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Dentin Bonding Agents

CONTENTS
SL. NO. 01. 02. 03. 04. 05. 06. 07. INTRODUCTION REVIEW OF LITERATURE HISTORY ADHESION FACTORS AFFECTING ADHESION CHEMISTRY OF ADHESION PARAMETERS AFFECTING THE CLINICAL PERFORMANCE OF ADHESIVES 08. STRUCTURE AND COMPOSITION OF ENAMEL AND DENTIN 09. 10. 11. 12. 13. 14. 15. 16. 17. 18. 19. 20. 21. ENAMEL BONDING SYSTEM SMEAR LAYER DENTIN BONDING SYSTEM CONDITIONING OF DENTIN SUBSTRATE PRIMERS HYBRID LAYER CLASSIFICATION OF DENTIN BONDING AGENTS AMALGAM BONDING SYSTEM PULP CONSIDERATION OF ADHESIVE MATERIAL CLINICAL APPLICATIONS OF DENTIN ADHESIVES LIST OF GUIDELINES TO ENSURE CLINICAL SUCCESS CONCLUSION REFERENCES 74 81 84 89 99 107 113 156 158 162 172 175 176 64 1 5 17 21 34 50 61 TITLE PAGE NO.

Dentin Bonding Agents

INTRODUCTION
During the last three decades clinicians have been confronted with a continuous and fairly rapid turnover in adhesive materials. It started in the mid-60s with the advent of the first commercialized restorative resin composites, followed in the early 70s with the introduction of the acid etch techniques clinical practice. Since then, there has been ongoing progress in developing more refined and diversified restorative composites along with the production of steadily improved bonding agents. Effective adhesion to enamel has been achieved with relative ease and has repeatedly proven to be a durable and reliable clinical procedure for routine applications in modern adhesive to a restorative density. Although adhesion to dentin is not as reliable as adhesion to enamel, todays adhesives produce superior results in laboratories, along with improved clinical effectiveness, approaching enamel-bonding performance1.

Early one-step dentin bonding agents became multi-step systems with more complicated, time-consuming and technique-sensitive application procedures. In the early `90s, the selective enamel-etching technique was replaced by a total-etch concept. Since then, universal enamel-dentin conditioners have been simultaneously applied to enamel and dentin. Now that todays total-etch adhesives have reached a clinically acceptable bonding effectiveness, most recent research and development efforts have focused on simplifying the multi- step bonding process and reducing its sensitivity to errors of inaccurate or incorrect clinical handling.

The concept and practice of esthetic dentistry now is common to most clinicians around the world. Retention of restorative materials to the surface of

Dentin Bonding Agents

tooth structure by means of adhesion is carried out routinely. So successful have been adhesion techniques that retentive pins are seldom, if ever, incorporated into dental practice. The long sought after dream of bonding virtually any type of material to the tooth surface has been realized2.

This momentous change in the way and dentistry currently is practiced can be attributed to the contribution of many scientists. There are, however, three individuals who made the most significant contributions. The first is Michael Buonocore who demonstrated the concept of bonding acrylic resin to the surface of enamel. The second is Rafael Bowen who developed composite resin as an esthetic restorative material.

The third investigator who contributed to the field of esthetic restorative dentistry is Nubuo Nakabayashi. His efforts have led to the techniques for bonding resin composites to the surface of dentin.

The production of a stable, long-term bond to tooth substance is an ideal requirement for the success of all restorations, both metallic and non-metallic. The magnitude of this bond must be sufficient to with stand the stresses caused by the polymerization contraction of resin-based materials and steps must be taken to prevent these stresses from compromising the restoration3.

After observing the industrial use of phosphoric acid to improve adhesion of paints and resin coatings to metal surfaces, Buonocore in 1955, applied acid to teeth to render the tooth surface more receptive to adhesion. Buonocores pioneering work led to major changes in the practice of dentistry. Today, we are in the age of adhesive dentistry. Traditional mechanical methods of retaining restorative materials have been replaced, to a large extent, by tooth-conserving adhesive methods4. 3

Dentin Bonding Agents

One major problem in restorative dentistry is the lack of proper union between the restorative material and the tooth surface. The process of inventions over a period of time have led to the development of various techniques and modalities, which help in adhesion there by reducing the tooth restoration gaps5.

In the present era improved oral hygiene habits have resulted in a dramatic decrease in the incidence of carious diseases and prosthetic treatment needs. This has progressively called into question the traditional concepts of the profession and placed restorative dentistry on a center stage, giving a new impulse to the more conservative adhesive techniques.

During the last two decades adhesive restorative dentistry has increasingly proven its tremendous clinical potential, first in the anterior and more recently in the posterior segments of the mouth. The major driving force for this evolution has been threefold i) The continuous search for specific, less invasive restorative modalities, ii) The patients ever-increasing demand for natural looking esthetics and iii) The intense controversy related to the use of dental amalgam.

Adhesive techniques have greatly expanded the horizon of aesthetic dentistry. Correction of shapes, positions, dimensions and shades of teeth are now possible with the restorative materials. Repair of fractured teeth can be carried out using the fractured tooth fragments there by maintaining original esthetics5.

Although significant progress has been made in preventing the premature loss of failure of restorative materials because of breakdown at the tooth-restorative interface, many questions and challenges remain. The 4

Dentin Bonding Agents

continued developments of adhesive materials is now focused on gaining a better understanding of factors affecting adhesion in the oral environment to improve the clinical longevity of restorative materials.

Dentin Bonding Agents

REVIEW OF LITERATURE
JR Holtan et al (1995)22 compared the shear bond strength to enamel of Scotch bond Multi purpose dental adhesive systems bonding resin following etching of enamel with 10% maleic, 1.6% oxalic, 10% phosphoric, and 35% phosphoric acid for 15,30 and 60 seconds and adhesive resin applied. They found that significant differences exist for shear bond strength values by type of etchant (10% phosphoric, 35% phosphoric > 10 % maleic > 1.6% oxalic acid). Further analysis revealed that the bond strength values for three etchants increased as the applications time increased from 15 to 30 seconds. Bond strength values for the etchants used in this either decreased or did not significantly improve as the application time increased from 30 to 60 seconds. PT Triolo, EJ Swift, W.W. Barkmeier (1995)26 evaluated the shear bond strength of All bond 2 (Bisco), Imperva bond (Shofu), Optibond (Kerr), Permagen (Ultradent), Probond (dentsply) and Scotch bond Multipurpose (3M) and found that the bond strength of Scotch bond Multi purpose and All bond 2 were significantly greater than those of Permagen and Probond. The bond strength of Imperva bond and Optibond were statistically equivalent to Scotch bond Multi purpose and All bond 2. M. Miyazaki et al (1996)27 carried out a study to determine the influence of dentin primer application methods on bond strength to human dentin. Two dentin bonding restorative systems, Imperva bond /Lilefil IIA (Shofu) and Scotch bond Multipurpose/Z-1 00 (3M) were employed. Two experiments were designed 1) effect of the primer application procedures (inactive and active application), and 2) effect of air-drying time (0,1,5,10,20 and 30 seconds). They found that the bond strength with active application

Dentin Bonding Agents

were higher than with inactive group. The maximum shear bond strength was obtained with 20 seconds of air drying time for Imperva bond and with 5 seconds of air drying time for Scotch bond Multi purpose. The bond strengths of each bonding system were lower when the primed dentin surface was not air-dried. T. Nikaido et al (1996)35 evaluated the effect of low-pressure air abrasion with alumina and glass beads on bonding to tooth substrates. They found that air abrasion with glass beads significantly decreased the bond strengths to enamel and dentin, where as air abrasion with alumina decreased adhesion to enamel but not to dentin. The SEM photographs suggested that air abrasion might weaken the tooth surface, which could account for the decrease of the bond strengths. JC Meiers, GA Miller (1996)29 evaluated antibacterial effect of Syntac, Probond, Gluma 3-step using cariogenic bacteria S. mutans, L salivarius and S. sobrinus and A. viscosus in vitro with a modified cylinder drop plate agar diffusion assay. They found that primer and adhesives of Probond and Syntac and the conditioner and primer of Gluma 3 step displayed bacterial inhibition against all four bacteria. Geroge Eliades, Georgios Palaghias, George Vougiouklakis (1997)35 did a study to evaluate the effect of some acidic conditioners on dentin morphology, molecular composition and collagen conformation in situ. The specimens were subjected to conditioning treatments with CA agent (Kuraray), Scotch bond Etchant (3M) and Scotch bond MP Etchant (3M) gels. They concluded that all the conditioners removed the smear layer, funneled the tubules, increased the intertubular roughness and contaminated the dentin surface with residues from irreversibly adsorbed thickening agents. CA agent 7

