaneous etching of enamel and dentin with
phosphoric acid or other acids. An improvement in dentinal bond strength by etching was first demonstrated by
Fusayama in 1979 and became common in Japan. This gained acceptance in US much later. This is because etching
of dentin has been traditionally discouraged because of pulpal inflammation but it is found that very little acid actually
penetrates dentin.
These systems were also known as Universal bonding systems as these bonds to dentin, enamel, amalgam, porcelain
and composite.
Mechanism of bonding
1.Acid Etching
Removes the smear layer
Opens the dentinal tubules
Increases dentinal permeability
Decalcifies intertubular and peritubular dentin

Depth of decalcification is affected by
PH of the acid
Concentration
Viscocity
Application of time of etchant
Removal of hydrxyapetite crystals leave a collagen meshwork that can collapse.After the conditioner is rinsed off,
primer(containing hydrophilic resins )is applied.
The primer wets and penetrates the collagen meshwork raising it to almost its orginal level.The primer also
increases the surface energy and hence the wettability of the dentinal surfaces.Then the unfilled resin is applied and
penetrates the primed dentin co-polymerizing with the primer to form a intermingled layer of collagen and resin
termed as hybrid layer or resin reinforced zone or resin infilterated layer.
This is thought to be the primary bonding mechanism of current adhesive systems.
Ex:
All Bond(BISCO)
Amalgam Bond Plus
Scotchbond Multipurpose
ProBond
Liner Bond 2
ALL BOND 2
All Bond 2 is a unique development in the field of adhesive.It is a universal bonding system that will bond
composite to all dental related surfaces.
i.e. Dentin
Enamel
Metal Alloy
Amalgam
Porcelain
Composite
ALL BOND 2 (BISCO)
Conditioner: SA+HEMA(4.4)
Primer: 2% NTG-GMA
16%BPDM
Adhesive: BIS-GMA,UDMA,HEMA
SCOTCHBOND MULTIPURPOSE
Conditioner: 10%Maleic acid
Primer: HEMA+Polyalkenoic acid
Adhesive: Hydrophobic BIS-GMA
Hydrophilic HEMA
Photoinitiators
AMALGAM BOND
Conditioner: 10% Citric acid
19% Ferric Chloride
Primer: HEMA with water
Adhesive: 4-META
MMA-TBB
Advantages:
Bond strength-18Mpa
Wets better
Bonds to wet surface
Disadvantages:
Unless the primer and adhesive are applied consequtively,the overlying composite resin will not bond to the
surface.
In case of 4th generation bonding systems the clinician had an optionof converting the dentin bonding agents from a
light curing to a dual curing one.this was carried out by incorporation of a self-activating agent(sulfinic acid
derivative)to the bonding agent(1:1 ratio).
Fifth Generation Dentin Bonding Agents
To simplify the clinical procedure by reducing the bonding steps and thus the working time, a better system

was needed. Also clinicians needed a better way to prevent collagen collapse of demineralized dentin. So, the 5th
generation bonding systems were made.
Here,the primer and adhesive are combined in one step.These were marketed as one bottle bonding
systems.However,etching was required so these are not treated as one bottle system.
The etching is carried out for 15-20 secs.this system creates a mechanical interlocking with etched dentin by
means of resin tags ,hybrid layer formation.
Ex: Primer&Bond NT(Dentsply)
Opti Bond Solo Plus(Kerr)
One Step(Ivoclar)
Single Bond(3M)
Scotchbond MP Plus(3M)
1. PRIME &BOND NT
Conditioner: 35%Phosphoric acid
Adhesive: PENTA,UDMA,Resin
R5-62-1,T&D Resin
Nanofiller,Cetylamine
FL&Acetone
Sixth Generation Dentin Bonding Agents
The sixth generation dentin bonding agents were introduced in the late 1990’s(1999).Here ,the primer and etchants
are combined in one step(self etch primers-SEP’S)
The sixth generation bonding systems are characterized by the possibility to achieve a good bond to enamel
and dentin using only one solution. The first evaluation of these systems showed sufficient bond to conditioned
dentin while bond to 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 refereshed continuously and have a pH that is not
enough to properly etch enamel.
Recently, a H2O based bonding has been introduced which combines with the functions of a conditioner, the
primer and the adhesive in a so called self-conditioning primer adhesive.The active solution is mixed from two
components resulting in the formation of an acidic(self-conditioning) monomer which superficially etches dentin and
enamel. The dentin bond mediated by this bonding agent seems to be adequate. However, the etching pattern of
enamel appears to be less retentive than that produced by phosphoric acid etching.
Ex:
Prompt -L-Pop
It has 3 compartments
Compartment 1: Containing methacrylated phosphoric acid, esters, photo initiators, stabilizers
Compartment 2: Contains water, complex fluoride and stabilizers
Compartment 3: Has a micro brush
The blister is activated by squeezing compartment 1, thereby releasing its content into compartment 2. The mixing
ratio is 4:1 and the freshly mixed solution is released on the micro brush into compartment 3.
On applying this to dentin, the smear layer will be dissolved. Then the demineralized dentin is loaded with
prompt-l- pop monomers leading to the formation of a hybrid layer.
Seventh generation Bonding Agents
This is the latest addition in the series of bonding systems.
According to manufactures, it a fluoride releasing, self-etching type of bonding agent. It also has a colour
changing capacity.
The etching, priming and bonding is a simple application with no rinsing or drying.It is available in two bottles,
which have to be mixed and filled in the cavity.
It is being manufactured by a company called J Monta (USA) and the product is ONE UP BOND F.
This is the only bonding system, which provides visual confirmation of complete
polymerization by color charge.
Yellow Pink White
(Liquid A and B) (Liquid A & B mixed) (Completely cured)
Manufactures are claiming that this bonding system also blocks postoperative sensitivity.
Another manufacturing company H KULZAR have brought a product “BOND” in the market. This Is a
single bottle system having self etch priming and bonding along with desensitizing capacity.
It has the advantage of single bottle system and no need of mixing of any liquids.
2. Classification based on the number of clinical application steps and how they interact with the tooth structure
This new classification based on adhesion strategies has been given by Van Meerbeek&Others i998,2000
1.Total etch adhesives
3 step

