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Adhesion of restorative material to mineralized tooth structure has been a goal of dental researchers for many years. Accomplishing such a bond has many principle advantages like: 1. Retention of restoration, 2. Conservation of tooth structure, 3. Elimination of marginal microleakage, 4. Reinforcement of remaining tooth structure 5. Increasing the clinical life time of restorations.

Due to lack of adhesion between dental restorative resins and tooth structure, microleakage of salivary components and bacteria occur, which may lead to: i. Marginal staining. ii. Breakdown at the margins of the restoration interface.

iii.Secondary caries.
iv.Post operative sensitivity. v. Pulp pathology.


Acid-Etching- Process of roughening a solid surface by exposing it to an acid and thoroughly rinsing the residue to promote micromechanical bonding of an adhesive to the surface. Adhesion- A molecular or atomic attraction between two contacting surfaces promoted by the interfacial force of attraction between the molecules or atoms of two different species; adhesion may occur as physical adhesion, chemical adhesion, mechanical adhesion (structural interlocking) or a combination of all types. Adhesive- Substance that promotes adhesion of one substance or material to another. Adherend- A material substrate that is bonded to another material by means of an adhesive.

Adhesive Bonding- Process of joining two materials by means of an adhesive agent that solidifies during the bonding process. Dentin Bonding- The process of bonding a resin to conditioned dentin. Dentin Bonding Agent- A thin layer of resin between conditioned dentin and the resin matrix of a composite. Dentin Conditioner- An acidic agent that dissolves the inorganic structure in dentin, resulting in a collagen mesh that allows infiltration of an adhesive resin. Hybrid Layer- An intermediate layer of resin, collagen, and dentin produced by acid etching of dentin and resin infiltration into the conditioned dentin.

Microleakage- Flow of oral fluid and bacteria into the microscopic gap between a prepared tooth surface and a restorative material. Primer- A hydrophilic, low viscosity resin that promotes bonding to a substrate, such as dentin. Resin Tag- Extension of resin that has penetrated into etched enamel or dentin. Smear Layer- Poorly adherent layer of ground dentin produced by cutting a dentin surface. Wettability-Relative affinity of a liquid for the surface of a solid. Wetting- Relative interfacial tension between a liquid & the solid substrate that results in a contact angle less than 900.

An adhesive joint is the result of interactions of a layer of intermediate material (adhesive) with two surfaces (adherends) producing two adhesive interfaces. . CLASSIFICATION The interactions which occur at the interface are classified generally in terms of types of atomic interactions which may be involved. Adhesion is classified as: 1. Physical. 2. Chemical. 3. Mechanical. Micro Macro

Physical bonding involves Vander waals or other electrostatic interactions that are relatively weak. It may be the only type of bonding if surfaces are smooth and chemically dissimilar.

Chemical bonding involves bonds between atoms formed

across the interface from the adhesive to the adherend. Because the materials are often dissimilar, the extent to which this bonding is possible is limited and the overall contribution to bond strength is normally quite low. Mechanical bonding is the result of an interface that involves undercuts and other irregularities that produce interlocking of the materials.


The oral hard tissues and their environment are complex. In general, the following factors can play major or minor roles in achieving adhesive bonds: 1. Wetting 2. Interpenetration (formation of a hybrid zone) 3. Micromechanical interlocking

4. Chemical bonding

Wetting is essential for the success of all other adhesion mechanisms. An

adhesive cannot form micro mechanical interlocks, chemical bonds, or

interpenetrating networks with a surface unless it can intimately contact the surface, spread onto the surface, and fill microscopic and

submicroscopic irregularities. These conditions are achieved if the

adhesive wets the surface. Although wetting is an essential requirement for intraoral adhesion, it is not sufficient to ensure durable bonding. For

example, one can readily form strong, durable bonds between sheets of
plate glass by using an epoxy resin. This combination involves no primary chemical bonding between adhesive and adherend, no micro

mechanical interlocking, and no interpenetration. However, one cannot

expect the same result when tooth structure is the substrate.

Wetting of tooth structure alone does not achieve lasting intraoral bonds because the principal substrates (adherends), enamel and dentin, are hydrated, hydrophilic, and permeable to water. Such adherends require a hydrophilic, hydrolytically stable adhesive for wetting to occur. However, even if the surface is initially dried before adhesive application, diffusion results in one or more monolayers of water that strongly bond to both the tissue and the adhesive. Unfortunately, water has a very low shear strength, so the net shear bond strength between two perfectly flat surfaces is insignificant.


Perhaps the most significant discovery in dentistry during the last three decades is that of Dr. Michael Buonocore in 1955. Working in New York, he discovered that the bonding strength between human enamel and acrylic resin could be tremendously enhanced by exposing the tooth to a mild acidic solution before applying resin to the enamel surface.

He etched the enamel surface with acids and then placed an acrylic

restorative material on the micromechanically roughened surface. The

monomers of the acrylic resin wet the etched surface, flowed into the etch pits, and generated retentive resin tags. One of the surface conditioning agents he used, phosphoric acid, is still the most widely used etchant today for bonding to enamel and dentin.

