Dentin bonding agents

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 provide improvement is it wise to pursue?

How we determine improvement depends on our paradigm, our view of the objectives of restorative dentistry. Traditionally, dentists have believed that slowing down the restorative cycle as much as possible is the ideal persuit. that challenges that paradigm. e have in the time

The earlier performance standard is centered on the concept of longevity. The longer the restoration lasts, the fever the number of times a tooth will re!uire 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.The main disadvantage of any of these restorations is "colour#. Increasing environmental conserns and public awareness for tooth colored materials have heralded patients to demand more esthetic, biocompatible materials such as composites, glass inomer cements and porcelain.

$f all the innovative esthetic materials available today, the direct placement of resin composite has assumed the current thrust in restorative dentistry .$ne of the principle advantages in the use of these resin composites is the bondalility to the enamel and dentin% which has been possible due to mostly improved bonding systems.

&entin 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 in dentistry is attributed to great scientists like 'ichal (uonocore, )afel (omen, *ubo *akabayashi, +usyama.

)ecent improvement in adhesive systems have generated a revolution in dentistry, placing adhesive restorations on the front stage.,linicians have been confornted with this continuous and rapid turnover is adhesive materials. There has been an ongoing 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 better.

This library dissertation discuses dentin bonding agents, with complete coverage of the bonding systems, hoping that this would help dental professionals in understanding bonding systems better.

HISTORY

&(A have developed over several decades. The various historical events, which

took place have led to our present day &(A. -./0 -.31&evelopment of epo2y molecule by ,astan 1&evelopment of glyerophosphoric acid dimetharylate molecule by &r.$scar Hagger. This molecule permitted seen adhesion to dentin. -.34 15sage of glyrerophosphoric acid dimethacrylate by 6ramer and 'clean 7earliest description of hybrid layer8 -.33 1(uonocore introduces etching of teeth any phosphoric acid% was he found that an acrylic resin binds well with etched enamel. -.39 1(uonocore pioneers the work on adhesion to dentin. Initial &(A developed was based on the glycerophospheric acid dimethacrylate molecule and bonds to hydrochloric acid etched dentinal surfaces, but bond strength diminishes greatly on immersion in water. -.3: 1(owen starts work on bis1phenol glycidyl methacrylate 7(I;1<'A8 resin systems. -.94 -.93 -.04 1(owen conducts first workshop on adhesive restorative dental materials. 1,auston describes how primers work. 1(owen, ,obb, )apson develop the multilayer adhesive system.

-.04 -.0: -..-..:

1*akabayashi reports the presence of hybrid layer. 1+usayama described the concept of total etching and bonding. 1=.6anca successfully promoted total etching 1+errari et al establish the bonding mechanism of one bottle adhesive system to condition dentin.

4>>>

1?valuation of bonding ability of si2th generation bonding systems done by +errari et al.

4>>/ -..-

1seventh generation by +errari et al. 1=. 6anca successfully promoted total etching.

Enamel

?namel is the hardest of the minerali@ed tissues of the body.

It covers the

anatomical crown of the tooth. This tissue is very brittle in nature but protects the underlying structure ie. dentin and pulp.

The inorganic component of enamel is principally appetite in its, hydro2yl, fluoro carbonate forms. ,alcium and phosphate are the two major inorganic elements

7(rudefold, steadmar and ;mith -.9>8 minor narration occurs is composition is with aluminum, barium, magnesium, strontium, radium and vanadium among others can be found in the little.

,rystallites are embedded is as organic matri2 with comprises less than -A of the nature of enamel 7?stoe, -.9/8 less than one half of the organic component contains protein high glycolic acid and sig anlt of proliferation and glucose contains protein. &uring minimi@ation of the crown, a significant shift occurs in the value of organic material. The amenoblasts produce large amounts of organic matri2 among early phases of enamel development, then as crown saturation proceeds, the number of organic matri2 decreases while the number of inorganic material issues and minirali@ation gradient 7,hable and &arling -.9>8 e2ists in mature enamel, thus, the outer portion of enamel is relatively more minerali@ed than the inner portions. H4$ e2ists in enamel in a significantly larger amt 7up to BA by value8. About 43A of H4$ is loosely bound to the crystallites.

A dynamic gradient anushing fluid e2ists bCw the pulp and oral environment 7(ergman -.9/8 in with enamel participates through its porous, permeable structures, but enamel is selectively permeable 7&arliag and $thers -.9-8 allowing the passage of H4$ and cons but including large molecules 7Doole, +achy and (erry, -.9/8.

Histo1chemical studies have shown the comple2 nature of the surface integument. This fully reacted low energy surface confers significance in the bonding e!uations, as does the traumatically or operatively imposed tissue. An understanding of the micro1morphological properties have been significant is remaining interactions bCw enamel and bonding agents.

Dentin &entin forms the largest portion of the tooth structure. It is removed by the enamel on the anatomical crowns and by root on the anatomical root internally it forms the walls of the pulp cavity.

The dentin comprise of dentinal tubule that are small canals that e2tend across the entire width of dentin, from &?=C&,T to the pulp. ?ach tubule contains cytoplasmic cell process 7=ames +iber8 of an odontoblast. ?ach dentinal tubule is lined with a layer of peri1tubular dentin that is much more minerali@ed than the surrounding inter1tubular dentin. The number of tubules increases from &?= 7-3>>>14>>>>Cmn 48 to the pulp 7B31 93>>>Cmn48. The dentinal tubules are filled with dentinal fluid which makes it a difficult surface to bond.

The chemical composition of dentin comprises of :3A inorganic 4>A organic and 3A H4$ and other materials. It is less minerali@ed than enamel but more

minerali@ed than cementum or bone. The minimal content of dentin increases with age. This mineral phase is composed primarily of hydro2yapetite crystallites. The organic phase is primarily collagen 7Type I with traces of type IE of8.

They consist of carbo2yl, amino, hydro2yl surface groups.

The other non1

collagerous constituents that can be found are dentin phospho1protein, sialoproteins of ostecalcins. &entin permeability is highly variable.Eariation in permeability may arise from tubular irregularities associated with mineral deposits, organic components of the

odontoblasts processes. An outward flow of dentinal fluid occurs because of a small but positive pulpal pressure 7->1-3 mm Hg8.

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 dentin7Transdentinal Dermeation8. )esin penetrates into tubules to form tags that can contribute to resin adhesion. 'ore important factor is permeation of resin intointer1tubulardentin7Intra1dentinalDermeation8. &entinal permeability is reduced with age and also in caries affected dentin as the

lumina becomes narrow or may get obliterated by deposition of intra1tubular crystals and deposition of irregular scleroticCreparative dentin.

ADHESION Adhesion is definition by to FAmerican society for testting and materials as FA substrate capable of holding material togetherG. The word adhesion is derived from the Hatin word adherer, which means FadG1to andG hearerG to stuik. Adhesion refers to the attraction bCw the atoms and molecules at the contacting surface of different materials 7&e (rayer et al -.3-, ake -.048.

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 Cbonding 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 re!uirement for any of these interphase phenomenons to take place is that two materials being joined must be sufficiently close and in an intimate contact and besides this sufficient wetting of the adhesive only occurs if its surface tension is less than the surface energy of the adherent. If the adhesive had a high surface

tension, then it would roll up into droplet and not wet the surface.

(ased on this theory of melting 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 hydro2yapetite without has a high free surface energy whereas dentin has a low free surface energy because it is composed of two distinct materials hydro2yapetite and collagen. 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 ade!uate wetting of the adhesive. 'oreover, 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 pretreated prior to bonding procedures to increase the free surface energy. Types of Adhesion Ean *oort in -..B suggested that one or more of the following mechanisms can create an adhesive bondI 1. Me hani al Adhesion

Here, retention is by the interlocking of one phase into surface of another. This type of adhesion can be due to a. !eomet"i al effe ts These are caused by microscopic porosity or roughness of the surface ie.mechanical locking provided by undercuts, grooves etc.

b. Rheologi al effe ts This is caused by flow of materials in both li!uid and semisolid phase 'echanical adhesion also referred to as micro mechanical adhesion ,results from the presence of surface irregularities that give rise to microscopic undercuts. The li!uid adhesive can penetrate these undercuts and once set is locked in them. A prere!uisite 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.