2 step
2.Self etch adhesives
2 step
1 step
3.Resin modified glass ionomer adhesives
TOTAL ETCH ADHESIVES
These adhesives involve a separate etch &rinse phase.The conditioning step is foolowed by a priming step and
application of adhesive resin.This results in a 3 step total etch adhesive(4th generation)
In the 2 step total etch adhesive,primer &adhesive are combined in one application.i.e.
Conditioning (I Step)
+
primer+adhesive(II Step)
This correlates with the 5th generation of adhesive
Mechanism of adhesion
Bonding to acid-etched enamel enamel requires an air-dried surface to allow the photo-polymerization hydrophobic
bonding agent to be drawn by capillary attraction into the pits created by acid-etching.As a result,two kinds of tag-like
resin extensions are formed(Permans&Others,1999;Van Meerbeek&Others;2000b)
Macrotags are circularly formed between enamel prisms and peripheries.Microtags are formed at the cores of
enamel prisms where the resin cures into a multitude of distinct crypts of dissolved hydroxyapetite crystals.
The underlying mechanism for the 3-step &2-step total etch adhesive is alike.The dentin smear layer produced during
cavity preperation is removed by etch&rinse phase,which results in 3-5m deep demineralization of the
dentinsurface(Perdigao1999).Coolagen fibrils are completely removed from hydroxyapetite and form a microretentive
network for micromechanical interlocking of monomers(Hybrid Layer).
Advantages and Disadvantages of 3-step total etch adhesive
Three Step Total Etch Dentin Bonding Agents
Ex
? All Bond 2(Parkell)
? Clearfil Liner Bond(Kurray)
? Gluma BS(Bayer)
? Scotch BondMP Plus(3M)
Advantages
Separate application of conditioner,primer&adhesive
Low technique sensitivity
Bonding to enamel is good
There is a possibility of particle filled adhesive
Most efficient&consistent results
Disadvantages
Risk of overstretching of collagen fibres
Time consuming procedure
Post conditioning,rinse is required
Sensitive to over-dry*over-wet conditions
Weak monomer-collagen interaction
Two Step Total Etch Dentin Bonding Agents

Ex
Gluma Comfort Bond(Kulzer)
Prime&Bond NT
Prime&Bond2.1
Advantages
Simpler application
Possibility for particle filling
Possibility for single dose packaging
After priming,the surface should appear glossy without any dry spot.This is a climical indication that resin is
adequately and sufficiently applied.
Monomers are sufficiently applied not only to saturate the exposed collagen network but also to establish a
thick resin layer on top of the hybrid layer.This layer may act as a flexible intermediate shock absorber.This shock
absorber may also help to protect the adhesive joint against early failure.
Prime&Bond NT
This is a successor of prime*bond 2.1.it contains nanofillers which have a diameter of about 7m.These nanofillers help
to form a uniform resin film that stabilizes the hybrid layer.
They also serve as an additional cross-linker,i.e.the average dentinal tubule is about 8m in diameter and the
channels between the collagen fibrils is about 20nm wide with a diameter of 5-10nm.The nanofiller is able to
penetrate these channels to provide nanoretention.This is a fluoride releasing mechanism.
SELF ETCH ADHESIVES
This adhesive system is based on the use of non-rinse acidic monomers that simultaneously condition&prime dentin
and enamel.The concept of self-etch primers was first introduced by Scotchbond 2(3M),In the early 90’s.However,this
system was advocated to be applied on dentin alone,and therefore required clinically selective enamel etching in a
separate step.
More recently one step SEP’s or all in one adhesives are available that combine the conditioning,priming and
application of adhesive resin into a single application.
Two step SEP
Ex:
Clearfil Liner Bond 2V(Kurray)
Prime&BondNT+NRC
Scotchbond(3M)
Optibond(Kerr)
One step SEP
Ex:
Prompt-L-Pop(ESPE)
Syntac
Etch&Prime 3.0(Degussa)
Single component DBA
Advantages
No acid etching required
No light curing of DBA
Well defined hybrid zone
High bond strength
Depth of demineralization corresponds to depth of penetration
Disadvantages