In his first experiments Dr. Buonocore was actually following the lead of industry. By the mid-1950s it was already commonplace to pre-treat surfaces, such as metals, with

phosphoric acid before applying resins or paint. In fact, his

original trial used 85% phosphoric acid, which had by then

become the industrial standard.

Almost every case of dental adhesion is based primarily on mechanical bonding. Chemical bonding may occur as well, but generally makes only a small contribution to the overall bond strength. Common method for producing surface roughness for better mechanical bonding is to grind or etch the surface. Grinding produces gross mechanical roughness but leaves a smear layer of hydroxyapatite crystals and denatured collagen that is approximately 1 to 3 microns thick.

Acid etching or conditioning dissolves this







undercuts on the surface to create an opportunity for mechanical bonding. If the interlocked adhesive and adherend with dimensions less than about 10 microns, then the situation is described as micro-

mechanical bonding.

It is fortunate that there is a difference between the resistance of the enamel prisms and the inter-prismatic enamel to acidic attack. Thus, as Dr. Buonocore discovered, placing a weak acidic solution on the enamel surface causes a differential etch rate between these two areas; this results in

an irregular and pitted surface.

Type II

Type I & Type II

Acid etching of enamel is one of the most effective ways to improve mechanical bonding and to ensure sealed interfacial gaps. This procedure

has markedly expanded the use of resin-based restorative materials

because it provides a strong bond between resin and enamel, forming the basis for many innovative dental procedures, such as resin-bonded metal

retainers, porcelain laminate veneers, and bonded orthodontic brackets. It

has also solved, to a great extent, all of the previous problems that plagued resin-based restorations, namely, marginal staining caused by

interfacial leakage

Phosphoric acid at a concentration between 30% and 50%, typically

37%, is the preferred etching agent. Concentrations greater than 50%

result in the deposition of an adherent layer of monocalcium phosphate monohydrate on the etched surface, which inhibits further dissolution.





as an aqueous gel to allow precise placement over a specific area. These gels are often made by adding colloidal silica (the same fine particles

used in microfilled composites) or polymer beads to the acid. Brushes

are used to place the acidic gel material, or the acid may be supplied in a disposable syringe from which it can be expressed onto the enamel and

dentin. During placement, it is important to be aware of the risk for air

bubbles that may be introduced at the interface. If these voids remain, these regions will not be etched. The optimal application time for the

acid is generally believed to be 60 to 90 seconds.

When properly etched, the tooth should exhibit a dull, frosted, matte finish. Under-etching results in a tooth that retains its gloss. Over-etching

results in a surface chalky in appearance due to the formation of an

insoluble salt during the etching process. The popular current choice is orthophosphoric acid, which is commercially available in concentrations ranging from approximately from 30% to 65%.

This surface must be kept clean and dry until the resin is placed to form a sound mechanical bond. Although enamel etching raises the surface energy of the enamel, contamination can readily reduce the energy level of the etched surface. Reducing the surface energy, in turn, makes it more difficult to wet the surface with a bonding resin that may have a higher surface energy than that of the contaminated surface. Thus even momentary contact with saliva or blood can prevent effective resin tag formation and severely reduce the bond strength. Another potential contaminant is oil that is released from the air compressor and transported along the airlines to the air-water syringe. If contamination occurs, the contaminant should be removed, and the enamel should be etched again for 10 see.


Physiochemical properties of Enamel and the effect of acid etching: # Inorganic content : 96-97 % by weight # Water : 4% # Organic Content : 1% Collagen Bonding to enamel is poor because organic pellicle covers the enamel surface. Etching raises the critical surface tension of enamel. The creation of such a high energy surface together with the increase in bonding area and surface roughness make the bonding of hydrophobic resins possible.

Physiochemical properties of dentin that complicate dentin adhesion

The ultrastructure and chemical composition of dentin does not permit micromechanical interlocking as occur with the enamel. Dentin consists 70% hydroxyapatite, organic material (Collagen) and 12% water. 18%

Etching of dentin leaves a sponge-like structure with little compression, tensile or shear strength (Standford 1985 ) .

Dentinal canals at the external surface of roots or near dentinoenamel junction have small diameters. Dentinal canals closer to the dental pulp become larger, older dentin has small dentinal canals. Dentinal bonding agents use some form of mechanical attachment into dentinal canals. In small canals attachment is less and in larger canals attachment is enhanced.

Dentinal smear layer and dentin permeability

When the tooth structure is worked with rotary tools, cutting debris is smeared over the enamel and dentin surfaces. (Pashley 1984 and 1988). EDTA was found to be the most potent conditioner in removing the smear layer and opening up the orifices of the dentinal tubules. Other Conditioners include:- citric acid, poly acrylic acid, Lactic acid, Phosphoric acid. (In vitro study). The depth of the smear layer depends on the type of instruments and the condition of irrigation employed normally varying from 1 to 5 mm (Elick and others 1970 Pashley 1984).