The adhesive disengages from the substrate by fracturing because it cannot be withdrawn from the undercut. This is not unlike the concept of retention used for

placement of restorations e2cept that it occurs at a microscopic level. However, one important difference is that good wettability is not a per!uisite for micro1retention

whereas for micro1mechanical interlocking it is of paramount importance. ?2amples of micro1mechanical adhesion oneI a. )esin to enamel bond b. )esin to ceramic bond for veeners and inlays c. )esin metal bond for resin bonded fi2ed partial denture

II. #hysi al Adhesion hen two surfaces come in close pro2imity to one another secondary forces of attraction can be generated through dipole1dipole 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 is a permanent bond is desired. It follows that non1polar li!uids will not readily bond to polar solids and vice1verse, because there is no interaction between the two substances at the molecular level even if there is good adaptation. A familiar e2ample of this problem is the inability of hydrophobic silicone rubber impression materials to adapt to the hydrophilic moist surfaces of the soft tissue 7This problem is overcome by the use of surfactant8. III. $hemi al Adhesion

If an adsorbed molecule dissociates on contact with a surface and constituents alone rearrange themselves in such a way that as for covalent, a strong adhesive bond can result. This form of adhesion is called as chemisorption. The features that

distinguishe 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 re!uire identical reactive groups on both surface.

,ovalent bonding occurs for an isocyanate adhesive which can bond to soft tissues via surface hydro2yl and amino groups. Another such bond is believed to occur bCw the hydro2yl groups of the glass polyalkonate and the calcium ions in the enamel and dentin.

In some instances the formation of a chemical bond will not take place spontaneously. This is the case with the metal to metal bond where high temperatures ellicited by soldering, bra@ing or welding are needed to encourage the formation of a bond .Another e2ample is the porcelain to metal bond with is formed when the ceramic o2ide fuses with the o2ides on to the metal surface when the restoration is faces high temperature.

I% Adhesion th"o&gh mole &la" entanglement

;o far it has been assumed that there is a distinct surface bCw the adhesive and the substrate. In effect, the adhesive as adsorbed on the surface and can be If the substrate is permissive to adhesive is able to

considered surface active.

penetrate through the surface of the substrate and absorb into rather than adsorb oncto the substrate. If the absorbing molecule is a long chain molecule or better still forms polymers within the pretreated layer, the resultant enlargement bCw the adhesive and the substrate is capable of producing very high bond strength.

This approach is being adopted for resin bonding system.

The coupling agent utili@es the concept of hydrophilic and hydrophobic groups i.e. it consists of a bi1functional molecule one part of outers into a chemical union with the tooth surface whilst the other attaches to resin. The coupling agents have basically the formula. M'R'( '1 'ethacrylate group, which eventually becomes bound to the resin by copolymers. J1 represents a reactive group with interacts with the tooth surface. The reactive groups are end groups. )1 is the clearing and spacing group spacing group must be able to provide the necessary fle2ibility to the coupling agent to enhance the potential for bonding of the reactive group. If the molecule is e2cessively rigid, the

ability of the reactive group to find a satisfactory conformational arrangement is jeopardi@ed ?g1etyl C o2ypropyl.

In *1 Dhenyl, glyine glycidyl mehacrylate a shelate bond is found between the *1 phenyl glycine group is the calcium of the tooth, while the methacrylate group becomes incorporated into the resin during polymeri@ation. Another coupling agent with works by chelating with adhesive is B1'?TA.

(ond strength of these coupling agents can be increased by pre p2 with certain mordant sons such as ferric and aluminum cons in the form of a!ueous solutions of their chloridesCo2alate salts. A strongly bond surface layer concentrated in cons ;ystems based on the

capable of reacting with the chelating species is formed.

complied used of mordant cons and coupling agents are non1becoming available. The e2act mechanisms or role of these mordent cons is not known. (ut it is possible that the ionic solutions are supplying acting as weak acid without solubli@e and re1precipitate the dentin smear layer. In some cases the acid may etc the dentin, opening up the dentinal tubules and encouraging mechanical attachment.

A procedure with can be classified as multiplayer system has been suggested. This system enacts the )2 of the mechanically prepared cavity with a ferric o2alate solution and an acetone solution of *D<1<'A or *TA1<'A. An acetone solution of D'&' 7the reaction product of promellitic dia2hydride and 41 hydro2yl

ethylmethacrylate8 is placed and surface is air brown. +inally, the composite restorative materials is inserted and polymeri@ed.

The chemistry of such )2 is based on the assumption that the )2 with ferric o2alate solution initiates several reaction with the smear layer, resulting is a process layer cross1linked with metal ions. The layer constitution insoluble icon phosphospate and calcium o2alate attached to a continuous structure.

&uring )2 with *D<1<'A these monomer are bonded to icon 7III8 ions by coordinative bonds. A continuous film is formed by polymeri@ation of the methacrylate groups *D<1<'A contains ben@ers wings rin#s in II electrons. &uring )2 with D'&' monomer, this monomer is bonded to *D<1&'A by II comple2 or change transfer comple2 formation. The disadvantage of this system is discolonathprine due to reaction products of ferric o2alate. In FtenureG ferric o2alate has been replaced with aluminum o2alate.

$ther coupling agents with primarily bond to the inorganic component of dentin contain reactive phosphate groups. The interfaced bond is stabili@ed through

attractions bCw the negative changes of o2ygen on the dentin surface.

The bond strength to. dentin produced by this type of adhesive is typically around 3'DA although it is not certain how double this bond is in moist environment.

This )1$1D bond is thought to becomes hydroly@ed leading to a gradual reduction in strength '1)1J, here JK $1D

,oupling agents utili@ing this concept of hydropholic and hydrophilic groups are the monomers based on phosphates or phosphonates. The hydrophilic D$ B group is thought to interact with the calcium cons of dentin.

All the systems are basically adhesive molecules with a potential for calcium bonding. It can be decided into / groups -8 Dhosphate based adhesive '1)-1D$LM 48 Adhesive based on amino acid '1)41*M1)/1,$$H /8 Adhesive based on dicarbo2ylic acid '1)B1,$$H ,$$H All these involve attraction between negative changes on the adhesive and positive changes on the tooth calcium ions.

$hemist"y of adhesi)e systems

&entin bonding systems contain monomers that have hydrophilic and hydrophobic groups these provide a stable back with the dentin and the restoration.

The chemistry of adhesive agents can be e2plained as. ,hemical adhesion. Adhesion by coupling agents. Adhesion by grafting reaction.

$HEMI$A* ADHESION There are two types of chemical adhesion Drimary valence +o2es ,ovalent bonds ,o1ordinative bonds Ionic bonds.

;econdary valence fo2es Intermolecular adhesion 7Eander Hydrogen bonds. aal#s fo2es8

ADHESION +Y $O,#*IN! A!ENTS

;ampling agents utili@ing the concept of hydrophobic and hydrophilic groups are the monomers based on phosphate or phospho2ate.

The hydrophilic D$B group interacts with ,aN ions in dentin. adhesion us seen to occur with the non1electrolyte adhesion.

This type of

(onding can be

accomplished to the organic part of the dentin hydro2yapetite, or to the organic part else of coupling agents for bonding leads to only minor improvement in the bond strength. $ne coupling agent was /1methacryloylo2y propyl trimetho2ysilane. Another coupling agent was a butylanylate acrylic and copolymer with free carbo2ylic acid groups. *D<1 <'A is another coupling agent used.

I. $lini al fa to"s affe ting Adhesion Sali)a"y o" blood ontamination &ifficulty in controlling saliva or blood while accomplishing restorative dental therapy is a significant challenge. These contaminants act in a negative manner for adhesion. Although dentin is a not substance, the constituents of saliva and blood create an environment that can destroy dentin bonding. It has been prove that if contamination soon after etching the bond will fail while if contamination occurs after enamel and dentin surface are etched and a bonding agent has been used over these surfaces, the bond will not be compressed. )ubber dam and other dry field acids should be used to prevent contamination.

Moist&"e and Oil ontamination f"om Handpie e

ater leakage fro ioroter hand piece or air H 4$ syringes is an unrecogni@ed problem in most situation. The moisture of H 4$ with restorative or bonding resin is interferes with adhesion of bonding agent to the tooth stuitane. The oil contamination may be due to oil coming from air compresses without not maintained well, ,ontamination with oil provides compredictable with oil provides im1 predictable clinical results and potential clinical features.

S&"fa e Ro&ghness of tooth st"& t&"e Increased surface area created by surface roughness results in cutting bonds with dentin mechanical retention may be increased by the microscopic roughness produced on dentin or enamel by rotary cutting instrument tungsten carbide thus when used create more irregular surface than diamond layers.