High cost
Used only with direct resin restoration
Depending on pH and etching potential SEA are classified into
Mild SEA(pH 2.0) and Strong SEA(Ph 1.0)
Mechanism of bonding
The mechanism of bonding differs for mild and strong self etch adhesives
Mild SEA
Here, two types of bonding are seen,hybridization+intermolecular bonding
The hybrid layer is of sub-micron size and resin-tag formation is less pronounced.In the hybrid layer,hydroxyapetite is
not removed completely because of the weak acid.So, a second type of bonding occurs,i.e.hydroxyapetite acts as a
receptor for additional molecular interaction with specific carboxyl or phosphate groups.
Ex,the primary ionic bonding of Unifil Bond GC;2 carboxyl groups of 4-META with hydroxyapetite were
confirmed in XPS and TEM.
This two-fold mechanism may be advantageous in terms of restorative longevity.
Strong SEA
This is similar to the total etch bonding system.Mechanism of bonding is by hybrid layer formation ,i.e. nearly all
hydroxyapetite is removed from the collagen and thus any chemical reaction between hydroxyapetite and functional
monomer is excluded.
GLASS IONOMER ADHESIVES
A third adhesion strategy that differs from the former approaches(persued by resin-based systems),as it involves glass-
ionomer based interaction with the tooth substrate
,with the development of resin modified glass ionomer adhesives that can bond resin to the tooth structure.
A two-fold mechanism is predicted with this system with a short polyalkenoic acid pretreatment which cleans the
tooth surface,exposes surface collagen to a depth of o.5-1.0m.
Here.a micromechanical bond;due to resin interdiffusion and a chemical bond; due to ionic interaction of the carboxyl
groups of polyalkenoic acid with calcium of hydroxyapetite that remained attached to collagen fibrils,takes place.The
underlying mechanism of glass ionomer adhesives is similar to that of mild etch adhesives.
A network of “hydroxyapetite-coated”collagen fibrils interspread by pores is typically exposed to a depth no
deeper than 1m.Upto 0.5m thick layer,oftenreffered to as gel-phase remains attached to the tooth surface despite the
conditioner being rinsed off.
3. According to their chemical composition (Craig)
? Polymethanes
? Polyacrylic acids
? Organic phosphonates
? Mellitic anhydride and methylmethacrylate (4-META)
? Hydroxyethyl methacrylate + Gluteraldehyde (HEMA+GA)
? Ferric oxalate + NPG-GMA (N-phenyl glycine and glycidyl methacrylate)+PMDM pyromellitic dianhydride
and 2HEMA)
4. On the basis of treatment of smear layer
The smear layer of limited strength, so it must be either removed or modified before application of bonding
agent
a. Removed
Example: -
Tenure (nitric acid)
Mirage bond
Clearfil liner bond systems
b. Modified

Example: -
All bond
Scotch bond 2
XR bond
c. Preserved
Example: -
Scotch bond dualcure
Prisma universal bond
5. On the basis of shear bond strength (Eick et al.)
Included dentinal adhesives without produce shear bond strength of 5-7Mpa
Example: -
Dentin adhesit
Scotch bond dual cure
Gluma
Category 2
Included the experimental and commercial products derived from Bowers work with ferric and aluminium
onalalates and have produced shear bond strength between 8-14 Mpa
Example: -
Tenure
Mirage bond
Category 3
Included dentinal adhesives, without produced shear bond strength values of about 17-20Mpa
Example: -
Super bond
Scotch bond 2
Scotch bond multipurpose
All bond
(Decreased failure was cohesive in nature)
6. According to their mode of curing
Chemical cure
Example: -
Amalgabond plus
Light cure
Example: -
One bond
Gluma comfort bond
Dual cure
Example: -
Clearfil linear bond 2V
Prime and bond NT dual cure
SMEAR LAYER
Introduction
Knowledge of the nature, structure and composition of the prepared surfaces of the teeth is the key to the
formulation and understanding of adhesive restorative systems.
Smear layer was first suggested by Skinner (1961). It was first described in detail and termed as “smear

layer” by Boyde et al (1963)
The smear layer encompasses of any debris remaining on enamel, dentin after conventional methods of
cavity preparation.
The smear layer can be discussed under the following:
? Composition
? Formation
? Size
? Attachment to dentin
? Potential advantages/disadvantages
Composition
Smear layer in composed of debris generated during cavity preparation. Sculein lists the following as its components.
Inorganic tooth particles
Bacteria and tissues
Saliva
Blood
.
Smear layer is rich in nitrogen, sulphur, carbon. The organic component consists of coagulated proteins
denatured by frictional heat during cavity preparation.
The presence of hydroxyapetite crystals in smear layer is because of its breaking away from the organic
matrix and then resetting in the smeared matrix.
Formation
Smearing occurs when hydroxyapetite within (the tissue) is either plucked out or broken or swept along the
resets in the smeared out matrix.
Studies have shown that temperature will rise up to 6000C in dentin when it is cut without a coolant. This
value is significantly lower than the melting point of appetite (15000C - 18000C) and has led to conclude that smear
layer formation is a physiochemical phenomenon rather than a thermal transformation of appetite involving
mechanical shearing and thermal dehydration of the protein. Plastic flow of hydroxyapetite is believed to occur at low
temperatures than its melting point.
Size
The smear layer thickness is about 5-10 microns but according to some studies it may range from 1-5.
The size of the smear layer is influenced by the type of bur used, it speed of rotation and presence or absence
of coolants.
The steel and tungsten carbide bur produce an undulating pattern. There is a rapid deterioration of the cutting edges.
The cutting efficiency of these burs increase the frictional heat resulting in the smear layer formation.
This smear layer formed is irregular in shape and non- uniform in size and distribution, and remains on the
prepared surface even after thorough levage with water.
The diamond burs produce relatively deep and uniform groves. Significant difference exists between
diamond burs used with and without a coolant (water spray). The smeared debris does not form a continuous layer but
exists as localized islands with discontinuities exposing the underlying dentin. The water spray does not prevent
smearing but significantly reduces its amount and distribution.
The smear layer consists of two separate layers
Superficial layer (outer) loose debris
Layer loosely attached to underlying dentin (Inner) plug formation
Attachment to the underlying tissue
The smear layer is not always firmly attached to or continuous over the substrate. It may lift free in come
cases.
Potential Advantages & Disadvantages of the smear layer
The main advantages of the presence of smear layer on dentin.
Reduction of dentin permeability to toxins and oral fluids.
Reduction of diffusion (usually inwards) & convection (outwards by hydrostatic pressure or inwards eg. by
cementing restorations) of fluids, prevents wetness of cut dentin surfaces.
Bacterial penetration of dentinal tubules is prevented.
.
The main disadvantages are:
It may harbour bacteria, either from the original carious lesions or saliva which may multiply taking