Dentin Bonding Agents

manifested a significantly lower extent of dentin decalcification that Scotch bond Etchants. Richard B.T Price, Gordov C. Hall (1999)41 did a study to evaluate 24 hr shear bond strength of six dentin bonding systems with 10 minute dentin bonding system and concluded that 10 minute shear bond strength were significantly less than the 24 hour values. P N R. Pereira et al (1999)54 investigated the influence of intrinsic wetness on regional bond strength of adhesive resin to dentin Group one- no pulpal pressure Group two- pulpal pressure of 15cm H2O Group three- dentin dried overnight in a dessicator

They found that no significant regional differences were observed for group 1 and bond strengths significantly decreased at the pulp horn regions. They concluded that dentin adhesive system should be chosen according to the substrate and region to be bonded, since bond strength vary according to the intrinsic wetness, region and the adhesive system. C Prati, S. Chersoni, D.H Pashlay (1999)24 did a study to evaluate the effects of NaOCl at removing the demineralized layer by examining the morphology of hybrid layer and measuring shear bond strengths after dentin treatments. They observed that collagen fibrils were completely removed from acid- etched surface by NaOCl treatment. The diameter and size of dentinal tubules and number of lateral branches of tubules were increased following NaOCl treatment.

Dentin Bonding Agents

K Miyasaka, N. Nakabayashi (1999)55 did a study to examine a new bonding system combining an ethylene diaminetetraaceticacid (EDTA) conditioner and the 2 methacryloxyloxyethyl phenyl phosphoric acid (Phenyl p)/2 hydroxyethyl methacrylate (HEMA) self etching primer with a dumb bellshaped specimen for tensile test. They found that combining the EDTA conditioner and phenyl P/HEMA primer afforded high quality hybridization and good bond strength. M. Hashimoto et al (2000)36 evaluated the correlation between hybrid layer thickness and bond strength using specimens acid conditioned for varying lengths of time. They found that bond strength decreased with increase in period of acid conditioning. The distance between resin tags within the hybrid layer of the specimen acid conditioned for100 S can be seen to be less than that between the resin tags in a specimen acid conditioned for 60 seconds. H.LI, M.F. Burrow. M.J Tyas (2000)38 evaluated the nanoleakage pattern of four dentin-bonding systems. They did study on Single bond, One coat bond Prime and bond NT/Non rinse conditioner and Perma Quick samples were immersed in a 50% solution of silver nitrate for 24 hrs. This study demonstrated the nanoleakage pattern of four dentin-bonding systems. Different leakage patterns were observed with the different type dentin bonding agents employed. Prime and bond NT/NRC showed a dense silver deposition. Perma Quick showed better sealing ability. Single bond and one coat are intermediate. Bruno T. Rosa, Jorge Perdigao (2000)29 did a study to determine enamel and dentin bond strengths of non rinsing all in one adhesive and of a non rinsing conditioner combined with a one bottle adhesive. Prompt L -Pop, No etch plus Prime and bond NT, NRC plus prime and Bond NT, Phosphoric 9

Dentin Bonding Agents

acid plus prime and bond 2.1. They found that for resin composite, etching with phosphoric acid resulted in the highest bond strength to enamel. For compomer, the highest enamel bond strength was achieved with both phosphoric acid and Prompt L- Pop. Treating dentin with Prime and bond NT with out etching provided the highest mean bond strength for composite. For compomer treating dentin with Prime and bond NT resulted in the highest mean bond strengths, regardless of the conditioner. M. Tanumiharja, M.F. Burrow, M.J. Tyas (2000)32 evaluated the micro tensile bond strengths of seven dentin adhesive systems (Solid bond, EBS Multi, Perma Quick, One coat bond, Gluma one bond, Prime and bond NT/NRC and Clearfil liner bond 2V). They found that conventional and single bottle systems had similar bond strengths except for one of the conventional systems, Perma Quick. The self- etching priming systems, Clearfil liner bond 2 V and Prime and bond NT/NRC, had higher bond strengths than the other systems. Siavoljub Zivkovic (2000)28 assessed in vitro quality of marginal sealing of composite dentin adhesive system and human dentin. After the enamel layer was removed, class V cavity was formed on buccal surface, and a wedge cavity was formed on lingual surface.

Denthesive/Charisma, Tripton/Opalux, Syntax/Helioprogres, Gluma/ Pekafil Scotchbond Multipurpose/Valux, XR- bond/Herculite, Superlux universal bond 2/ Superlux solar. They found that best marginal sealing was achieved by the Scotch bond Multi purpose /Ssyntac/helioprogres, XR bond/ Herculite, Gluma/ Pekafill, and Superlux Universal bond 2/ Superlux solar system, the greatest microleakage was noted with the tripton/ Opalux and Denthesive/charisma system. 10

Dentin Bonding Agents

Franklin R. Tay, David H, Pashley (2001)23 conducted a study on the aggressiveness of three self-etching adhesive systems in penetrating dentin smear layer of different thickness. Adhesive were Clearfil Megabond, NonRinse conditioner/Prime and bond NT and Prompt L- Pop. They found that for Mega bond, thin authentic hybrid layers between 0.4-0.5mm were found. Smear layer and smear plugs were retained as part of the hybridized complex. For non-rinse conditioner/Prime and bond NT, the authentic hybrid layers were between 1.2-2.2 mm thick. Smear layer and smear plugs were completely dissolved in dentin with thin smear layers, but were partially retained as part of the hybridized complex in those with thick smear layers. For Prompt L-Pop, authentic hybrid layers were 2.5-5mm thick and smear layer and smear plugs were completely dissolved even in dentin with thick smear layers. R. Frankenberger et al (2001)40 compared the adhesive capability of the new adhesive Prompt L Pop (ESPE) with that of two total etch adhesive systems- EBS multi (ESPE) and Prime and bond NT (Dentsply) combined with Pertac II (Composite) or Hytac Aplitip (Compomer). They found that 1). The use of prompt L-Pop as a multi step adhesive system resulted in higher bond strengths than when used as per manufacturer directions 2.) When applied on multiple coats, Prompt L- Pop resulted on bond strengths that were not statistically different from those of P & B NT, a total etch adhesive. The bond strengths obtained with EBS multi, a water- one -based total etch adhesive, were significantly higher than those obtained with Prompt L-Pop. David H. Pashley, Franklin R- Tay (2001)39 studied the aggressiveness of three self-etching adhesives unground enamel.