Me hani al &ndents in tooth p"epa"ation The mechanical underints placed in the tooth structure hold the restorative material from bodily displacement from the preparation, microscopic movement caused by thermalC polymeri@ation influences. This type of retention is further argument with the cement generation of &(A.

Dentinal anal ha"a te"isti s &entinal canals at the e2ternal surface of tooth roots or near the &?T have small diameters. As dentinal canals are observed loser to the dentinal pulp, they become larger. $lder dentin has small dentinal canals, while younger dentin has larger

dentinal canals.

;uperficial abounded dentin may have included canals.

If the

canals are small, attachment is less and vice versa.

#"esen e of pla-&e. al &l&s. e/t"insi stains0deb"is Any enamelCdentin surface that re!uires bonding must be scrupulously cleared before the bonding procedure begins. Dla!ue present on the tooth surface prevents etcher with /:A phosphoric acid. Denetration of pla!ue by the acids used in &(A is not possible and will result in a clinical adhesive failure. Tooth surface stains and dental calculus if not removed will not permit bonding.

#"esen e of basis on line"s on 1 The presence of varnish eliminates the potential to bond restorative material to the tooth surface. Hiners may result in creating moderate bonds with dentin but the bond strength is significantly lower than that created by placing seen on acid etched enamel surfaces.

Tooth dehyd"ation ?ver drying the tooth preparation before placing bonding agents should be considered to be a negative factor. &rying only till the obvious shine of moisture is a good clinical guide. Dentin +onding Agents The &(A are di or multifunctional organic molecules that contain reactive group, which interact with dentin and the monomer of the restorative resin.

,o NA & A

,omponents of &(A

,onditioner Dremier Adhesive

Re-&i"ements of D+A Ideally, dentin1bonding system should have ;ufficient bond strength, optimum --14> 'pa (e compatible with dental tissues Drovide in immediate permanent high strength bond to dentin 'inimi@e micro1leakage at the margins of the restoration Drevent recurrent caries and marginal staining ?asy to use and less techni!ue sensitive )easonable shelf life ,ompatable with all resins *o reduction in bond strength when applied to moist surface *o potential for sensiti@ation of patient on gerator

#"oblems in +onding to dentin

The developments of adhesives that adhere to dentin have still been and still remain a challenge to researchers. &entin consists of 3>A of volume inorganic HAD, />A organic material and 4>A volume of fluid. &entinal HAD is randomly arranged in an organic matri2 The high fluid content of dentin places certain re!uirements on restorative dental material 7resin are hydropholic8. The tubular nature of dentin provides a valuable area through which the dentinal fluid might flow to surface and adversely affect adhesion. ;ucrosed dentin if present is difficult to penetrate 7results from aging or mild irritation and causes a change in the structure of primary dentin is the peri1tubular dentin becomes wider, gradually filling the tubular with calcified material. The areas are harder, denser, less sensitive8 Dresence of inter1tubular and peri1tubular dentin, each tubular is suspended by a collar of gyper1minerali@ed dentin called peri1tubular dentin. The less minerali@ed dentin between the tubules is called inter1tubular 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. Dermeability of dentin differs at different sites variation is permeability may arise due to tubular irregularities associated with mineral deposits. It also increases resin the pulp and pulp horns than the adjacent areas. $*ASSI1I$ATION O1 D+A

-. &epending on chemical composition 4. According to generation /. According to treatment of linear layer B. According to chronology, chemistry and sear bond strength 3. According to mode of curing 9. According to their adhesion strategy towards enamelCdentin or on the basis of number of clinical application :. According to type of solvent

1. A

o"ding to thei" hemi al omposition 2$"aig3 Dolymethanes Dolyacrylic $rganic phosphonates 'ellitic anhydride and methylmethanylate 7'1'?TA8 Hydro2yethyl methacrylate N <lutealdehyde 7H?'AN<A8 +erric o2alate N *<D1<'A 7*1phenyl glycine and glycidyl methacrylate8 ND'&' pyromethalic dianhydride and 4H?'A8

4. On the basis of t"eatment of smea" laye" The smear layer of limited strength, so it must be either removed or modified before application of bonding agent a. Remo)ed E/ample4 ' Tenure 7nitric acid8

'irage bond ,learfil liner bond systems

b. #"ese")ed ?2ampleI 1 ;cotch ond dualina Drisma universal bond

. Modified ?2ampleI 1 All bond ;cotch bond 4 J) bond

I% on the basis of shea" bond st"ength 2Eli5 et al.3 Included dentinal adhesives without produce shear bond strength of 31:'pa ?2ampleI 1 &entin adhesit ;cotch bond dual cure <lynia

$atego"y 6 Included the e2perimental and commercial products derived from (owers work with ferric and aluminium onalalates and have produced shear bond strength between 01-B 'pa ?2ampleI 1

Tenure 'irage bond

$atego"y 7 Included dentinal adhesives, without produced shear bond strength values of about -:14>'pa ?2ampleI 1 ;uper bond ;cotch bond 4 ;cotch bond multipurpose All bond

7&ecreased failure was cohesive in nature8

%. A -

o"ding to thei" mode of &"ing ,linical sure

?2ampleI 1 Amalgabond plus

1 Hight cure ?2ampleI 1 $ne bond <lunia comfort bond

1 &ual cure ?2ampleI 1

,learfil linear bond 4E Drime and bond *T dual cure

$atego"y III4 Included 7dentinal adhesives, which produced shear bond strength values of about. -:14> 'Da. ?2I ;uper bond ;cotch bond 4 ;cotch bond multipurpose All (ond The failure was mainly cohesive in nature A 1. ?2I 6. o"ding to thei" mode of &"ing $hemi al &"e Amalgam bond plus *ight &"e

?2I $ne (ond <luma comfort (ond 7. D&al &"e ?2I ,learfil liner (ond 4E Drime and (ond *T &ual cure

On the basis of !ene"ations4 1.1'!ene"ation Dentin +onding Agents &eveloped by (owen 1 -.93. Agents used in this generation areI

a. b. c. d.

<lycerophosphoric acid dimethacrylate, ,yanoacrvlates *D< 1 <'A Dolyurethanes (uonocore four decades ago found that a resin containing <DA1'A could bond to

Hcl etched dentin surfaces. However, the bond strength was by water. To overcome this problem (owen synthesi@ed *D<1<'A a surface1active comonomer that theoretically produced water resistant bonds. *D<1,, 'A acted as an adhesion

promoter bCn the toot1h structure and resin material by chelating with surface calcium. Disad)antages4 Door clinical results Hydrolysis of <DA1&'A in oral environment &ifficulty 1 in bulk polymeri@ation of cyanoacrylates Instability of *D<1<'A in solution Hydrophobic resin How bond strength 74.- 1 4.0 'pa8 E/4 ,ervident 7;.;. hite ,o.8 +irst commercially available dentin bonding agent. ,osmic bond 7Amalgamated &ental8 Dalakav 76ul@er, 5;A8 6. II !ene"ation Dentin +onding Agents4 In general, the second1generation dentin bonding agent was much improved compared with the first generation. These were developed during the early -.0>Os.

'ost of the agents were primarily 1 7polylmeri@able phosphates in (I;1<'A8 resin -. Halophosphorous esters of (I;1<'A. bonding systems. 2. Dolyurethane based compounds were also used. Hence they were called as phosphate1

The bonding mechanism involves a surface wetting Dhenomenon as well as ionic interaction bCn phosphate groups and dentinal calcium. The --1generation systems re!uired a smear laver intact. This was to create a ,aN rich layer where the phosphate can combine with ,aN. Disad)antages4 1. How bond strength 7-1/ 'pa8 7studies by )elief and others -.09 and ;olomon P (eech8 4. Hydrolysis of phosphate ,aN 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. E/4 ;cotch bond dual cure 7O$' &ental8

(ond Hite, 76err8 &entin (onding Agent 7=ohnson P. =ohnson8 Drima 5niversal ,reation &entin (onding Agent ,learfil 76uraray8 7. III gene"ation Dentin +onding Agents

&eveloped in mid -.0>s

The third generation dentin adhesives showed increased bond strength and improved clinical performance. These systems re!uired either total or partial removal of the dentinal smear laver. In addition they re!uired a surface1conditioning step. They used a solution or a series of solutions to increase the wettability of dentin 7i.e. priming solution8. 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. Disad)antages4 Time consuming 7'ore of number of steps8 Techni!ue sensitive E/4 <luma 7(ayer &ental8 ,onditionerI ?&TA -:A DrimerI /3A -1i?'A 7Adhesion Dromoter8 3A <lutaraldehyde )esinI 33A (I;<'A B3A T?<&'A

(onding was achieved by <lutaraldehyde bonds to amino groups in collagen ,harge compounds )eacts with $H group of H?'A And causes mechanical interlocking in the opened ends of dentinal tubules

6. Ten&"e4 $2alate was the first available dentin1bonding agent developed by (owen. Conditioner: 2.5% nitric acid + ferric oxalate (stains the teeth). SYSTEM 4 <luma ;cotchbond $ONDITIONER ADHESION -:A ?&O+A #ROMOTER /3A H?'A 3A <A 33A H?'A 4.3A / T?*5)? 7->.41-0.4 B -A *itric acid 4A Dhos. Acid +A 33A (I;<'A

T?<&'A (I;1<'A

'aleic H?'A

acid 3A *T<1 <'A (I;1<'A D'&' />A H?'A 9A D?*TA T?<1 &'A 3>A 5&'A 43AT?<1 &'A B.3A D?*TA >.3A <A

'pa8 4.3A Alo2alate B. Drisma 5niv. (ond 4

8.