The intermediate link between dentin and/or enamel and unfilled resin is known as dentinal bonding or dentin bonding. The relatively thin resin layer is referred to as a dentin bonding agent. An important breakthrough in dentin bonding occurred when Fusayama et al (1979) used 37% phosphoric acid to etch both enamel and dentin. This study demonstrated that the procedure did not increase pulp damage and that it did improve the restoration retention substantially. A subsequent study by Nakabayashi et al (1982) revealed that hydrophilic resins infiltrated a surface layer of collagen fibers in demineralized dentin to form a hybrid layer consisting of resin-infiltrated dentin. Adhesion by Hybrid Zone/Layer:When the primer is applied to a properly treated dentin surface, they form micro-tags into the dentin substrate, there by creating a zone of primer/resin infiltrated dentin at the interface. Eg: All Bond II,, Scotch bond multipurpose, prime and Bond.

Ideally, dentin adhesives should be hydrophilic to wet the surface of

slightly moist, conditioned dentin. Because most matrix resins of composites are hydrophobic, the bonding agent should contain hydrophilic groups to interact with the moist dentin surface and hydrophobic groups to ensure bonding to the restorative resin. The key to adhesion is to develop hydrophilic monomers that can easily infiltrate the collagen mesh produced by etching dentin with an acid often called a conditioner.


Dentin bonding agents are often grouped into generations, based on their bonding procedures and the relative bond strength they could achieve.

First Generation bonding materials were far

more useful for enamel than dentin. These bonding agents were designed for ionic bonding to hydroxyapite or for covalent bonding (hydrogen bonding) to collagen. These materials

tended to be hydrophobic. With bond strength of

2 Mpa 6 Mpa, they had a tendency to debond within a short time. The bond strength, was limited by strength of the bond of the smear layer to the dentin.

Materials: A surface active comonomers, Nphenylglycine glycidyl methacrylate (Bowen, 1965) was developed that acted as a primer or adhesion promoter between enamel / dentin and resin materials by chelating with surface calcium. E.g. Cervident. Disadvantages 1. Poor bond to dentin familiar amalgam type retentive cavities. 2. Used only for small class III and class V restorations where there was adequate enamel in which to bond. 3. Post operative sensitivity in attempted posterior occlusal restorations.

Second Generation Dentin Bonding Systems

Performed better than the 1st generation products. The 2nd generation of dentin adhesives primarily used polymerizable phosphates added to BIS-GMA resins. Adhesives that used phosphate group to promote bonding to the calcium in mineralised tooth structure were referred as phosphate bonding systems. These materials had a weak bond to dentin (4 to 6 Mpa), hydrophobic. The bond strength was limited by relative attachment strength of the smear layer to dentin substrate.

Materials a) Clearfil b) Scotch Bond c) Prisma Universal Bond d) Dentin Adhesit Disadvantages 1. Weak bond to dentin 2. Mechanical retention form was still necessary since bond strength alone was inadequate. 3. Margins on dentin were problematic since the low dentinal bond strengths permitted extensive marginal microleakage. 4. Restoration failure occurred most commonly due to hydrolytic decomposition.

Third Generation Bonding Systems

A Newer generation adhesive system have
been developed that use a conditioning step on dentin in conjuction with a bonding agent. Bowen (1982) developed a multistep adhesive system. Importantly third generation adhesives were the frist to bond to metal and ceramics. Components are :
a) Dentin-conditioner b) Dentine primers / adhesive c) Bonding agent

Dentin Conditioners


Are agents that either modify or

remove the smear layer and subsequently interact with superficial dentin and rinsed off after application.

Chelators :- are used to remove the smear layer without

decalcification or significant physical changes to the underlying substrate.

Dentin Primer / Adhesive (Adhesion promoters)

A primer is an agent which enhances the wettability of a bonding agent onto the dentinal surface. The primer usually contains an adhesion promoter in a solvent such as water, ethanol or acetone

Fourth Generation Dentin Bonding System

The fourth generation dentin bonding system are characterized by hybrid zone formation in the dentin. The concepts of total etch and moist dentinal bonding (for acetone containing primers) are also hallmarks of the fourth generation materials.

Fifth Generation Bonding System

The current state of the art in bonding materials is the single component bonding systems. This system provide entire priming and bonding sequence in a single liquid and single bottle. Dentin adhesives are based on combinations of conventional hydrophobic resins such as BIS-GMA, together with hydrophilic resins and solvents. HEMA (Hydroxyethyl methacrylate) is often used as a hydrophilic monomer. Acetone, alcohol or a combination of both can be used as hydrophilic solvents. Several systems include water in various quantities to make the compound as an aqueous solution.

1) Prime & Bond 2) One Step Bond

3) Tenure Quick
4) Syntac single

5) Opti Bond

1) Dentin bond strength are well above 15mpa.

2) Post-operative sensitivity is extremely rare.

3) Some of the 5th generation systems have incorporated fluoride release and elastomeric components to improve marginal integrity. 4) Time saving, and simplicity of use.