Ultrastructural features and microtensile bond strength was examined. Study group included Clearfil Mega bond, Non- rinse, conditioner or Prompt L-Pop and a control group with 32% phosphoric acid. Clearfil Mega bond exhibited 11

Dentin Bonding Agents

the mildest etching patterns, while Prompt L-Pop produced an etching effect that approached that of total etch control group. Microtensile bond strength of three experimental groups was all significantly lower than control group. G. Eliades, G. Vougiouklakis, G. Palaghias in (2001)53 did a study to investigate whether monomer separation occurs in single bottle adhesives applied on acid- etched dentin surfaces. The single bottle adhesives used were One step, Prime and bond 2.1, Scotch bond 1 and Syntax- sprint All the adhesives demonstrated separation of monomer components on etched dentin. Atila Stephan, Zafer C. Cehreli and Burcin Sener (2001)52 studied the antibacterial effects of dentin bonding systems Single bond, Prime and bond NT, and Excite using the bacteria streptococcus mutans ATCC 25175, Streptococcus intermedius, Lactobacillus acidophilus, Prevolella oris,

Prevolella denticola, Porphyromonas gingivalis, Porphyromonas endodontalis, and Clostridum ramosum with a disk diffusion method. Prime and bond NT showed growth inhibition for all bacterial strains. Lactobacillus acidophilus and streptococcus mutans were remarkably resistant to Single bond, whereas Excite produced no inhibitory effect on Porphyromnas edodontalis. Johan Blomlof et al (2001)25 did a study to compare EDTA conditioning and phosphoric acid conditioning of dentin in combination with two principally different commercial dentin-bonding systems (All bond- 2 and Prime and bond NT). They found that combination of conditioning with EDTA and bonding with all bond 2 was significantly better than all other combinations. Jorge Perdigao et al (2001)50 did a study to determine the microtensile bond strength of 3 dental adhesives (Clearfil SE bond, Prime and bond NT, 12

Dentin Bonding Agents

Single bond) when applied to dentin decalcified with EDTA.For each adhesive the control group (not decalcified) resulted in higher bond strengths than the treatment groups. Lorenzo Breschi et al (2002)51 evaluated the ultra-morphological effects of maleic acid and citric acid in dentin by means of a field emission in lens scanning electron microscope. Both acids were tested on human dentin at pH 0.7 and 1.4 in aqueous solutions. They found that both acids removed smear layer and partially removed smear plugs. Maleic acid at pH 0.7 showed the highest depth of demineralization of all the tested samples, citric acid, showed a higher depth of demineralization values when tested at pH 1.4 than at pH 0.7. M. Miyazaki et al (2002)56 examined the relationship between the bonding agent application duration and the dentin bond strength of several single applications bonding systems. The restorative material/bonding systems used were Reactmer, with Reactmer bond, Paltique Estelite with One up bond F, and F 200 compomer adhesives were applied for 5,10,20,30 and 60 seconds. No significant differences were found among the 10-60 second application duration groups for the systems used. Demineralization of the dentin surface was more pronounced with longer application duration. Y. Shimada et al (2002)30 compared the microshear bond strength of two adhesive systems to primary and permanent tooth enamel. Two commercially available resin adhesives, a self etching primer system (Clearfil SE bond) and a Single bottle adhesive system (Single bond) used with a total etch wet bonding technique were tested. No statistically significant differences of shear bond strength values were found between the primary and permanent enamel in the adhesive systems used. The SEM observations showed that both 13

Dentin Bonding Agents

adhesive systems etched the primary enamel deeper than the permanent enamel, suggestion that the action of acid etch seemed to be more intense on primary enamel than on permanent enamel. Bonding of the adhesive systems to primary enamel was almost identical to permanent enamel. Y. Shimada et al (2003)31 investigated the bonding of current resin adhesives to the region approximating the DEJ, where the etch pattern to enamel or dentin may be different. Three kinds of tooth substrates were chosen for testing enamel, dentin and the DEJ region. A self- etching primer system (Clearfil SE bond) and total etch wet bonding systems (Single bond and One step) were used. Confocal laser scanning microscopy observation showed that the DEJ region was etched more deeply by phosphoric acid gel than enamel or dentin. No significant differences of shear bond strength values were observed between the DEJ region and enamel or dentin. Amer Abu Hanna, Valeria V. Gordan Ivar Mjor (2003)34 studied the effect of variation in etching times effect depth of dentin demineralization and the thickness and morphology of the hybrid layer. Different etching times of 5,15 and 30 seconds. There was a direct correlation between etching time and depth of demineralized zone.The hybrid layer thickness correlated directly to the etching time. Reducing etching time reduces the depth of the demineralized zone and may be effective for achieving complete penetration and for sealing the dentin surface. Sofia S.A et al (2003)57 did a study to determine the effect of dentin smear layers created by various abrasives in the adhesion of a self etching primer (SE) and total etch (SB) bonding systems. Shear bond strength of SB system was not sensitive to the abrasive used except for the very smooth surfaces produced by the 0.05mm-alumina slurry. Compared with those 14

Dentin Bonding Agents

produced by the diamond burs, the carbide bur yielded the highest bond strength and the thinnest smear layer. G.C. Lopes et al (2003)33 verified whether there are differences between bonding to hypermineralized dentin and normal dentin and if longer acid etching can improve the bond strength to this modified substrate without damaging the bond to normal dentin. They found that the thickness of the hybrid layer formed on sclerotic dentin is less than normal dentin, showing this tissue to be more resistant to demineralization caused by acid etching. Bond strength of sclerotic dentin is not as high as normal dentin. Murat Turkun, Sebnem Turkun, Atakan Kalender (2004)42 evaluated the effect of three different cavity disinfectants on the microleakage of two current non rinsing dentin bonding systems, Prompt L- Pop and Clearfil SE bond. They found that consepsis and tubulicid red could be used as cavity disinfectants with Clearfil SE bond and prompt L-Pop without affecting their sealing ability. Ora- 5 is not an appropriate disinfectant to use with these dentin-bonding systems because of alters their sealing abilities. Sigurdur O. Eriksson et al (2004)46 evaluated the effects of saliva contaminated on microtensile bond strength between resin interfaces and to determine which decontamination methods best re-established the original resin- resin bond strength.. Saliva contamination significantly reduced bond strength between resin composite surfaces regardless of materials evaluated. Blowing the saliva off quickly or rinsing with water did not restore bond strength to normal levels. Sigurdur O., Eiriksson et al (2004)45 evaluated the effects of blood contamination on microtensile bond strength between resin interfaces and to 15

Dentin Bonding Agents

determine the best decontaminaion method to re-establish the original resinresin bond strength Blood contamination significantly reduced the bond strength between resin composite increments regardless of materials evaluated. Rinsing with water restored the bond strength significantly for all materials. G. Schmaiz, Z.Ergucu and K.A. Hiller (2004)47 examined the antibacterial effects of different dentin bonding agents and two components of dentin adhesives, HEMA and TEGDMA against carieogenic bacteria Streptococcus mutans, S.Sorbinus and Lactobacillus acidophilus. Antibacterial activities associated with some dentin bonding agents and chlorhexidine are modified by the presence of dentin. Bora Ozturk and Fusun Ozer (2004)58 evaluated the effects 5% NaOCl on bond strengths of four bonding sytems- Clearfil SE Bond, Prompt L-Pop, Prime and Bond NT, and Scotchbond Multi purpose plus- to pulp chamber mesial walls. Results showed that, in general, NaOCl application decreased the bond strength values of the bonding agents. Esra Can Say et al (2004)44 evaluated the effect of two cavity disinfectant, a 2% chlorhexidine and a 1% benzalkonium chloride solution on the shear and tensile bond strengths of dentin bonding systems it denture. Results indicate that the use of 2% cholrhexidene and 1% benzalkonium chloride solution as cavity disinfectants after etching the dentin did not affect the shear and tensile bond strength. Hagay slulzky, Shlomo Matalon and Ervin I. Weiss (2004)43 evaluated the antibacterial surface properties of polymerized single bottle bonding agents such as Bond-1, OptiBond sole, One-step, Gluma, Prime and

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Bond NT and Synergy, using the direct

contact test (DCT). The results

showed that all tested bonding agents exhibited potent antibacterial properties. Arlin Kiremitci, Filiz Yalcin and Saadet Gokalp (2004)48 evaluated the effectiveness of prime and Bond NT, Clearfil SE Bond and Prompt L-Pop on adhesion of resin composite to both dentin and enamel. Results showed that Prompt L-Pop exhibits significantly higher bond strength values to enamel than all other groups. There were no statistically significant difference for shear bond strength to dentin among adhesives. Maria Carolina Guilherme Erhardt et al (2004)49 evaluated the influence of carisolv on the shear bond strength of hydrophilic adhesives to dentin. Results showed that carisolv did not interfere in the adhesion to dentin.