nourishment from the smear layer or dentinal fluid.
The smear layer is permeable to bacterial toxins.
The smear layer may prevent the adhesion of composite resin systems, bonding agents, glass ionomer and
polycarboxylate cements.
Hybrid layer
Bonding to acid etched tooth surface requires an air-dried surface to allow the photo-polymerizable
hydrophobic bonding agent to be drawn by capillary attraction into the pits created by acid etching. As a result, two
kinds of tag- like resin extensions are formed.
Macro-tags are circularly formed between enamel prisms and peripheries.
Micro-tags are formed at the cores of enamel prisms where the resin cures into a multitude of distinct crypts of
dissolved hydroxyapetite crystals.
The underlying mechanism of dentin is alike for three or two step total etch adhesives The dentin smear layer
produced during cavity preparation removed by the etch and rinse phase which results in a 3-5m deep
demineralization of the dentin surface. Collagen fibrils are nearly completely uncovered from hydroxyapetite and
form a macro-retentive network for micromechanical interlocking of monomers. This interlock was first discussed by
Nakabayashi, Kojima & Masuhma in 1982 and is commonly referred to as HYBRID LAYER.
Concurrent with hybridization, resin tags seal the unplugged dentinal tubules and offer additional retention
through hybridization of the tubule orifice wall.
Three specific ultra morphologic features have been described as resulting from this hybridization process.
Shag carpet appearance stands for the loose organization of collagen fibrils that are directed towards the
adhesive resin and often unravled into their micro-fibrils.
This feature typically appears when the dentin surface, after being acid-etched, has been actively scrubbed
with an acidic primer solution. The physical rubbing action combined with chemical action of the citric acid was
found to enhance the removal of acidically dissolved inorganic dentin material and surface debris. This resulted in a
deeply tufted collagen fibril surface whose topography is similar to appearance of a shag carpet.The combined
mechanical or chemical action of rubbing the acid etched dentin with an acidic primer dissolves additional mineral
while fluffing and separating the entangled collagen at the surface. This active rubbing application is thought to
promote infiltration of monomers into the loosened collaged scaffold by a kind of “massaging effect”.
A second typical hybridization characteristic has been termed as tubule- wall hybridization and represents the
extension of the hybrid layer into the tubule wall area. Resin tag formation in the opened tubules is circularly
surrounded by a hybridized tubule orifice wall that is thought to be favourable in hermetically sealing the pulpo-
dentinal complex against microleakage and the potential subsequent ingress of microorganisms. This effect may be
especially protective when the bond fails either at the bottom or top of the hybrid layer, which are considered the two
weak links in the micromechanical attachment. Then, the resin tags usually break off at the hybrid layer, surface
keeping he dentin tubules and thus the direct connection to the pulp sealed.
Thirdly, lateral tubule hybridization has been descried as the formation of tiny hybrid layer into the walls of
lateral tubule branches. This micro-version of a hybrid layer typically surrounds a central core of resin, called a
microresin tag.
Reverse Hybrid layer
The acid etched surface of dentin is further subjected to treatment with sodium hypochlorite. This results in
dissolution of the collagen fibrils that are exposed. Further, the use of self-etching primers results in superficial
etching of the surface. Here, the hybrid layer is surrounded by more of inorganic material unlike the normal hybrid
layer where the collagen fibers are encapsulated by resin, and so this layer thus formed is termed as reverse hybrid
layer.
Inter-tubular Bonding
The hybrid layer has been considered to provide micromechanical bonding to dentin but resin tag formation
may also contribute to the bond strength. Penetration of the bonding agent into the tubules may provide increased
retention, as there will be no path of withdrawal until same tags fracture. So, dentin near the pulp has more retention
due to increase number of tubules.
The action of these mechanisms is by :
? The resin tags, which significantly increase the bonding width.
? Hybrid layer, which creates an elastic layer between the restoration and dentinal tissue (elastic bonding).
Conditioning of dentin

Conditioning of dentin can be defined as only alteration done after the creation of dentin cutting debris,
termed the smear layer. The objective of this to create a surface ,capable of micromechanical and possible chemical
bonding to a dentin bonding agent.
The principal effects of conditioning of dentin may be classified as
a) Physical changes.
b) Chemical changes.
Physical changes are principally
? Removal or modification of smear layer.
? Opening of dentinal tubule orifices.
Chemical changes are principally
Modifications of the fraction of organic matter.
Decalcification of the inorganic portion.
Removal of smear layer generally results in increased permeability of the dentin (Pashley, Michelich, Kehl
1981). The small particles comprising of smear layer have a large surface to volume ratio. The particles dissolve
more easily then the intact dentin. If the smear layer and smear plugs within the tubules are lost, the exposed dentin
becomes more permeable and sensitive. For clinical success the conditioned dentin must be sealed to prevent
sensitivity and pathology (Brannstrom 1981).
Conditioning of dentin same be done by
1) Chemicals
a) Acids
b) calcium chelators
2) Thermal
Lasers.
3) Mechanical
Abrasion.
Acid conditioners
Manufactures generally use the terms conditioners or etchant to describe agents that are rinsed off the dentin.
Mode of action of chemical conditioners
It has been suggested that mineralized collagen matrices have appetite crystallites arranged not only around
collagen fibrils but also within them. The depth of demineralizationb depends on the type of dentin present. In
sclerotic dentin because of either hypermineralization or formation of more acid resistant forms of calcium phosphate
(Pashley 1992),more time and stronger acid is required for etching.
Effect of chemical conditioners
Chemical conditioners remove the smear layer and expose a microsporous scaffold of collagen fibrils thus
increasing the microporosity of intertubular dentin. Because this collagen matrix is normally supported by the
inorganic dentinal fraction, demineralization causes it to collapse. In intertubular dentin the exposed collagen fibrils
are randomly oriented and are often covered by an amorphous phase with reletively few microporosities and variable
thickness. Sometimes fibrous structures probably remanants of odontoblastic processes are pulled out of the tubules
and smeared over the surface. With aggressive acid etchants ,the acids may tend to pull the collagen fibers away from
the intact dentin or unaffected dentin leaving a submission space termed as hiatus. With increasing aggressiveness of
the conditioning agent ,a circumferential groove may be formed at the tubule orifice separating a cuff of mineralized
peritubular dentin from the surrounding intertubular dentin. Alternatively, the mineralized peritubular dentin may be
completely dissolved to form a funnel shape structure.
Historically, several acids have been used as dentin conditioners. These include hydrochloric acid, pyruvic
acid, phosphoric, citric and nitric, acids.
Phosphoric acid
It was the first dentin conditioner that was successfully used to remove the smear layer, etch the dentin and
restore with adhesive composite resin by Fuzayama and Others (1979). This helps in removing the surface dentin,
leaving a clean, well-defined etching pattern where the tubules are enlarged into a funnel shape. Phosphoric acid is
the acid of choice recently for the etching purpose. However, the controversy remains about the optimal concentration
of this acid. The most widely used concentration in clinical practice is 37% of H3 PO4. Chow and Brown (1973)
demonstrated that the application of phosphoric acid solutions greater than 50% resulted in the formation of