1o&"th !ene"ation Dentin +onding agent4 In these systems there was complete removal of smear layer. ,onsists of primer and adhesive. These bonding systems involved the QTotal etchQ techni!ue 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 +usayama in -.:. and became common in =apan. This gained acceptance in 5; 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 5niversal bonding systems as these bonds to dentin, enamel, amalgam, porcelain and composite. Me hanism of bonding The mechanism of bonding offers for mild and strong etch adhesives

Mild Sea 2#H' I63 In this type of adhesive, 4 types of bonding are seen i.e. Hybridi@ation Ninter1 molecular bonding. Here, the H.H is of such micron si@e and resin formation is less pronounced. In the H.H, HAD is not removed completely because of the weak acid. ;o a second type of bonding occurs, is a HAD act as a receptor for additional molecular interaction with specific carbonyl or D$B groups of the monomer.

?g1 The primary sonic bonding, potential of unifil bond <,., 4 carbonyl groups of L'?TA with HAD were conformed in JD3 PT?' this 4 fold bonding mechanism may be advantage in terms of restoration longevity.

St"ong SEA 2#H 13 This is regular to the total etch systems.

'echanism of bonding is by hybrid layer. +ormation he nearly all HAD is removed from collagen and thus any chemical reaction between HAD and function of monomers are e2cluded.

AD%ANTA!ES ;implified bonding process 71no post condition pani2 simultaneous deminerali@ed and resin infiltration8. *o etch and rinse phase. *ano1leakage is reduced. &entin is covered at all times. )educed postoperative sensitivity. Dossibility of single dose packaging. ,onsistent staple composition ,ontrolled solvent evaporation Hygienic application 7chances of noss infertum are less8 Dossibility of particle filled adhesive carts as shock absorber8. Ade!uate monomer collagen infiltration. ?ffective dentin desensiti@er Time saving.

DISAD%ANTA!ES

Insufficient long1term clinical research. Adhesion potential to enamel needs to the clinically proved yet.

!*ASS IONOMER ADHESI%ES A third adhesion strategy differs from former approaches 7perused by resin1 based systems8, as it involves glass1ionomer based interaction with the tooth substrate with the development of resin modified glass ionomer adhesives have that can bond resin to the tissue. A two1fold mechanism of adhesion is predicted acid pre1)2 without creases the tooth surface and e2poses and surface collagen fluids to a depth of >.3 to -m depth. Here, micro1mechanical bond 7due to resin inter1diffusion8 and a chemical bond 7due to ionic interaction of the carbo2yl groups of polyalkenoic acid with ca of HAD that reward attached to the collagen fibrils8 take places. The underlying mechanism of glass ionomer adhesives and is similar to that of mild etch adhesives. A network of hydro2yapetite1 coatedG collagen fibrils interpenetrated by povers is typically e2posed to a depth no deeper than - m. 5p to >.3 m thick layer, often referred to, as Fget1phaseG remains attached to the tooth surface despite the conditioner being rinsed off. The basic difference with the +irst 7I8 <eneration &entin (onding Agents This was developed by (owen in -.93. Agents used in this generation are a8 <ylycerophosphoric acid airrethacrylate. b8 ,yanoacrylates.

c8 *D<1<'A. d8 Dolymethanes. (uonocore four decades ago found that a resin containing <DA1'A could bond to H,H etched dentin surface. However, the bond strength was affected by the matter content. To overcome this problem, (owen synthesi@ed *D<1<'A, a surface1active ionomer that theoretically produced water resistant bonds, *D<1<'A acted as an adhesion promoter between the tooth structure and resin material by relating with surface calcium. 7*1phenyl glycine and glycidyl methacylate8.

Disad)antages Door clinical results Hydrolysis of <DA1&'A in oral environment &ifficulty in bulk polymeri@ation of cyaroarrylater In stability of *<D1<'A in solution Hydrophobic resin How bond strength 74.-14.0 'pa8

?2ampleI 1 -. ,ervident 7;. ;. hite ,o8 7first commercially available &(A8

4. ,osmic bond 7Amalgamated dental8 /. Dalakar 76ul@er, 5;A8

Se ond !ene"ation Dentin +onding Agents

In the late -.:>#s, the second1generation systems were introduced. 'ajority of these had halo phosphorous stress of unfilled resins such as bisphenol1A glycidyl methacrylate 7(is1<'A8, hydro2yethyl methacrylate 7H?'A8. These were weak bonds seldom increasing -1/ 'pa. (ut were an improvement over the first generation

systems. However, in these systems the phosphate bond to calcium in dentin was not strong enough to resist the hydrolysis resulting from H 4$ immersion. This hydrolysis resulting either from saliva e2posureCmoisture from the dentin caused micro1leakage. In these systems dentin was not etched, hence much of the adhesion was due to bonding to the smear layer. The inethane C isocyanate groups from covalent bonds with hydro2yl groups in both organic and inorganic part of dentin. The adhesive mechanism of these second generations bonding agents involved enhanced surface wetting as well as ionic interaction between negatively charged D$ B group and positively charged ,a. It was speculated that the clinical failure was due to inade!uate hydrolytes stability in the oral environment and become then primary bonding was to ;H rather than the underlying dentin. The presence of an intermediate ;H presented intimate resin contact without is a prere!uisite for a chemical reaction.

Disad)antages How bond strength 7-1/ 'pa8 7studies by relief and others -.09 and ;olomon and beech8 Hydrolysis of and D$B, ,aN bond E/ample4 '

 ;cotch bond dual cure (ond lite Drima universal ,learfil

Thi"d !ene"ation +onding Agents There were developed in the mid -.0>#s. In this generation, the acid etching of the dentin partially removed or modified the smear layer. The acid opens the dentin tubules partially and increases their bonding permeability. The acid must be rinsed completely before application of primer. The primer contains hydrophilic resin modifies like hydro2yethyl trimellitate anhydride and bio1phenyl dineth arylite. The primers

contain a hydrophilic group that infiltrates the dentin and the hydrophilic group that adheres to the resin. The dentin primers usually used in this generation system were 9A D$B penta1acrylate 7D?*TA8 />A H?'A and 9BA ethanol. After the application of primer the unfilled resin adhesive is applied. The most of these systems, the D$ B primer modified the ;H by softening it after penetration. The adhesive is then applied attaching the cured primer to the composite resin. However, bonding was not the

successful decrease the resins did not resin penetration is superficial penetrates the ;H and ;H was may weak.