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HISTORY
Pioneers of enamel and dentin bonding : Research into bonding agents for attachment of resins to tooth structure was started in early 1950s. The first attempt to develop on adhesive system for bonding acrylic resins to tooth structure was made by Hagger, a Swiss chemist working for the Amalgamated Dental Company in London and Zurich in 1949. A commercial product, Sevriton cavity seal was then marketed in conjunction with a chemically cured resin, Sevriton for use in restorative dentistry: A patent was applied for in Switzerland on July 21 1949, granted November 15 1951 and expired on July 21 19645.

At that time, this invention by Hagger was revolutionary and almost unrecognized in current literature since it was the first time that chemical bonding to tooth structure became a commercial possibility. The system was very sophisticated for that period and was based on glycerophosphoric acid dimethacrylate, which could be catalytically polymerized by the action sulphinic acid in a 5 to 30 minute period at 200c. of

In 1952, Kramer and Mc Lean were among the first to use glycerophosphoric acid dimethacrylate (GPDM) to bond to dentin. Reports soon demonstrate the interest in using these molecules to bond restorative materials to dental tissues, and at the same time provided the first description of what was to be called the hybrid layer.

In 1955 the foundation for adhesive restorative and preventive dentistry was laid, when Buonocore proposed that acids could be used to alter the surface of enamel to render it more receptive to adhesion. His hypothesis

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was based on the common industrial use of phosphoric acid to improve adhesion of paints and acrylic coatings to metal surface.

In 1955 Buonocore, conducted experiments on enamel surfaces employing a 30 seconds treatment of 85% phosphoric acid to achieve a simple acid decalcification. In 1956 Michael Buonocore pioneered the work on adhesion to dentin. Buonocores idea resulted in a bonding agent being used as an intermediary between dentin and restoratives resin. The strength of this was however low initially but later more effective systems of bonding based on the original idea of Buonocore appeared. In 1956 Michel Buonocore, Wileman W Brudevald reported a resin composition capable of bonding to human dentin surfaces.

In 1957 R.L. Bowen did the initial work on Bis-phenol glycidyl methacrylate resin systems. In 1962 R.L. Bowen conducted the first workshop on adhesive restorative dental materials and demonstrated that surface active agents having an affinity for the surface of hydroxyapatite powder contained groups which were capable of forming five membered chelate ring with calcium5.

In 1965 the infiltration of resin monomers into demineralized dentin created a new structure, which was, first described invitro for enamel by Gwinnett and Buonocore. Simultaneously R. L. Bowen advocated that

bonding to dentin could be improved by pre-treatment and the use of surfaceactive co-monomer.

In 1968 Bunocore, Matsui, and Gwinnett conducted pioneering studies in which the physical relationship between acrylic restorative resins and etched enamel surfaces was clarified paving way for the acceptance of the acid etch 19

Dentin Bonding Agents

techniques as an integral part of restorative procedures involving composite restorative resins.

In 1970 Eick and others described the nature of smear layer for the first time. In 1971 Lee and others developed a polymethane resin to be used as an adhesive for composite restoration. In 1974 R.L. Bowen in Adhesive bonding of various materials to hard tooth tissues VII reported that metal salts acts as mordant for coupling agents.

In 1979 Fusayama and others were the first to report the successful use of phosphoric acid to remove smear layer, etch the dentin and restore with adhesive composite resin.

In

1979

Yamauchi,

Nakabayashi,

and

Masuhara

developed

methacryloxyethyl phosphoric acid ester, which appears to be the basis of the Clearfil bond system.

In 1980 Nakabayashi and Masuhara developed acrylic bonding agents containing the polymerization initiator tributyl boron, which is said to induce grafting of the methyl methacrylate to dentin collagen. Brannstrom later in the year 1981 reported that for clinical success the conditioned dentin must be sealed to prevent sensitivity and to prevent the pathology associated with increased permeability of the dentinal tubules.

Later Causton in the year 1982 illustrated the principle of primers, which react with the tissue surface and which compete with and displace water for durable bonding. Bowen, Cobb and Rapson later developed the multilayer adhesive system. 20

Dentin Bonding Agents

In 1982 Nakabayashi reported the presence of hybrid layer of resinreinforced dentin. In 1982 Den Mat separated enamel bonding from dentin bonding. In 1987 -Tenure system was used. In 1990 Fourth generation dentin bonding agents was developed Later in year 1991 Kanca technique, was introduced which is also referred to as All-etch technique. 1995 fifth generation bonding agent were developed. 2000 New classification of adhesive was introduced based on number of different working steps and treatment of smear layers.

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ADHESION
The word adhesion comes from the Latin word adhaerere (to stick to). The American society for Testing and Materials (ASTM, specification No 907) defines adhesion as the state in which two surfaces are held together by interfacial forces which may consist of valence forces or interlocking forces or both. Adhesion describes the attachment of one substance to another whenever they come into close contact with each other. Therefore it can be defined as a force that binds two dissimilar materials together when they are brought into intimate contact6.

Adhesion is the attraction of molecules at surfaces. The bond strength depends on the amount of force present of each contact site. At an atomic level solid often have rough surface, which means that they contact each other only at certain points. To get a better contact between two materials, an intermediate layer called adhesive has to be placed. An adhesive is a material frequently a viscous fluid; that joins the two substrates together and solidifies, therefore able to transfer a load from one surface to other. The surfaces or substrates that are adhered to are termed the adherends. Adhesive strength is a measure of load bearing capacity of an adhesive joint.

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Schematic summary of dental adhesion and dental adhesive joint

Mechanism of adhesion: 1. Mechanical adhesion: Interlocking of adhesive with irregularities in the surface of the substrate, or adherend. 2. Adsorption adhesion : Chemical bonding between the adhesive and the adherend. The forces involved may be primary (ionic & covalent) or secondary (hydrogen bonds, dipole interaction, or Vander waals valence forces). 23

Dentin Bonding Agents

3.

Diffusion adhesion: Interlocking between mobile molecules, such as the adhesion of two polymers through diffusion of polymer chain ends across an interface.

4.

Electrostatic diffusion: an electrical double layers at the interface of a metal with a polymer that is part of the total bonding mechanism.

Bonding of resins to tooth structure is a result of four possible mechanisms: 1. Mechanical: Penetration of resin and formation of resin tags with in the tooth surface. 2. Diffusion- Precipitation of substances in the tooth surface to which monomers can bond mechanically or chemically. 3. AdsorptionChemical bonding to the inorganic component

(hydroxyapatite) or organic components (mainly type 1 collagen) of tooth structure. 4. A combination of the previous three mechanisms.

Theories of adhesion: Two main theories for the observed phenomenon of adhesion are.

Mechanical theory: States that the solidified adhesive interlocks micro mechanically with the roughness and irregularities of the adherend surfaces.

Adsorption theory: Includes all kinds of chemical bonds between the adhesive and the adherend including primary and secondary valence forces.

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Several types of bond may be classified under the two general headings. ADHESIVE BOND Mechanical adhesion Primary valence forces . Ionic bonds Covalent bonds Metallic bonds Microscopic penetration

Secondary valence forces (Vander waals forces) Vander waals forces Hydrogen bonds

Chemical adhesion

MECHANICAL ADHESION : Strong attachment of one substance to another can also be accomplished by mechanical bonding or retention rather than by molecular attraction. Mechanical bonding may also involve more subtle mechanisms such as the penetration of the adhesive into microscopic or submicroscopic irregularities in the surface of the substrate. On hardening the multitude of adhesive

projections embedded in the adhesive bond surface provides the anchorage for mechanical attachment (retention).