monocalcium phosphate monohydrate that is not readily soluble and would not be completely washed away in the
clinical situation.
If H3 PO4 is applied on dentin when 50 of dentin was remaining it resulted in pulpal damage as the acid
liberated gas that passed through the pulp producing thrombus and haemorrhage (Kozam and Burnett).
NITRIC ACID
It is stronger than phosphorus acid.
Easily removes the smear layer.
Concentration of 2.5% causes funneling of the orifice of dentin to a depth of 5m in 40 seconds.
CITRIC ACID
10% citric acid is used for the purpose of removing the smear layer. It has been reported by Nakabayashi
(1989) that such treatment tends to lower the porosity or permeability of the demineralized surface, possibly by
denaturing the collagen.
Nakabayashi developed 10% citric acid plus 3% ferric chloride combination. The divalent cation seems to
stabilize the dentin matrix during its demineralization by citric acid. This combination was found to be particularly
effective for methacrylate based adhesives containing 4-META.
Ferric appears to be necessary since the sitric acid alone yield poor results with this system. The higher bond
strengths of 4-META/ MMA- TBB products conditioned by 10% citric acid and 3% ferric chloride solution can also
be achieved by substituting cupric chloride for the ferric ions, example Super Bond C and B metabond and amalgam
bond.
Kuraray Introduced 10% citric acid and 20% calcium chloride in the latest generation of clearfil linear bond
system. This high concentration of calcium may stabilize collagen during surface etching. It also decreases the extent
of the demineralization of hydroxyapetite by a common ion effect. Here, the depth of decalcification is about 8-
microns compared to the phosphoric acid etching which results in 16- micron depth of decalcification (Inokshi and
others 1989).
PYRUVIC ACID
Pyruvic acid and pryuvic acid buffered with glycine have been reported to satisfactory acid etch both enamel
and dentin (Asamussen and Munksgaard, 1988) when using the Gluma Bonding system .Glycine was used to adjust
the pH and perhaps to facilitate polymerization reactions.
MALEIC ACID
It removes the smear layer but not the smear plugs. It is used in scotch bond 2 and Dexthessive as a
conditioner. Although it is grate acidic, it does not appear to decalcify deeply. The hybrid layer formed in this is
comparatively thin.(10% maleic acid is used).
POLYACRYLIC ACID
These acids are being used more recently. A 10 second application of Durelon liquid (40% polyacrylic acid)
results in opening of dentinal tubules. There is no chance of potential harm to the dental pulp here, due to the large
molecular size which prevents the acid to more through the dentinal tubules.
HYDROCHLORIC ACID
The hydrogen ions from these acids diffuse into the dentin while etching. The surface reactions are violent as
carbonate is converted to carbon dioxide and as calcium and phosphate are liberated. These products may be liberated
faster than they can diffuse from the site leading to formation of reaction products that may limit further penetration of
protons. Further, the hypertonic solutions when osmotically draw the fluid from the dentin towards the surface could
restrict the inward proton diffusion.
CALCIUM CHELATOR
Chelators are used to remove the smear layer without decalcification or significant physical changes to the
underlying substrate as apposed to the strong acid etchants.
EDTA(ETHYLENE TRIAMINE TETRAACETIC ACID)
Brannstrom’s concern that bacteria might be incorporated into smear layer and infect the dentin surfaces of
cavities led him to develop a dentin conditioner containing 0.1% ethylene diaminetetracetic acid and 0.15%
Benzalkonium chloride as a surface active disinfectant (1980). This agent was marked under the name “Tubulicid”.
It is scrubbed on the surface of the smear layer for a few seconds, then left passively for another 60 seconds followed
by additional scrubbing .Such treatment removes the smear layer and generally leaves the smear plug intact. The
dilute solution of EDTA removes some calcium that is thought to be important in the mechanism of bonding. This
was probably responsible for the fall in bond strength. EDTA was developed for its use in the Gluma system by
Munksgaard and Asmussen in 1984. It removes the smear layer but does not form significant surface concavity nor is
the funnel shape change associated with phosphoric acid evident. The smear plugs in the dentinal tubules are not for