Disad)antages4 Time consuming Techni!ue sensitive

?2ampleI 1 ;cotch bond and dentin bonding systems J) bonding system <luma bonding system Tenure dentin bonding system B1'?TA Dhenyl I1D 'irage bond ;uper bond Drima universal bond 4 and / ,learfil liner bond

1o&"th !ene"ation Dentin +onding Agents This generation appeared in the early -..>#s. The complete removal of the ;H was achieved in this generation. +usayama and colleagues tried to simplify bonding to enamel and dentin by the preparation of B>A phosphate acid for etching of enamel and dentin. 5nfortunately, it was not understood that dentin and resulted in the collapse of e2posed collagen fibers due to over drying and acid. The use of total etch was one of the main characteristics of this generation. This techni!ue permits the etching of

enamel and dentin simultaneously using phosphate acid for -314>seconds. The surface must be left moist should not be over dried, however in order to avoid collagen collapse. The application of a hydrophilic primer can infiltrate the e2posed collagen network forming the hybrid layer 7*akahayashi resin -.048. The formation of resin tags and

adhesive lateral branches complete the bonding mechanism between the adhesive material and etched dentin substrate. The minerali@ed tissue of the peri1tubular and inter1tubular dentin are dissolved by the acidic caution, the initial surface penetration e2poses the collagen fibulas. In this area, for a depth of 41B micrometer 7*akahayashi -.048 hybridi@ation taken place and resin tags can seal the tubule orifice purely. This is thought to be the primary boning mechanism of most of the current adhesive system. There are bonding systems that use etching of denting with phosphoric acid or other acids. The fourth generation is commonly known as multi1purpose bonding systems as, -. They can be used in cavities for both enamel and dentin 4. ;ame of their components can also be used for bonding to substrates such as porcelain and alloys. In each case, the mechanism of bonding is micro1

mechanical into etched C grit blessed surfaces.

The components of this generation are a set of chemical agents that proceed in a se!uence from an initially hydrophilic component through to gradually more hydrophilic components. The term bonding agent no longer covers this multi1step application,

procedure and has been replaced by adhesive system. +usiyama in -.:., but the concept of total etch gained would wide acceptance only recently. It was mainly discouraged before became total acid etching was thought to produce pulp inflammation. The bonding system of this generation is basically a /1 step process. This was also called as a mineral binding system. -. ,onditioning

4. Drimer /. Adhesive ?2ampleI 1 $pti bond Drobond ;cotch bond multipurpose ,learfil liner bond Amalgam bond plus Ad)antage
'ets

better to met surface

(onds

Disad)antages

5nless the primer and adhesive are applied conse!uently, the overlying composite resin will not bond to the surface.

In the fourth generation system, the clinician had an option of converting the &(A from a light curing to a dual curing one. This was carried out by a self1activating agent 7sulfuric acid derovative8 to the bonding agent 7II - ratio8.

1ifth !ene"ation Dentin +onding 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 may to prevent collagen collapse of deminerali@ed dentin. systems were made. ;o, the 3 th generation bonding

It consists of different types of adhesive materials F$ne bottle systemG 7=I&A 'ason and 6arca -..:8.

One bottle system These systems complained the primer and adhesives into one solution to be applied after etching enamel and dentin simultaneously with /3 to /:A of phosphoric acid for -3 to 4> seconds. These bonding systems create a mechanical interlocking etched dentin by means of resin tags, adhesion lateral branches and hybrid layer formation and show high bond strength values both to etched enamel and dentin.

Si/th !ene"ation Dentin +onding Agents The si2th generation bonding systems are characteri@ed by the possibility to achieve a good to enamel and dentin using only one solution. The first evaluation bond to conditioned dentin while bond to enamel was less effective. This may be due to the fact that the si2th generation systems are composed of an acidic solution that cannot be kept in place, must be refused continuously and have a DH that s not enough to properly etch enamel. )ecently, a H4$ based bonding has been introduced with centries with the functions of a conditioner, the primer and the adhesive. The active solution is mi2ed from two components resulting in the formation of an acidic 7self conditioning8 'oreover, without superficially etches dentin and enamel. The dentin bond mediated by this bonding agent seems to be ade!uate. However, the etching pattern that produced by phosphoric acid etching

?2ampleI 1 It has / compartments

,ompartment -I ,ontaining methgcrylated phosphoric acid, enters, photo initiators, stabili@e

,ompartment 4I ,ontains water, comple2 fluoride and stabili@es ,ompartment /I Has a micro brush

The blister is activated by s!uee@ing comportment -, they reali@ing its content into compartment 4. The mi2ing ratio is BIB.- and the freshly mi2ed solution is released on the micro brush into compartment /. $n applying this to dentin, the ;H well be dissolved. Then the deminerali@ed dentin is leading with group with prop monomers leading to the formation of a hybrid layer.

Se)enth gene"ation +inding Agents His e2ample is the latest addition in the saves of bonding systems. According to manufactures, it a fluoride releasing, self1etching type of bonding agent. It has a color changing capacity.

The etching, priming and bonding is one simple application with no rending or drying.

It is available in two bottles, which have to be mi2ed and filled in the cavity. 'anufactured by a company called = 'onta 75;A8 and the product is $*? 5D ($*& +. This is the only bonding system, which provides visual confirmation of complete

polymeri@ation by color charge.

L?HH$ 7Hi!uid A and (8

DI*6 7Hi!uid A P ( mi2ed8

HIT? 7,ompletely cured8

'anufactures are claiming that this bonding system blocks postoperative sensitivity. Another manufacturing company H 65HMA) have brought a product F($*&G in the market this has a single bottle system having self etch priming and bonding along with desensiti@ing capacity. It has the advantage of single bottle system and no need of mi2ing of any li!uids.

SMEAR *AYER Int"od& tion 6nowledge of the nature, structure and composition of the prepared surfaces of the teeth is the key to the formulation and understanding of adhesive destructive systems.

;mear layer was first suggested by ;kinner 7-.9-8. It was first decreased in detail and termed as Fsmear layerG by (oyde et al 7-.9/8 The ;H encompasses of any debris remaining on enamel, dentin or insertation after instrumentation and conventional methods of cavity preparation.

The ;.H can be discussed under the followingI

,omposition. +ormation. ;i@e. Attachment to dentin. Dotential advantagesCdisadvantages.

$omposition

;mear layer in composed of debris generated during cavity preparation. ?culian 6& lists the following as its components.

Inorganic tooth particles. (acteria and tissues ;aliva. (lood. ;mear layer is rich in nitrogen sulphur, carhon. The organic component consists

of coagulated proteins denatured by functional heat during cavity preparation. The presence of hydro2yapetite crystals in ;.H is because of its breaking away front the organic matri2 and then resetting in the smeared at matri2.

1o"mation ;mearing occurs when hydro2yapetite within 7the tissue8 is either phuked out or broken or swept along the resets in the smeared out matri2. ;tudies have shown that temperature will rise up to 9>> >, in dentin when it is cut without a coolant. This valve is significantly comer than the melting point of appetite 7-3>>>, R -0>>>,8 and has led to collude that smear layer formation is a physiochemical phenomenon rather than a thermal transformation of appetite involving mechanical shearing and thermal dehydration of the protein. Dlastic flow of

hydro2yapetite is believed to occur at low temperatures that its melting point.

Si9e The smear layer thickness is about 31-> microns but according to some studies it may range from -13. The si@e of the smear layer is influenced by the type of bur used, it speed of rotation and presence on 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 increases the frictional heat resulting in the smear layer formation. This smear layer formed is irregular in shape and non1 uniform in si@e and distribution, and remains on the prepared surface even after thought levage with mater. The diamond burs produce relatively deep and uniform groves.

;ignificant difference e2ists between diamond burs used etch and without a coolant 7water spay8. The smeared debris does not form a continuous layer but e2ists as locali@ed islands with discontinuities e2posing the underlying dentin. The mater

spray does not prevent smearing but significantly reduced its amount and distribution.

The smear layer consists of two separate layers ;uperficial layer 7outer8 loose debris plug formation

Hayer loosely attached to underlying dentin 7Inner8 Atta hment to the &nde"lying tiss&e

The smear layer is not always firmly attached to or continuous over the substrate. It may lift free in come cases. #otential Ad)antages : Disad)antages of the smea" laye" The main advantages of the presence of smear layer on dentin.

)eduction of dentin permeability to to2ins and oral fluids. )eduction of diffusion 7usually inwards8 P connection 7outwards by hydrostatic pressure or inwards e2ample by cementing restorations8 of fluids prevents wetness of but dentin surfaces all to (rannstorm et al 7-.:B8 and =ohnson et al 7-.:98.

(acterial penetration of dentinal tubules is prevented 7Eojinovic et al -.:/, 'ichelich et al -.0> $rgart et al -.:B8.

The main disad)antages a"e4

It may harbour bacteria, either from the original various lesions or saliva without may multiply taking nourishment from the ;.H or dentinal fluid.

The ;.H is permeable to bacterial to2ins. The ;.H may prevent the adhesion of composite resin systems, bonding agents, glass ionomer polycarbo2ylate cements all to ;chullen 7-.008, &ahl 7-.:08, Dowis et al 7-.048, Asmussen et al 7-.008 and ?rickson 7-.0.8.