An example of the mechanical adhesion is resin impregnation. Before insertion of the resin, the enamel is treated with phosphoric acid for a short period. The acid produces minute pores in the enamel surface into which the resin subsequently flows when it is placed into the preparation. On hardening

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these resin projections provide improved mechanical retention there by reducing the possibility of interfacial marginal leakage.

Thus it is an example of how bonding between the dental material and tooth structure can be attained through mechanical mechanisms ,not through molecular adhesion.

CHEMICAL ADHESION: The chemical adhesions are basically interatomic bonds, which may be classified as primary or secondary. The strength of these bonds as well as their ability to reform after breakage, determines the physical properties of the material.

Primary atomic bonds may be of three different types 1. 2. 3. Ionic Covalent Metallic

Ionic Bonds : These primary bonds are of simple chemical type, resulting from the mutual attraction of positive and negative charges. The classic example is sodium chloride (Na+ Cl-). Because the sodium atom contains one valence election in its outer shell and the chlorine atom have seven electrons in its outer shell, the transfer of the sodium valence electron to the chlorine atom results in the stable compound NaCl.

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Covalent bond: In many chemical compounds, two valence electrons are shared by adjacent atoms. The hydrogen molecule, H2 is an example of covalent bonding.The single valence electron in each hydrogen atom is shared with the other combining atom, and the valence shell become stable.

Covalent Bond Metallic bonds : Certain atoms of a few crystals like gold can easily donate electron from their outer shell and form a gas of free electrons. The contribution of free electrons to this cloud results in the formation of positive ions that can be neutralized by acquiring new valence electrons from adjacent atoms. 27

Dentin Bonding Agents

Gas of free electrons

Metallic Bond Formation Interatomic secondary bonds: In contrast with primary bonds, secondary bonds do not share electrons instead; charge variations among molecules or atomic groups induce polar forces that attract the molecules.

a. Hydrogen bonding: In a water molecule attached to the oxygen atom are two hydrogen atoms. These bonds are covalent because the oxygen and hydrogen atom share electrons. As a consequence, the protons of the hydrogen atoms pointing away from the oxygen atom are not shielded efficiently by the electrons. Thus the proton side of the water molecule becomes positively charged. On the

opposite side of the water molecule, the electrons that fill the outer orbit of the oxygen provide a negative charge. When a water molecule intermingles with other water molecules the hydrogen portion of one molecule is attracted to the oxygen portion of its neighboring molecules, and hydrogen bridges are formed.

28

Dentin Bonding Agents

Hydrogen Bonding

Vander Waals Forces: Normally the electrons of the atoms are distributed equally around the nucleus and produce an electrostatic field around the atom. However this field may fluctuate so that its charge becomes momentarily positive and negative. A fluctuating dipole is thus created that will attract other similar dipoles. Such interatomic forces are quite weak.

FACTORS ASSOCIATED WITH ADHESION:

Surface energy : For adhesion to exist, the surfaces must be attracted to one another at

their interface. Such a condition may exist regardless of the phases-solid, liquid (or) gases of the two surfaces, with the exception that adhesion between two gases is not be expected because of the lack of an interface6.

The energy at the surface of a solid is greater than in its interior e.g.: space lattice. Inside the lattice, all of the atoms are equally attracted to each other. The interatomic distances are equal and the energy is minimal. At the

29

Dentin Bonding Agents

surface of the lattice, the energy is greater because the outmost atoms are not equally attracted in all directions. The increase energy per unit area of surface is referred to as the surface energy (or) surface tension.

The tendency of a soap film to contract and drops of a liquid to form spherical shapes due to surface tension can be understood on the principle of a system achieving a state of lowest energy by minimizing its surface area. The surface atoms of a solid tend to form bonds to other atoms that come onto close proximity to the surface in order to reduce the surface energy of the solid. This attraction across the interface for unlike molecules is called adhesion.

E.g.: Molecules in the air may be attracted to the surface and to be absorbed by the material. Silver, platinum and gold absorb oxygen readily. With gold, the bonding forces are of the secondary type but in case of silver, the attraction may be by chemical or primary bonding and silver oxide may form.

The surface energy and there fore adhesive qualities of a given solid can be reduced by any surface impurity such as gas adsorption or oxidation. The functional chemical groups available or even the type of crystal plane of a space lattice present at the surface may affect the surface energy.

Wetting : It is very difficult to force two solid surfaces to adhere. Regardless of how smooth their surfaces may appear they are likely to be very rough when they are viewed at the atomic or molecular dimensions. Consequently, when they are placed in apposition, only the peaks or asperities are in contact. Since these areas usually constitute only a small percentage of total surfaces, no perceptible adhesion takes place. The attraction is negligible when the 30

Dentin Bonding Agents

surface molecules of the attracting substances are separated by distances greater than 0.0007 m or (0.7nm)6.

One method of overcoming this difficulty is to use a fluid that will flow into these irregularities and this provides contact over a great surface of the solid.

E.g.: when two polished glass plates are placed one on top of other and are pressed together, they exhibit little tendency to adhere. However if a film of water is introduced between them considerable difficulty is encountered in separating the two plates. The surface energy of the glass is sufficiently great to attract the molecules of water.

To produce adhesion in this manner, the liquid must flow easily over the entire surface and adhere to the solid. This characteristic is referred to as wetting. If the liquid does not wet the surface of the adherend, the adhesion between the liquid and the adherend will be negligible or non-existent. If there is a true wetting of the surface, adhesion failure should not occur. Failure in such cases actually occurs cohesively in the solid or in the adhesive itself, not in the interface where the solid and adhesive are in contact .The ability of an adhesive to wet the surface of the adherend is influenced by a number of factors. Cleanliness of the surface is of particular importance, a film of water, only one molecular thick on the surface of the solid may lower the surface energy of the adherend and prevent any wetting by the adhesive. Like wise, an oxide film on a metallic surface may inhibit the contact of an adhesive.

The surface energy of some substances is so low that, few if any liquids will wet their surfaces. E.g. some organic substances are of this type (dental waxes). Close packing of the structural organic groups and the presence of 31

Dentin Bonding Agents

halogens may prevent wetting. Teflon (poly tetra fluoroethylene) is often used in situations in which it is desirable to prevent the adhesion of film to surface. Metals on the other hand, interact vigorously with liquid adhesives because of their high surface energy.

In general, the comparatively low surface energies of organic and most inorganic liquids permit them to spread freely on solids of high surface energy. Thus formation of a strong adhesive joint requires good wetting.

Contact Angle: The extent to which an adhesive will wet the surface of an adherend may be determined by measuring the contact angle between the adhesive and the adherend. The contact angle is the angle formed at the interface of the adhesive and the adherend. If the molecules of the adhesive are attracted to the molecules of the adherend as much as, or more than, they are attracted to themselves, the liquid adhesive will spread completely over the surface of the solid, and no contact angle will be formed.

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Dentin Bonding Agents

A. When the contact angle is 00, the liquid contact the surface completely and spreads freely. B. Small contact angle on slightly contaminated surface. C. Large angle formed by poor wetting

Thus the forces of adhesion are stronger than the cohesive forces holding the molecules of the adhesive together.

However, if the energy of the adherent surface is reduced slightly by contamination or other means, the surface tension of solid (rsv) decreases and a slight increase in contact angle. If a monolayer film of a contaminant is present over the entire surface, a medium angle must be obtained. Where as very high angle would result on solid of low surface such as Teflon. Since

the tendency for the liquid as the wetting angle decreases contact angle is a useful measure of spreadability or wettability.

Complete wetting occurs at a contact angle of 00, and no wetting occur at an angle of 1800, Thus the smaller the contact angle between an

adhesive and an adherend, the better the ability of the adhesive to flow into and 33

Dentin Bonding Agents

fill in irregularities with in the surface of the adherend. Also the fluidity of adhesive influences the extent to which these voids or irregularities are filled. Solid flat surfaces are not actually planar. Surface imperfections represent potential impediment to the achievement of an adhesive bond. Air pockets may be created during the spreading of the adhesive that prevent complete wetting of the entire surface.