removed completely by 30 secs of application of the conditioner.
Thermal Modifications
Lasers
Hard tissue lasers in dentistry are an emerging technology. A pulsed Nd:YAG laser will not disturb the pulp,
even the approached is as close as 1m. Heat is dissipated b/w the 10 to 30 secs pulses per second. Most of the
research has been conducted on dry dentin, but the laser operates on dentin immersed in saliva or H2O. The
mechanism of dentin removal is through microscopic explosions caused by the thermal trannents. The carbonized,
black soot that results is easily washed off with water. Lased surface results in desensitized dentin, presumably by
occlusion of the open and permeable dentinal tubules. Microorganisms and organic debris are eliminated from the
lazed surfaces. The laser decreases the organic fraction of the dentin surface.
The bond strength is increased by about 60% when this was done presumably by increasing the bondable
inorganic fraction of the dentin surface. The laser may create micro-mechanical retention.
Mechanical Modifications
It is a mechanical mean of modification of dentin aluminum oxide is used for the purpose of micro-abrasion.
It removes healthy as well as diseased dentin and results in a smear layer. Its abrasion action depends on the particle
size as well as the velocity. The 0.5-micron or larger particles create a smear on the dentin and increase the surface
area (Blacke, 1991). The smear layer formed might be used to eliminate the bond strengths of smear layer mediated
dentin bonding agents.
Primers
Major advances have been achieved by the introduction of primers that promote wetting of the dentin with the
bonding agent, and penetration of the bonding agent into the dentin.
Primer monomers are bifunctional molecules i.e they contain
1. hydrophilic groups (eg- OH-2-COOH) for better compatibility of the resin monomers with the moist dentin,
2. hydrophobic methacrylate groups for the co-polymerization with the bonding resin Primers are monomer dissolved
in solvents such as acetone, alcohol and water and are capable applied to the etched or conditioned dentin substrate
last are not rinsed off. Organic solvents aid in displacing water, expanding or re-expanding the collagen network and
thus promoting the infiltration of the monomer into the submicron or nanometer sized spaces with in the collagen
fiber network. The first dentin bonding mechanism that gave reliable, high bond strengths reported by Nakabayashi et
al (1982) was based on the use of 4- META/ methyl methacrylate tri-n butyl borane (MMM- TBB) and 3% ferric
chloride in 10% citric acid as a conditioner.
Effective primers contain monomers with hydrophilic properties that have an affinity for the exposed collagen
fibril and hydrophilic properties for co-polymerization with adhesive resins. The objective of this step is to transform
the hydrophilic dentin surface into a hydrophilic state. Besides HEMA primers contain other monomers, such as
NTG-GMA, PMDM, BPDM an PENTA. Present day primers also include a chemical or photo polymerization
initiator so that these monomers can be polymerized in sitiu.
Solvents used in adhesives
ACETONE
Highly volatile
Excellent water chaser
Strong drying agents (risk of over-drying dentin)
Storage and dispense problems
Ex- One Step (Bisco)
Prime and Bond NT (Dentsply)
Gluma One Bond
ETHANOL
Excellent penetration capacity
Good compromise in respect of evaporation
Good surface energy
Ex- Excite(Vivadent)
Optibond Solo Plus(Kerr)
WATER
Good penetration capacity
Enables self-etching of acid monomers
Slow evaporation difficult to remove
Remaining H2O may hamper the resin penetratum air polymerization
Ex- Amalgam bond plus (Parkell)
Prompt-L-Pop

Etch bond multipurpose
Solvents may also be used in combination i.e.
.
Acetone -H2O
Ex- tenure-quick
Acetone-Ethanol
Ex-All Bond 2(BISCO)
Ethanol-water
Ex-Gluma comfort bond
Scotchbond
DRY BONDING
This refers to the bonding in which the acid etched dentin is dry and uses adhesive systems that provide water based
primers.These rehydrate and re-expand the collagen fibres ,allowing the resin to infilterate.
WET BONDING
This refers to the bonding in which the acid etched dentin surface is moist .This uses acetone based primers which
have water chasing capacity.This technique was introduced by Kanca(1992) and Gwinnet(1992).
There are 2 types of bonding systems
Water Based Primers
The first approach to create a hybrid layer in wet dentin is the use of water-soluble primers containing
HEMA. Examples of this type of monomer are Scotch bond 2, Scotch Bond Multipurpose. After application of the
water- HEMA mixture, the surface is air-dried to evaporate the H2O. As the H-2O concentration falls, the HEMA
concentration rises, until theoretically there should be no H-2O and 100% HEMA on the surface. Water has a much
higher vapour pressure than does HEMA. In fact, at atmospheric pressure, HEMA can be regarded as almost volatile.
This permits its retention as a solvent; water is evaporated during air-drying.
Use of water Miscible primer solvents
The second method of creating hybrid layers in this category of bonding is to sequentially acid etch, rinse,
leave moist on dry prime and them bond then HEMA will be in 2 types
1) 35% HEMA in water
2) 13% polyalkenoic acid copolymer in 50% HEMA.
The intrinsic wetness of dentin varies from about 1% in superficial to about 22% in deep dentin. Tay et al using all
Bond 2, Bisco, have described the consequences of applying acetone based premiers to overwet dentin; the authors
found that small globules were formed within dentinal tubules. These were formed when the first one or two layers of
primer were applied, i.e. in the tubules filled with dentinal fluid there was too much water available to dilute the
acetone with result that the monomer came out of the solution. As more globules formed, they accumulated on the
walls of the tubule, reducing the permeability of the tubules, permitting successive primer applications to dehydrate
the tubules enough to form normal resin tags.
If successive extrinsic water is left on to surface prior to the application of primer (All Bond 2), which tends
to bridge the excess water droplets to four a tiny blister. This prevents resin tag formation in those tubules beneath the
water droplet, clinically if the clinician sees a rough texture on the primed surface that might be caused by this
phenomenon , these droplets can be destroyed with the tip of brush, which can be used to add more primer .
Steps for effective priming
Microscope examination of attachments produced by primer has shown deficiencies like
? Incomplete surface coverage
? Incomplete interfibrillar saturation within the hybrid zone
? Incomplete penetration to a full depth of demineralized dentin
Steps
A - One method of improving surface coverage and diffusion of the primer is by the application of multiple coats. A
second coat of primer is shown to increase the shear bond strength significantly.
B-The surface of dentin should not be over dried or over wet.
C-The etching time should not exceed the time recommended by the manufacturers.
The primer reacts with the side chain grouping of the amino acids in the collagen structures especially -NH2, -OH2
and COOH. Masuhara and coworkers developed analysis bonding agents containing the polymerization initiator
tributyl boron, which is said to induce grafting of the monomers and polymers on to the collagen structure.