HY+RID *AYER ;ending to acid etched tooth surface re!uires an air1dried surface to allow the photo1polymeri@able hydraulic bonding agent to be drown by capillary attraction into the pits created by acid etching. As a result, two kinds of tag1 like resin e2tensions are formed. 'acro1tags are formed at the cores of enamel primes where the resin curves into a multitude of distinct hypts of dissolved hydro2yapetite crystals,

The underlying mechanism of adhesion to 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 /13 m deep deminerali@ation of the dentin surface. ,ollagen fluids are nearly completely uncovered front hydro2yapetite and form a macro1retentive network for micro1mechanical interlocking of monomers this interlouh was first discussed by *akabayashi, 6ojima P 'asuhma in -.04 and is commonly referred to as Hybrid layer.

,oncurrent etch hybridi@ation, resin tags seal the implugged dentinal tubules and offer additional retention through hybridi@ation of the tubule orifice mall.

Three specific ultra morphologic features have been described as resulting from this hybridi@ation process.

;hag carpet appearance stands for the loose organi@ation of collagen fibrils that are detected towards the adhesive resin and often unrevealed into their micro1fibrils. This feature typically appears when the dentin surface, after being acid1etched, has been actively scrubbed with an acidic primer solution. The physical insuling 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 collaged fibril surface topography similar to appearance of a shag carpet thickness, the combined mechanical chemical action of mubling the acid etched dentin with an acidic premier dissolves additional chemical while fluffing and separating the entangled collage at the surface. This active rubbing application is thought to promote infiltration of monomers into the loosened collaged scaffold by a kind of Fmassaging effectG. A second typical hybridi@ation characteristic has been termed as tubule1 wall hybridi@ation and represents the e2tension of the hybrid layer into the tubule wall area. )esin tag formation in the opened tubules is circularly surrounded by a hybridi@ed tubule orifice wall that is thought to be farmable in hermetically sealing the pulp1dentinal comple2 against micro leakage and the potential subse!uent ingress of

microorganisms. This effect may be especially protective when the bond fails either at the bottom or top of the hybrid layer, without are considered the two weak links in the micro1mechanical attachment. Then, the resin tags usually break at the hybrid layer surface keeping he dentin tubules and thus the direct connectors to the pulp sealed. In particular the resin tag necks at the top 31-> m of the tubule orifice are thought or contribute most to retention and sealing effectiveness.

Thirdly, lateral tubule hybridi@ation has been descried as the formation of tiny hybrid layer into the walls of lateral tubule branches. This micro1version of a hybrid layer typically surends a central core of resin, called a micro1resin tag.

Re)e"se Hyb"id laye"

The acid etched surface of dentin is further sulyected to )2 with *aocl. This results in dissolution of the collagen fibrils that are e2posed. +urther, the use of self1 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.

Inte"'t&b&la" bonding

The hybrid layer has been considered to provide micro1mechanical bonding to dentin but resin tag formation may also contribute to the bond strength. Denetration of the bonding agent into the tubular may provide much retention, as there will be so path of withdrawal until same tags fracture this mechanism plays an important role in areas where dentinal tubules are large in number 7i.e. in areas of dentin nearer to pulp8. 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 7elastic bonding8.

$ONDITIONIN! O1 DENTIN

,onditioning of dentin can be defined as only attention don after the creation of dentin cutting debris, termed the smear layer the objective of this to create a surface capable of micro1mechanical and possible chemical bonding to a &(A. The principal effects of conditioning of dentin may be classified as a8 Dhysical changes. b8 ,hemical changes.

#hysi al hanges a"e p"in ipally

Increase or decrease in the thickness and morphology or the ;.H. ,hanges in the shape of dentinal tubules.

$hemi al hanges a"e p"in ipally 'odifications of the fraction of organic matter. &ecalcification of the inorganic portion.

)emoval of ;.H generally results in increased permeability of the dentin 7Dashley, 'ichelich, 6ehl -.0-8. The small particles comprising of ;.H have a large surface to volume ratio. The particles dissolve more easily then the intact dentin. If the ;.H and smear plugs with in the tubules are last, the e2posed dentin becomes more permeable and sensitive. +or chemical success the conditioned dentin must be scaled to prevent sensitivity and pathology 7(rannstrons -.0-8.

,onditioning of dentin same be done by -8 48 /8 ,hemicalI a8 Acids b8 calcium chelators ThermalI Hasers. 'echanicalI Abrasion.

A id onditione"s

'anufactures generally use the terms conditions or etchant to describe agents that are mashed off the dentin.

Mode of a tion of hemi al onditione"s

It has been suggested that minerali@ed collagen matures have appetite crystallites managed not only around collagen fibrils but also within them. The depth of

deminerali@ation because of either hyper1minirali@ation or formation of more acid resistant forms of calcium phosphate 7Dashlkey -..48

Effe t of hemi al onditione"s ,hemical conditioners remove the ;.H and e2pose a microspores scaffold of collagen fibrils thus increasing the micro porosity of inter1tubular dentin. (ecause this collagen matri2 is normally supported by the inorganic dentinal fraction,

deminerali@ation causes it to collapse. $n inter1tubular dentin the e2posed collagen fibrils are randomly oriented and are often covered by an amorphous phase with selectively few micro1porosities and variable thickness. ?tcharts thickened with silica leave residual silica particles deposited on the surface, but the silica does not appear to plug the inter1tubular micro1porosities. ;ometimes fibrous structures probably renarts of odonto1blastic processes are pulled out of the tubules and smeared over the surface. ith aggressive acid etchants the acids may tend to pull the collagen fibers away from the intact dentinCunaffected 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 minerali@ed peri1tubular dentin from the demanding enter1tubular dentin. Alternatively, the minerali@ed peri1tubular dentin may be completely dissolved to form a funnel shape structure.

Historically, several acids have been researched as dentin conditioners. These include hydrochloric acid, pycrimer acid, and phosphoric, citric, nitric, acids.

The hydrogen ions from these acids diffuse into the dentin while etching. The surface reactions are violent as carbonate is commented to carbon dio2ide and as calcium and phosphates are liberated. These products may be liberated faster than they can diffuse from the site leading to formation of reaction product that may limit further penetration of protons. +urther, the hypertonic solutions when osmotically draw the fluid from the dentin towards the surface could restrict the inward proton diffusion. The removal of smear layer and deminerali@ation of the dentin matri2 may facilitate bonding through a number of mechanisms they areI

)emoval of loose smear layer debris and e2posure of dentin matri2. ?2posure of collagen fibrils and their ?psilon1 Amino groups that may cataly@e H?'A polymeri@ation.

?2posure of intact collagen that serves as a scaffold for the creation of resin collagen hybrid layer.

#HOS#HORI$ A$ID

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 +u@ayama and $thers 7-.:.8. This helps in removing the surface dentin, leaving a clean, well1defined

etching pattern where the tubules are enlarged into a funnel shape. Dhosphoric acid is the acid of choice recently for the etching purpose. However, the controversy remains about the optimal concentration of H / D$B. The most widely used concertinos in clinical practice of H/ D$B ,how and (rown 7-.:/8 demonstrated that the application of H / D$B solutions greater than 3>A 7->14> m8 resulted in the formation of monocalcium phosphate monohydrate that is not readily soluble and mould not be completely washed away in the clinical situation. If H/ D$B is applied on dentin when 3> of dentin removal it resulted in pulpal damage as and liberated gas that passed through the pulp producing thropulus and hemorrhage 76o@am and (urnett8.

Nit"i A id It is stronger than phosphorus acid. ?asily removes the smear layer. 5sed in concentration of 4.3A causes funneling of the orifice of dentin to a depth of 3m in B> seconds.

$it"i A id ->A citric acid is used for the purpose of removing the smear layer. It has been reported by *akabayashi 7-.0.8 that such )2 tends to lower the porosity or permeability of the deminerali@ed surface possibly by denaturing the collagen.

Na5abayashi

de)eloped

1;<

it"i

a ids

pl&s

7<

fe""i

hlo"ide

ombination. The di)alent "athe" seems to stabili9e the dentin mat"i/ d&"ing its demine"ali9ation by it"i a id. This ombination =as fo&nd to be pa"ti &la"ly

effe ti)e fo" metha "ylate based adhesi)es ontaining 8'META. 1e""i appea"s to be ne essa"y same the sit"i a id alone yield poo" "es&lts =ith this system. The highe" bond st"engths of 8'META0 MMA' T++ products

conditioned by ->A citric acid and /A ferric chloride solution can also be achieved by substituting cupric chloride for the ferric ions e2ample super bond , and ( metabond and amalgam bond.