When the adhesive interfacial region is subjected to the thermal changes and mechanical stress, stress concentrations develop around these voids. The stress may become so great that it initiates a separation in the adhesive bond adjacent to the void. This crack may propagate from one void to the next, and the joint may separate under stress.

Requirements for long lasting adhesion : The most important requirement for adhesion is that the two materials to be bonded to each other must be in sufficiently close and intimate contact. To achieve this requirement for solid bodies, liquids or flowable materials can be used6. The intimate contact with the substrate depends on: 1. 2. 3. Wettability of the substrate Viscosity of the adhesive Morphology and roughness of substrate

34

Dentin Bonding Agents

FACTORS AFFECTING ADHESION


The effective adhesive of restorative resins to mineralized tissues has been a topic of active research. Bonding is the attachment of one substance to another. A bonding agent is a material that when applied to the surface of substances can join them together and resist separation. The extent of adhesive forces operating across an interface depends on several factors. Clinical factors affecting adhesion Factors affecting adhesion to mineralized tissue.

Clinical factors affecting adhesion: Salivary and or blood contamination Moisture contamination from hand piece or air water syringe. Oil contamination of hand pieces or air water syringe Surface roughness of tooth surface. Mechanical undercuts in tooth preparation. Fluoride content of teeth Presence of plaque, debris, calculus, extrinsic strains or debris. Tooth dehydration Presence of bases or liners on prepared teeth.

Salivary and Blood Contamination: Difficulty in controlling saliva or blood while accomplishing restorative dental therapy is a significant challenge7. These contaminants can influence some dental adhesion concepts in a negative manner. Although dentin is a wet substance, the constituents of saliva and blood create an environment that can destroy dentin bonding. As an example, consider the following common

clinical situation. A clinician has placed the first component of one of the 35

Dentin Bonding Agents

currently popular dentin bonding agents such as Universal Bond 3. At the clinical moment salivary or blood contamination becomes present, flooding the tooth preparation. The impulse is to wash the tooth preparation and place component once again. However, one of this example product is an acidic compound of pH 2-3, and washing it off creates essentially an etch or conditioning of the dentin, with removal of the smear or debris layer. Since Universal Bond 3 depends on smear layer retention of for its bond, what would be the actual bond to dentin in such a situation if the smear layer is etched away? A logical approach to this problem would be. a) b). c) Wash the tooth preparation Roughen the tooth preparation surface to make a new smear layer. Re-Do the dentin bonding steps, hoping to avoid further saliva and/or blood contamination.

Another common problem is contamination of the enamel and/or dentinal surfaces after the conditioning or etching solutions have been placed and a bonding agent has been cured over these surfaces. This is not a

significant problem if the clinician understands the concept of dentin and enamel bonding. The bonded tooth surface needs only 10 seconds of 37% phosphoric acid placement, followed by washing with water, drying and application of another thin layer of uncured bonding agent.

Use of rubber dam or other dry field aids are necessary to avoid salivary or blood contamination during placement of tooth adhesion materials.

Moisture Contamination from hand pieces or air-water syringes : An unrecognized problem in most dental offices is water leakage from air rotor hand pieces or air-water syringes. The source of leakage can be caused by several situations. Among them are 36

Dentin Bonding Agents

Lack of drying devices on air lines leading from the compressor, allowing wet air to be carried to the syringe or hand piece. Condensation of water in air lines after the compressed air has been dried, but before the hand piece or syringe location. Leakage of water through gaskets in plumbing at the dental chair unit.

Heat sterilization of hand pieces and air-water syringes, stimulated recently by an increased emphasis on infection control, has decreased the microorganisms present, but has increased water leakage in syringes and water contamination during adhesive dental procedures.

The mixture of water with restorative or bonding resin is a known problem, but recognition by clinician that this is happening during dental bonding procedures is less well known.

Blowing air from the hand piece or air syringe on to a dry surface as a test procedure will demonstrate easily if water contamination is present.

Oil contamination of hand pieces or /Air water syringes : Oil combined inadvertently with resins used for bonding is a major problem, and it is estimated that many dental offices have oil contamination in their air lines. The oil comes from air compressors, most of which are not maintained well in dental offices. Effective oil filter on air lines are not used in most dental offices. Any of the current dentin bonding agents combined with oil contamination provides an unpredictable clinical result and potential clinical failure. Additionally, combination of oil with the liners, including glass ionomer, resin, calcium hydroxide, and others have unknown results.

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Dentin Bonding Agents

Observation of oil present in air lines is not difficult. A simple test may be conducted by blowing air from an air syringe or hand piece on to a dry impermeable surface, such as a glass mixing slab or dry rubber glove and observing any residue that is present. As described previously, water will be present frequently. Water will evaporate from the test surface. Oil appears similar water on dry surface, but it will not evaporate.

Removing all oil from dental air lines should be an immediate objective. There are several brands of oil filters available from dental dealers. These devices are placed on the air lines after the air compressor and before the air syringe or hand piece. Filters must be changed frequently, as suggested by their respective manufactures.

Surface Roughness of Tooth surface : Most dentists use tungsten carbide steel burs to make tooth preparation. Those burs make scratches and irregularities in tooth surfaces that are retentive for subsequently placed restorative materials. Use of diamonds for tooth

preparation is most common in fixed prosthodontics, and there is increasing use of diamonds in operative dentistry. Diamonds cut irregularities in tooth structure that are related directly to the size of diamond particles used on the diamond abrasive instrument. These range from less than 10m to about 100m. Various investigations have reported the influence on adhesion

created by rough tooth surface. Increased surface area created by surface roughness may explain the slightly better bonds to dentin shown by some investigations. It is possible that mechanical retention may be increased

slightly by the microscopic roughness produced on dentin or enamel by rotary cutting instruments.

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Dentin Bonding Agents

Mechanical Undercuts in Tooth preparation : Since the beginning of dentistry, mechanical undercuts have been placed in tooth preparation to provide retention for subsequently placed restorative materials. If such undercuts are present in tooth structure, and they hold restorative materials from bodily dislodgment from the preparation, they may also resist some microscopic movement of the restorative material caused by thermal or polymerization influences. Therefore, restorations with

traditional dentin-placed undercuts, as well as chemically produced bonding may produce better clinical results, such as less leakage and less sensitivity, than those depending on adhesion alone. If the restoration cannot move due to large undercuts, the adhesive intensity and longevity may be enhanced.

Fluoride content of Teeth: Increased fluoride content of enamel has been shown to resist acid etching. This reduction in enamel acid- etch effectiveness is not significant clinically if the etching time is increased to allow more time for the acid to degenerate the enamel surface and produce more roughness. Clinicians are now etching apparently normal enamel for about 15 seconds and enamel that shows signs of fluoridation for double that time or more7.

Fluoride presence in dentin and its relationship to adhesion of dentin bonding agents is also a matter of concern, since most persons use fluoride so commonly. Fluoride presence in dentin appears to influence bonding dentin adhesion agents negatively. Many dental patients use fluoride gels and rinses and/or fluoride in trays daily for caries-preventive reasons or for desensitization of dentin surfaces. Most of the stannous fluoride gels and more concentrated Sodium fluoride have acidic pH (3-6). Research (Christensen & others, 1991) has shown degeneration of zinc phosphate and glass ionomer

39

Dentin Bonding Agents

cements caused by low pH bleach gels.

Other investigators have shown

fluoride gels to degenerate metal containing glass-ionomer cements significantly but other routinely used cements to a lesser degree. The influence of fluoride on bond of adhesive agents to dentin and enamel surfaces is a factor that needs additional research.

Dentinal canal characteristics: Dentinal canals at the extreme surface of tooth roots or near the dentinoenamel junction have small diameters. As dentinal canals are observed closer to the dental pulp, they become larger. Older dentin has small dentinal canals, while younger dentin has larger dentinal canals. Superficial abraded dentin may have occluded canals. When bonding to dentin, most of the current brands of dentinal bonding agents use some form of mechanical attachment into dentinal canals, as well as other alleged chemical bonds. If the canals are small, attachment should be less, and if canals are large, attachment might be enhanced.