WET BONDING
Earlier, placement of restoration on wet surface may have caused confliction between the dentist and his
training. However, the picture has changed now.
When the etched dentin is air dried the collagen network will collapse & the micro-channels opened by the
removal of the appetite systems will be closed from a compact coagulate that is impenetrable to resin.
Resulting in a layer of imperfect bonding termed as “Hybridoid region” (Tay, Guinett, 1995). This results in
microleakage at nanometer level (1/1000 th of a micron called “Nanoleakage”.
This type of bonding results with the bonding systems containing hydrophilic resin such as HEMA, which
tolerate moisture.
This clinical technique commonly reffered to as wet bonding has been introduced by Kanca and Gwinett,1992.
In acetone containing primers, when the acetone comes in contact with water; the bonding point of acetone is raised
and boiling point of water is lowered (AZEOTROPHISM),which causes evaporation of both the acetone and water and
resin is left behind.
Alternatively conditioned dentin may be are dried and remoistened with water or an antibacterial collection
such as chlorhexiden.e Also an aqueous sollution of HEMA (35%) (Aquaprep BISCO) are affective for compensating
the dryness induced on dentiin surface by air drying.
Over wetting phenomenon
When amount of water is present on dentine surface, this may interfere with the bonding because when
primer is applied the solvent evaporates leaving the resin, if water is not completely replaced by primer,
polymerization is affected.
In such conditions excessive water causes phase separations of hydrophobic and hydrophilic components
resulting in blister and globule formation at the resin dentin surface.
Advantages of wet bond
It is a technique sensitive procedure. Firstly, acetone quickly evaporates from the primer bottle, so that bottle
should be immediately closed and the dispensed solution is should be applied immediately on the etched surface.
The evaporation of solvent will increase the ratio of monomers to the acetone solvent that will have an effect
on the eventual permeability of monomers in the exposed collagen network.
To privent this, primers are be available in pre-dosed single patient use capsules Ex Primer and Bond NT
Quix (Dentsply).
In contrast to adhesive systems that provide acetone based primers and show a restricted “window of
opportunity” as far as precise amount of water that should remain post-conditionally on the dentin surface for efficient
bonding to be achieved, adhesive systems that provide H2O-based primers appear less technique sensitive and bond
equally well to varying degree of surface dry and wetness. Bonding to dry dentin has the advantage of being the
clinically accepted and utilized standard used by most clinicians.
ADHESIVES
The resin component of a bonding system consists of a combination of resins such as BIS-GMA or
otherdimethacrylate resins.These penetrate the primed dentin and co-opolymerize with the primer to form a hybrid
layer.Some of these systems may contain fillers ,which may be silica or glass,or fillers of nano size.
This is the final step of bonding process; application of adhesive layer. Spreading of the adhesive resin over the
surface to which it is bonded should be done preferably with a brush rather than air spray. The adhesive is copiously
placed and evenly spread with a brush tip that can be separately squeezed out between a paper tissue. The optimal
thickness of adhesive is about 100m when placed in a sufficiently thick layer, the adhesive resin may, due to its
relatively high elasticity, acts as a stress relaxation buffer. This will absorb by elastic elongation, in part, the tensile
stresses imposed by polymerization contraction of the resin composite subsequently placed over the adhesive resin.
The polymerization contraction stress generated during the placement of composite restoration was found to
be absorbed and relieved by the application of an increasing thickness of low-stiffness adhesive. Blowing the adhesive
resin layer may reduce its thickness too much, decreasing its elastic buffer potential to relieve polymerization
contraction stress.
A filled adhesive has
Greater film thickness
Greater ability to flex
Helps dissipate stress of polymerization
Ex- Prime&Bond NT 4%
Optibond Solo Plus 15%
AMALGAM BONDING
Although retention and resistance forms were the hallmark of traditional amalgam preparations, modern
conservative philosophy and the desire to extend the use of amalgam to more extensive restorations have stimulated a