6uraray Introduced ->A citric acid and 4>A calcium chloride in the latest generation of smearfil linear bond system. This dough concentration of calcium may stabili@e collagen during surface etching. It also decreased the e2tent of the Here, the depth of

deminerali@ation of hydro2yapetite by a common ion effect.

decalcification is about and microns compared to the phosphor acid etching with results in -91 micron depth of decalcification 7Inokshe and others -.0.8.

#y"&mi A id Dyrumic acid and prysumic acid suffered with glycine have been reposed to satisfactory acid etch both enamel and dentin 7Asanussen and 'unksgaard, -.008 when using the <luma (onding system <lyrine was used to adjust the DH and perhaps to facilitate polymeri@ation reactions.

$al i&m helato"s ,helators are used to remove the ;.H without decalcification or significant physical changes to the underlying substrate as apposed to the strong acid etchants.

EDTA (rannstrom#s concern that bacteria might be incorporated into ;.H and infect the dentin surfaces of cavities led bur to develop a dentin conditioner containing >.-A ethylene diamine tetracetic acid and >.-3A (en@alkomum chloride as a surface active disinfectant 7-.0>8. This agent was marked under the name FMubulicidG. It is scrubbed on the surface of the ;.H for a few seconds, then left passively for another 9> seconds folled by additional scrubbing such )2 removes the ;.H and generally leaves the smear plug intact the dilute solution of ?&TA removes some ,a that is thought to be important in the mechanism of bonding. This was probably responsible for the fall in bond

strength. ?&TA was developed for its use in the <luma system by 'urksgoard and Asmussen in -.0B. it removes the ;.H but does not form significant surface concavity nor is the funnel shape change associated with phosphoric acid avided. The smear plugs in the dentinal tubules are not for removed completely by /> sers of application of the conditioner. A significant hybrid layer is formed by the application of the prior

containing both gluteraldhyold and ?'A to the ?&TA conditioned substrate.

Malei A id

It removes the smear layer but not the smear plugs. It is used in scotch bond 4 and &e2thessive as a conditioner. Although it is grate acidic, it does not appear to decalcify deeply. The chybrid layer formed in this is comparatively thin.

The"mal Modifi ations *ase"s Hard tissue lasers in dentistry are an emerging technology. A pulsed *d1LA< laser will not disturb the pulp, even the approached is as close as - m. Heat is

dissipated bCw the -> to /> sers pubes per second. 'ost of the research has been conducted on dry dentin, but the laser operates on dentin immersed in salivaCH 4$. The mechanism .of dentin removal is through microscopic implosions caused by the thermal trannents. The carbo2yed, black root that results easily washed off with H 4$ based surface results in desensiti@ed dentin, presumably by occlusion of the open and permeable dentinal tubules. 'icroorganisms and organic debris are eliminated from the la@ed surfaces. The laser decreases the organic fraction of the dentin surface. The bond strength is increased by about 9>A when this was done presumably by increasing the bondable inorganic fraction of the dentin surface. The laser may create micro1mechanical retention. Me hani al Modifi ations

It is a mechanical mean of modification of dentin aluminum o2ide is used for the purpose of micro1abrasion. It removes healthy as well as diseased dentin and results in a smear layer. Its abrasion action depends on the particle si@e as well as the velouty. The >.31micron or larger particles create a smear on the dentin and increase the surface area 7(lacke, -..-8. The smear layer formed might be used to eliminate the bond strengths of smear layer mediated dentin bonding agents.

#olya "yli A id These acids are being used more recently. A -> second application of durelon li!uid 7B>A polyacrylic acid8 nanults in opening of d.t. There is no chance of potential harm to the dental pulp here, due to the large molecular si@e without prevents the and to more through the d.t.

#RIMERS 'ajor advances have been achieved by the introduction of primers that promote meting of the dentin with the bonding agent, and penetration of the bonding agent into the dentin. Drimer monomers are bifuntional molecules i.e they contain -8 hydrophilic groups 7eg1 $H41,$$H8 for better compatibility of the resin monomers with the moist dentin, and 48 hydrophilic emthanylate groups for the co1polymeri@ation with the bonding resin primers are monomer dissolved in solvents such as -8 aretone, 48 alcohol /8 metal and are capable applied to the etchedC conditioned dentin substrate last are not rinsed off organic solvents aid in displacing mater, e2panding or re1e2panding the collagen

network and thus promoting the infiltration of the monomer into the sulucron or monometer si@ed spaces with in the collagen fiber network. The first dentin bonding mechanism that gave reliable, high bond strengths reported by *akabayashi et al 7-.048 was based on the use of B1 '?TAC methyl methacrylate tri1n1 borane 7'''1 T((8 and /A ferric chloride in ->A citric acid as a conditioner.

?ffective primers contain monomers with hydrophilic properties that have an affinity for the e2posed collagen fibril and hydrophilic properties for co1polymeri@e with adhesive resins. The objective of this step is to transform the hydrophilic dentin surface into a hydrophilic state. (esides H?'A primers contain other monomers, such as *T<1 <'A, D'&', (D&' an D?*TA present day primers also underde a chemicalCphoto polymeri@ation initiator so that these monomers can be polymeri@ed in sitic.

The"e a"e 6 types of bonding systems >ate" +ased #"ime"s The first approach to create a hybrid layer in wet dentin is the use of water1 soluble primers containing H?'A. ?2amples of this type of monomer are scotch bond 4, scotch bond multipurpose. After application of the water H?'A mi2ture, the surface all devised to evaporate the H 4$. As the H4$ concentration falls, the H?'A

concentration rises, until theoretically there should be no H 4$ and ->>A H?'A on the surface water has a much higher napour pressure than does H?'A. In fact, at

atmospheric pressure, H?'A can be regarded as almost volatile. This permits its retention as its solvent% water is evaporated during air1drying.

,se of =ate" Mis ible p"ime" sol)ents The second method of creating hybrid layers in this category of bonding is to se!uentially acid etch, rinse, leave moist on dry prime and them bond the H?'A will be in 4 types -8 /3A H?'A in water 48 -/A polyalkenoic acid copolymer in 3>A H?'A.

The intringic metness of dentin varies from about -A in superficial to about 44A in deep dentin Iay et al using all (ond 4, (esco, have described the conse!uences of applying acetone based premiers to over net 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 funed, 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 e2trinsic H4$ is left on to surface prior to the application of primer 7All (ond 48 without tends to bridge the e2cess H 4$ droplets to four a tiny insuster. This prevents resin tag formation in those tubules beneath the H 4$ droplet, clinically if the

clinician sees a rough denture on the primed surface that might be caused by this phenomenon , these droplets can be destroyed with the tip of brush, without can be used to add more primer . The danger is that, this may occur somewhere in a comple2 cavity design that is not easily visuali@ed. This may result in a unbounded region, without changing its dimensions under thermial C ouhcal stress and produce sufficient fluid shifts to cause dentinal sensitivity 7(rannstrom, -..48. It may also permit the concentration of stress that may lead to bond failure in that portion of the restoration 7 atahe, -..48. Thus over drying Cover wetting of dentin can have undisuable effects 7Tay et al8.

The goal of priming is to replace all of the H 4$Caretone monomer mi2tures in the inter1fibular spaces with the polymeri@able monomers 'anel et al demonstrated that ->>A acetone% ethanol and H?'A all cause a time dependent stiffening of deminerali@ed dentinal matri2. $nce stiffened, the matri2 cannot collapse thus allowing efficient hybrid layer formation. Appli ation of p"ime" to smea" laye" o)e"ed dentin follo=ed by bonding agent (onding to the smear layer covered dentin was not very successful before -..> as the resins aid not penetrate through the ;.H. This led most manufacturers to use acidic conditioners. However, the resulting soft collagen with surface can collapse an interface with the number of bonding steps 7 atenbe, -..48 developed a new bonding system with out an a!ueous solution of 4>A phenyl Rp in />A H?'A .This self etching and self priming system provided important new information on ;.H as bonding substrates. The ideal self1etching self1priming bonding system is one that can penetrate

4.>m of ;.H and engage underlying dentin to a depth of - m. However, as ;.H are made up of dentin they have a significant buffer capacity and tend to buffer the acidity of the acidic monomer used as self1etching agent. This property in addition to the tight packing of ;.H particles limit the penetration of monomer is about 4 m. ;o Toida et al advised the removal of smear layer by a separating etching steps to produce more reliable and durable bonds.