Some research has shown that specific teeth in a given mouth have more or less bonding strength than others. Clinicians should be aware of the

differences in potential dentin bond related to size of dentinal canals or the resistance to bonding offered by specific teeth.

Presence of Plaque, Calculus, Extrinsic stains or debris: Every experienced clinician has seen the effect of leaving dental plaque on a tooth surface and trying to etch the surface. After etching, the plaque covered surface remains shiny. Plaque prevents an etch with 37%phosphoric acid. Penetration of plaque by the less-aggressive acids used in dentin bonding agents is not possible, and clinical adhesive failure will result. Tooth surface

40

Dentin Bonding Agents

stains and dental calculus are easier to see and are removed usually. If they are not removed, the bonding agents will not work.

Enamel or dentin tooth surfaces that are expected to bond to resin or other materials should be cleaned thoroughly before attempting bonding. Occasionally, this cleaning may require the use of sealers, abrasive prophylactic pastes or rubber cups, and even the use of abrasive rotary instruments. Any enamel or dentin surface that requires bonding must be clean before the bonding procedure begins

Presence of Bases or liners on prepared teeth : The multitude of bases and liners present today are confusing to clinicians, and their influence on the bond of subsequently placed restorations is not understood well in the profession.

Bases and liners can be classified in several groups.

Varnish : Copal, cellulose or polyamide varnishes are widely used and eliminates the potential to bond restorative materials to the tooth surface. Although these varnishes may reduce tooth sensitivity, they should not be used if bonding of subsequent materials to tooth surface is expected.

Glass ionomer liners: Placed directly on tooth surfaces, these liners create a moderate bond to dentin, but it is significantly lower than the bond created by placing resin on acid- etched enamel surface or the bonds reported for the current generation of dentin bonding agents to dentin. If resin is placed over glass ionomer liner, the

41

Dentin Bonding Agents

bond of the resin to the tooth can be no stronger than the bond of the glass ionomer to dentin or the bond of the resin to the glass ionomer.

Resin Liners : Numerous companies have marketed filled resins of various types for lining tooth structure. If the chemicals (fluoride, calcium etc) in the resin liners are used effectively, the liners should be placed directly on the dentin surface. If this is done, the liners have little or no bond to dentin, and

subsequent restoration placed over the resin liners will not bond to dentin.

If the dentinal surface does not appear to be pink, it generally means that they are more than one-half millimeter from the dental pulp. In such cases, use of liners may not be necessary, and bonding directly to dentin is often the treatment of choice.

An additional unknown factor is the influence of the chemicals in varnishes or liners on dentin immediately surrounding them, but not covered by the liner or varnish. Constituents of these materials could have a positive or negative influence on dentin bonding in other portions of tooth preparations. Clinicians must make the choice between. Using the desired chemical effect or desensitization effect of the liner or vanish or The reduced microleakage, desensitization and retention of the dentin bonding agents.

Tooth dehydration: Dentin is a wet tissue. Bond strength could be related to wetness of dentin. It may be that over drying could be damaging as placement of the bonding agents in a wet field. Clinical observation has shown that over drying 42

Dentin Bonding Agents

tooth preparations on to which crowns are to be cemented certainly increases tooth sensitivity. Until more conclusive research is available, over drying tooth preparations before placing bonding agents should be considered to be a negative factor. Drying only until the obvious shine of moisture is gone is a good clinical guide.

Constituents of temporary cements : Dentin or enamel that has been on contact with eugenol- containing temporary cements or stearate- containing non-eugenol temporary cements may have different bonding characteristics to resin than virgin tooth structure. Research is mixed on this subject, From research & clinical experiences, it has been concluded that if temporary cements have been in place on the tooth for several days, the liquid portions of the cements have been completely absorbed by the zinc oxide and are rendered relatively inert. No differences were noted in bonds of dentin bonding agents or resin cements to dentin or enamel surfaces that have had eugenol or noneugenol cements on them for two weeks when compared to virgin tooth surfaces. However, more research is certainly needed in this subject. Fresh liquid eugenol placed on dentin or enamel just before attempted bonding could be a negative factor in adhesion

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Dentin Bonding Agents

FACTORS AFFECTING ADHESION TO MINERALIZED TISSUES


For adhesion to take place there must be intimate contact between the adhesive and adherend. The ideal interface between dental restorative materials would be one that stimulates the natural attachment of enamel and dentin at the dentinoenamel junction. Intimate molecular contact between the 2 parts is a prerequisite for developing strong adhesive joints8. This means that the adhesive system must sufficiently wet the solid surface. The factors that affect this adhesion to mineralized tissues can be broadly classified as follows.

I. Factors related to the adherent : Physicochemical properties of dentin that complicate dentin adhesion The dentin smear layer and dentin permeability. Transformed dentin structure due to physiological and pathological processes.

II. Factors related to restorative resins : Physical properties of adhesives Polymerization contraction of restorative resins Contraction stress relaxation by flow Youngs modulus of elasticity Initial polymerization site The relaxation of contraction stress by hygroscopic expansion Thermal expansion co-efficient and thermal conductivity. Transmission of stress across the composite dentin interface

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Dentin Bonding Agents

Physicochemical Properties of dentin that complicate, dentinal adhesion : Mineralized dentin is relatively stiff (Modulus of elasticity of 14 to 19 GPa and has an ultimate strength of 230 to 370Mpa (compressive) or 45 to 138 Mpa (shear) which varies with dentinal depth and tubule orientation5.

Following acid etching the mineral phase of the dentinal surface and some non-collagenous proteins are solubilized and some of the proteins are extracted, exposing the collagen fibrils of the deminralized dentinal matrix. The demineralized dentinal matrix becomes very soft and elastic. Infact, the modulus of elasticity of wet demineralized dentinal matrix is only about 5 MPa, which is more than 1,000 times lower than that of mineralized dentin. The clinical implication of this low stiffness is that the fibril network can easily collapse when air dried, there by interfering with the up take of adhesive monomers.

The permeability of bonding substrates to monomer and the monomer diffusivity into the substrates are essential factor for the hybridization of resin in dental substrates. Mineralized dentinal matrix is relatively impermeable to resin monomers in the lengths of time that are required (clinically for bonding (30 to 60 seconds).

Permeability refers to the ease with which a substance can move into across a diffusion barrier (i.e. substrate). Two types of dentinal permeability must be considered. The diffusion of substances through tubules filled with dentinal fluid to reach the pulp intratubular dentinal permeability . The second important type of dentinal permeability is the diffusion of monomer into demineralized intertubular dentin, the dentin between the tubules. referred to as intertubular dentinal permeability. This is

45

Dentin Bonding Agents

After the surface is acid etched and rinsed with water, between the collagen fibers the spaces, are filled with water and are presumed to remain about 15 to 20m wide. It is through these spaces that adhesive monomer must diffuse if it is to infiltrate the demineralized dentinal matrix. Both

intratubular and intertubular dentinal permeability is important in dentin bonding.

Dentinal tubules permit adhesive monomer to flow down the tubules for varying distances. Most tubules contain multiple lateral branches that radiate 2 to 6 m from the lumen and they provide another route for monomer infiltration of hybrid layers.