search for improved methods for retaining amalgam restorations. Mechanical adjuncts, including threaded prins or
retentive groves placed in dentin have served well for years towards these ends.More recently,bonding agents
employing M-R-X type coupling agent have achieved some clinical success where,
M = a methacrylate molecule which bonds to the composite resin
R = a linking molecule
X = a molecule which interacts with the dentine surface or smear layer
One system uses 4-methacryloxyethyl trimelliate anhydride (4-META). However, the mechanism for
responsible foe the bonding amalgam to resin is predominantly mechanical in nature. It is produced by condensing
the plastic amalgam mass into an inset adhesive resin layer, thus producing an intimate mechanical interlocking as
macroretentive areas are produced within the resin after the resin has polymerized.
The results of controlled clinical trials have been mixed, but surely amalgam-bonding agents have placed an
adjunct to conventional retentive areas if properly employed.
BIOCOMPATIBILITY OF DENTIN BONDING AGENTS
Bonding of restorative materials to tooth structure ,either directly or through an intermediate has been a prime concern
of dental researchers and scientists for a long time.A material with good bonding capabilities will minimize gap
formation and microleakage between the tooth and the restoration and thereby reduce the risk of recurrent caries and
pulp injury.
A good understanding of the biological aspects of DBA is important for their proper use in dental practice.Many
dentin bonding agents require total or partial removal of the dentinal smear layer,resulting in opening of the dentinal
tubules,which may increase the dentinal permeability of the dentin extensively.An increased dentin permeability
enhances the possibility of pulp insult ,either by bacterial products diffusing into the pulp ,or by cytotoxic leachables
from the restorative material,since we know that some components of these adhesive systems are capable of
penetrating dentinal tubules upto 200-300m in pulpal direction.
Boilogical testing of DBA is a delicate and complex process.Unlike most dental materials dentin bonding systems are
made up of more then one material.Usage testing of DBA is further complicated by the fact that physical properties of
the test material may influence the results.Poor bonding leading to gap formation,thus allowing bacterial
ingrowth,may lead to an adverse pulp response which could be a result of an effect of the test material,of the
bacteria,or of a combination of both.All this may complicate yhe intepretation of results.
SUMMARY and CONCLUSION
Quoting from the Broadway musical “South Pacific”, "If you don't have a dream, how are you going to have that
dream come true?" Although reality almost always seems to fall short of conceptualization, a variety of dental
researchers have, in their separate ways, brought a long-standing dream to fruition -- that of providing the profession
with adhesives that can effectively bond dental composites to dentin and enamel simultaneously. Perfection has not
been achieved by any of them and much hard work remains as they seek to improve their various systems. But, given
the high tensile strength of dentin (Bowen & Rodriguez, 1962), the progress made in the last decade, and the currently
recognized need for dentin as well as enamel bonding, it is reasonable to expect that before the end of this decade the
intensive and extensive research efforts will succeed in providing clinicians with completely satisfactory materials and
methods for preventive and restorative dentistry by way of adhesive bonding to both dentin and enamel. This
dissertation comprehensively describes a number of dentin bonding systems already available to practitioners that are
beneficial for increased versatility toward improving the performance of restorative materials. The question of which
current dentin bonding system has the best evidence supporting it remains unresolved; the clinician is called upon to
put each system on trial before deciding which one is most suitable.
References
1. Al-Dawood,Wennberg
Biocompatibility of dentin bonding agents
Endodontics and Dental Traumatology, 1993:9:1-7
2. Andrew Watts,Robert C Paterson,Gordon B Gray
A review of current proprietary bonding systems
Journal of Restorative Dentistry,1991:56-60
3. Asmussen E
Chemical and physiochemical aspects
Operative Dentistry Supplement, 1992:5:68-74
4. Ayesgul Olmel,Tezer Uluru

Bond strength and clinical evaluation of new dentinal bonding agent to amalgam and resin composite
Quintessence Intenational ,1992:23:135-141
5. B Van Merbeek,M Vargas,S Inoue,Y Yoshida,M Peumans, P L ambrechts,G Vanherle
Adhesives and cements to promote preservation dentistry
Operative Dentistry Supplement ,2002:6:119-144
6. Bertolotti R.L
Conditioning of dentin substrate
Operative Dentistry, Supplement 1992:5:31-36
7. Butler W.T
Dentin extecellular matrix and dentinogenesis
Operative Dentistry ,Supplement ,1992:5 522-528
8. David H Pashley
Permiability of dentin to adhesive agents
9. Dietsch D
Influence of the restorative technique of new adhesives on the dentin marginal seal and adaptation of resin composite
class II restorations,in vitro
Quintessence International, 1995:26:25-30
10. David Eick,Scott J.Robinson,Charles M.Cobb,Robert p. Chappell,Paulette Spencer
The dentinal surface:its influence on dentinal adhesion.Part III
Quintessence International, 1992:23:43-51
11. D H Pashley, J A Horner,P D Brewer
Interaction of conditioners on the dentin surface
Operative Dentistry Supplement,1992:5:137-150
12. Edard J Swift Jr.
Bonding to enamel and dentin.A brief history and state of the art
Operative dentistry,1995:25:95-110
13. I Eystein Ruyter
The chemistry of adhesive agents
Operative Dentistry,Supplement, 1992:5:32-43
14. Garyson W .Marshall Jr.
Dentin: Microstructure and characterization
15. Gordon J Christensen
Clinical factors affecting adhesion
16. Hugo Retief
Clinical applications of enamel adhesives
17. J R Holtan,G P Nystrom,R A Phelps,T B A nderson,W S Becker
Influence of different etchants and etching times on shear bond strength
Opeartive Dentistry,1995:20:94-99
18. John Kanca III
Resin bonding to wet substrate.II.Bonding to dentin
Quintessence Intenational,1992:23:39-41
19. Jorge Peridago
Dentin bonding as a function of dentin structure
The Dental Clinics Of North America,2002:277301
20. Karl F.Leinfelder

Acid etching of dentin:too early to recommend
Quintessence International,1992:23:4
21. M.A.Marzouk,A.L.Simonton,R.D.Gross
Operative Dentistry- Modern theory and practice,Acid conditioning of suface enamel:181-183
22. N.Nakabayashi,M.Ashizawa,M.Nakamura
Identification of a resin-dentin hybrid layer in vital human dentin created in vivo:durable bonding to vital dentin
Quintessence Intenational,1992:23:135-141
23. Robert C Paterson, Andrew Watts
The dentin smear layer and bonding agents
Journal of Restorative Dentistry,1990:19-25
24. Sturedevant C M
The art and science of operative dentistry: Dental Adhesion
Pg:241-248

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