Steps fo" effe ti)e p"iming 'icroscope e2amination of attachments reduced y primer has shown deficiencies Hike Incomplete surface coverage. Incomplete inter1fibullar saturation within the hybrid @one. Incomplete penetration to a full depth of deminerali@ed dentin. A R $ne method of improving surface coverage and diffusion of the primer is by the application of multiple coats. A second coat of primer of multiple coats. A second coat pf primer is shown to increase the shear bond strength significantly. (SThe surface of dentin should not be over dried or over wet. ,SThe etching time should not e2ceed the time recommended by the manufacturers. The primer reacts with the side chain grouping of the amino acids in the collagen structures especially R*H4, 1$H4 and ,$$H 'asuhara and coworkers developed analysis bonding agents containing the polymeri@ation initiator tributyl boron, without is said to induce grafting of the monomers and polymers on to the collagen structure.

*atest de)elopments The latest developments in the field of self1etching bonding agents are self R etching bonding agents are self1etching premier1 adhesives for composers 7e2ample1 Dromp H1pop, +14>>>8 7it has been shown that prompt H1prop showed higher bond strength to enamel than to dentin8 ;everal concepts of the bonding mechanism of adhesive resins to dentin have been proposed.

(onding via tag formation in to dentinal tubules of etched dentin 7*ardennall and ()A**;T)$*, -.0>8.

+ormation of precipitates on pretreated dentinal substrate to with an adhesive resin may be chemically or mechanically bonded 7(owen, ,ohh and )apsdin, -.048

,hemical union to either inorganic or organic components of the substrate 7*akalrayashi, Hayta and 'a2chara, -.::8

&iffusion and impregnation of monomers into the sub surfaces of pretreated dentinal substrates and their polymeri@ation creating a hybrid layer of resin reinforced dentin.

There are two types of handing systems they are wet and dry bonding system. et bonding where dentin fluid us not removed completely e2ample acetone is based in bonding where dentin fluid is removed by using air H 4 $ (A;?& and drying method.

>et +onding

?arlier, placement of restoration on wet surface may have caused confliction bCw the dentist his tracing. However, the picture has changed now. hen the etched dentin is air dried the collagen restoration will collapse H P the micro channels opened by the removal of the appetite systems will be closed from a compact coagulate that is imponderable to resin. )esulting in a layer of imperfect bonding termed as FHybridoid regionG 7Tay, <uvett, -..38. This results in micro leakage at monometer level 7-C->>> ton of a micron called F*aroleakageG. This type of bonding results with the bonding systems containing hydrophilic resin such as H?'A, with tolerate moisture. 'ethods without are being followed for wet bondigae. This chamical techne!ue commonly refered o as wet1bonding has been introduced by 6area -..48 abd <rinnett -..48.

6eeping the substrate field dry and use adhesive systems that provide mater based pumers e2ample opti1bond +H, scotch bond multipurpose8. There rehydrate and re1 e2pand the collagen fibers allowing the resin to infiltrate.

6eeping the acid etched dentin surface moist and use acetone based primers 7All bo.nd 48 prime and (ond 48 without have H 4$ chasing capacity. This techni!ue was introduced by 6arca 7-..48 and <winett 7-..48.

In acetone containing primers, when the acetone covers in contact with H 4$% the bonding patient of acetone is raised and boiling patient of H 4$ is lowered

7AM?$T)$DHI;'8 without caused evaporation of both the acetone and H 4$ and resin is left behind. Alternatively conditioned dentin may be are dried and remoistened with H 4$ an antibacterial collection such as chlohenidere 7<arimett and 6anca8T Also an a!ueous collection of H?'A 7/3A8 <a!uapup (I;,$8 are affective for compensating the dryness induced on dentin surface by air drying.

O)e" =etting phenomenon hen amount of H4$ 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, polymeri@ation is affected. In such conditions e2cessive water causes phase separations of hydrophilic and hydrophilic components resulting in blister and globule formation at the resin dentin surface.

Ad)antages of =et bond It is a techni!ue sensitive procedure. +irstly, acetone !uickly 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 in have an effect on the eventual permeability of moners in the e2posed collagen network. To format this primers is be available in pre1dosed single patient use capsules is primer and bond *T Uui2 7&eulply8.

In contract to adhesive systems that provide acetone based primers and show a restricted minnow of opportunityG as far as premise amount of H 4$ that should remain post1condition a on the dentin surface for efficient bonding to be achieved, adhesive systems that provide H4$1based primers appear less techni!ue sensitive and bond e!ually well to varying degree of surface dry and wetness. (onding to dry dentin has the advantage of being the clinically accepted and utili@ed standard used by most clinician. ;ovents used in adhesives A,?T$*?

Highly nolatile. ?2cellent H4$chaser. ;trong duping agents 7risk of over1drying dentin8. ;torage and dispense problems. one step 7(I;,$8 Drime and bond *T 7&entsply8 <uma one bond

?2ample1

Ethanol

<old penetration capacity. ?nables self1etching of acid monomers. ;low evaporation difficult to remove. )emaining H4$ may hamper the resin penetratum air polymeri@ation. 1Amalgam bond plus 7Darkell8. 1Drompt1H1Dop. 1?tch bond multipurpose.

?2ample

>ate"

<ood penetration capacity. ?nables self1etching of acid monomers. ;low evaporation difficult to remove. )emaining H4$ may hamper the resin penetratum air polymeri@ation. 1Amalgam bond plus 7Darkell8. 1Drompt1H1Dop. 1?tch bond multipurpose.

?2ample

;olvents may also be used in combination i.e. Acetone RH 4$ ?2ample1 tenure1!uick Acetone1?thanot. ?2ample1All (ond 47(I;,$8 ?2ample1<uma comfort bond etch bond -.

Adhesi)es The resin component of a bonding system consists of a combination of resin such as (I;<'A, T?<&'A, 5<&'A or other methamylate resins.

These penetrate the preimed dentin and co1polymeri@e with the preimer to form the hybried layer some of these systems may contain fibers without may be silica or glass or fillers of nano si@e. A filled adhesive has

<reater film thickness. <reater utility to fle2. Helpers dispate stress of polymeri@ation.

?2ample1 Drime and (ond *T BA. 1$ptibond solo plus -3A. 1;urfaces resin film that stabili@er the hybrid layer. 1Improved bond strength or bond stability. This is the final step of bonding process% application of adhesive layer spreading of the adhesive resin over the surface to without it is bonded should be done preferably with a brush rather than are spray the adhesive is copiously placed and evenly spread with a brush tip that can be separately s!uee@ed out bCw a paper tissue. The when placed in a sufficiently thick layer, the adhesive resin may, due to its relatively higher elasticity, acts as a stress rela2ation buffer. This will absorb by elastic elongation, in part, the tensile stresses imposed by polymeri@ation contraction of the resin composite subse!uently placed over the adhesive resin.

The polymeri@ation contraction stress generated during the placement of composite restoration was found to be absorbed and relived by the application of an increasing thickness of low1stiffness adhesive. (lowing the adhesive resin layer may reduce its thickness to much, decreasing its elasticity buffer potential to relieve polymeri@ation contraction stress. Amalgam +onding Although retention and resistance forms were the hallmark of traditional amalgam preparations, modern consentive philosophy and the desire to e2tend the use of amalgam to more e2tensive restorations have stimulated a search for improved methods for retaining amalgam restorations mechanical adjuncts, including timeaded primsC retentive groves placed in dentin have served well for years employing '1)1J type coupling agent have achieved some clinical sources where,

' K a methacrylate molecule without bonds to the composite resin. ) K a linking molecule. J K a molecule without interacts with the dentine surface or smear layer. $ne system used y1methacrylo2yethyl trimelliate anhydride 7y1'?TA8. However, the mechanism for responsible foe the bonding amalgam to resin is predominantly mechanical is native. It is produced by condentensory the plastic amalgam mass into an inset adhesive resin layer, there producing an intimate mechanical interlocking as macro retentive areas are produced within the resin after the resin has polymeri@ed.

The results of controlled clinical trials have been mi2ed, but namely amalgam1 bonding agents have placed an adjunct to comentional retentive areas if properly employed. Adhesive1 there are unfilled resin components without is having low minority so that they can penetrate in the tags created by acid etching. 1?2ample1 (I; <'A.