Further experimental studies conducted on collagen fibers in dentin indicated that there is space between the collagen fibers for tissue fluid (i.e. water) During dehydration procedure this water may be lost and it could result in shrinkage of collagen fibers. Nakabaysashis original, innovative ideas about monomer infiltration into demineralized dentinal matrix, and the importance of maintaining the permeability of the collagen fibril network to monomers, resulted in a major advance in the understanding of how resin dentin bonding is the result of molecular intertwining of the resin within the collagen fibers. The resin

monomers penetrate acid- etched (i.e. partially denatured) collagen fibrils via spaces that can swell or shrink depending on bonding condition. Under some conditions (high water concentration, acidic pH), the collagen fibrils might swell slightly and reduce the width of the perifibrillar spaces, making it more difficult for primer monomers to infiltrate the collagen fibril network. Under other conditions (air drying, dehydration by water-miscible organic solvents) the collagen fibrils may shrink (decreasing their diameter) there by increasing 46

Dentin Bonding Agents

the width of the spaces. But air-drying causes collapsing of the collagen fibril network bringing the adjacent fibrils into intimate contact with each other. As a result the collagen peptides may form intermolecular hydrogen bonds with the nearest neighboring collagen peptides, which may contribute to further collapse of the network by causing shortening of the fibrils and an increase in stiffness. So overdrying of collagen fibrils should be avoided8.

The dentin smear layer and dentin permeability : When the tooth surface is instrumented with rotary and manual instruments during cavity preparation, cutting debris is smeared over the enamel and dentinal surface forming what is termed the smear layer. The smear layer has been defined as any debris, calcific in nature, produced by reduction or instrumentation of enamel, dentin/ cementum. The burnishing action of cutting instruments generates considerable amounts of frictional heat locally and shear forces, so that the smear layer becomes attached to the underlying surface in a manner that prevents it from being rinsed off or scrubbed away.

The composition reflects the structure of the underling dentin. It mainly contains pulverized hydroxyapatite and altered collagen, mixed with saliva, bacteria and other grinding surface debris. The smear layer thickness may vary from 0.5 to 5m. Smear debris occludes the dentinal tubules with the

formation of smear plugs .The smear layer is porous and penetrated by sub micron channels, and allows for a small amount of dentinal fluid to pass through. The smear layer is reported to reduce dentinal permeability by 86%.

In an in vivo study ethylene diamine tetracetic acid (EDTA) was found to be the most potent conditioner for removing the smear layer and opening up the orifices of the dentinal tubules. Acidic conditioner inorder of increasing 47

Dentin Bonding Agents

potential to remove smear layer include citric, polyacrylic, lactic and phosphoric acids. Cavity cleansers, such as Tubulicid and hydrogen peroxide, were found to have only a slight effect.

The dentinal permeability and, consequently, the internal dentinal wetness depend on several factors like the diameter and length of the tubules, the viscosity of dentinal fluid and the molecular size of substances dissolved in it, the pressure gradient, the surface area available for diffusion, the patency of the tubules, and the rate of removal of substances by pulpal circulation

The permeability of dentin is not uniform through out teeth, because the number of tubules/mm2 is not uniform. Dentin located just beneath the dentinoenamel junction has approximately 1500 to 1900 tubules/m that are about 0.8m in diameter, where as the dentin near the pulp contains 4500 tubules / mm that are about 2.5m in diameter9.
2 2

Schematic Diagram showing that there are fewer tubules/mm2 in superficial dentin than in deep dentin, and still fewer tubules per unit area in root dentin.

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Dentin Bonding Agents

Dentin near pulp horns more permeable than dentin further away because the density and diameter of tubules are highest near pulp horns. Axial dentin is more permeable than the pulpal floors of class II cavities Root dentin is less permeable than coronal dentin because there are fewer tubules per square millimeter. The dentin beneath carious lesion is much less permeable than normal dentin because the tubule of caries affected dentin is filled with mineral crystals.

The variability in dentinal permeability makes it a more difficult a more difficult substrate for bonding. Earlier bonding was difficult as the resins were hydrophobic but recent adhesive systems having a hydrophilic part and are not affected by increase in depth.

Transformed dentin structure due to physiological and pathological processes : Structural changes can occur in the dentinal tubule due to pathologic carious, erosive and abrasive processes and physiological aging. In carious instances the lumina of the dentinal tubules are very narrow or may even obliterated by deposition of intratubular crystals and apposition of irregular sclerotic dentin.

Dentin undergoes physiologic dentinal sclerosis as part of the aging process and reactive sclerosis in response to slowly progressive or mild irritation, such as mechanical abrasion or chemical erosion. Tertiary or reparative dentin is produced in the pulp chamber at the lesion site in response to insults such as caries, dental procedure or attrition.

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Dentin Bonding Agents

Hypermineralization, obstruction of tubules by Whitlockite crystalline deposits and apposition of reparative dentin adjacent to the pulp are welldocumented responses to caries.

Sclerotic dentin usually contains few patent tubules and therefore has low permeability. Heavily sclerotic dentin has areas of complete

hypermineralization without tubule exposure, even when etched with an acid.

All of these morphologic and structural transformations of dentin, induced by physiologic and pathologic processed result in a dentinal substrate that is less receptive to adhesive treatments than in normal dentin.

Obstruction of the dentinal tubles by whitlockite or caries crystals.

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Dentin Bonding Agents

CHEMISTRY OF ADHESION
There are two main types of chemical adhesion. By primary valence forces By secondary valence forces.

The strongest and most stable primary valence bonds are the covalent and coordinative bonds, which are both electron pair bonds. Ionic bonds may also give strong adhesion. Secondary valence bonds or intermolecular bonds are classified as Vanderwaals forces and hydrogen bonds.

The chemistry of the adhesive agents can be explained based on the type of adhesion. Adhesion based on ionic polymers. Adhesion by coupling agents Grafting to collagen.

Adhesion based on ionic polymer : There are two types of dental materials that are classified as polyelectrolytes. These are zinc carboxylate cements and glass ionomers or glass-poly (alkenoates).

The glass-poly (alkenoates) is based on poly (acrylic acid) and copolymers of, for example, acrylic acid-maleic acid or acrylic acid- itaconic acid.

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Dentin Bonding Agents

Structure of poly (alkenoid acid). The drawing shows two copolymers with the carboxylic acid units.

Investigators have shown that these materials can bond to both enamel and dentin with out acid etching.

Adhesion of the poly (alkenoic acid)-based materials to apatite can be achieved by ionic bonding with calcium ions acting as bridges. Hydrogen bond formation may occur, although to a lesser extent. Dentin is a composite material with approximately equal quantities by volume of hydroxyapatite and organic materials. The organic material is mainly collagen with both free carboxylic groups and amino groups. Hydrogen bonds can be formed between the carboxylic groups of the poly (alkenoic acid) and amino groups of the collagen.

Mechanism of adhesion of poly (alkenoic acids) to dentin collagen 52

Dentin Bonding Agents

Ions diffusing from the cement particles or from dentin apatite allow cat ion bridges to be formed between carboxylic groups of poly (alkenoic acid) and collagen.

The poly (alkenoic) materials showed good adhesion to enamel and somewhat poorer adhesion to dentin. Dentin etched with 50% citric acid showed the lowest strength values. During acid etching the calcium ions are removed from the apatite of the dentin, and the possibility for formation of calcium bridges between the carboxylic groups of the poly (alkenoic acid) and acid groups of both apatite and collagen is greatly reduced. Further more, there is an enrichment of organic material (collagen) at the surface of dentin during acid etching, so the bonding to dentin is weakened due to decreased bridge formation by calcium ions and reduced quantities of apatite at the dentin surface.

Adhesion based on coupling agents : This type of adhesion is seen to occur with the non-polyelectrolyte adhesives. Bonding can be accomplished to the inorganic part of dentin,

hydroxyapatite or to the organic part consisting mainly of collagen bonding can also be obtained to inorganic part of the dentin.

Treatment of acid-etched enamel with different coupling agents leads to only minor improvement of the bond strength. One coupling agent was the silane usually used for silanization of the filler particles in composites, 3methacryloyloxypropyl- trimethoxysilane. Another coupling agent was a

butylacrylate-acrylic acid copolymer with free carboxylic acid groups.

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Dentin Bonding Agents

N-2 hydroxy-3-methacryloyloxy-propyl (NPG-GMA) can co-ordinate to metal ions (e.g. ca++) by a chelating effect of the carboxylate group, the amine group, and the hydroxyl group.

The binding of organic coupling agent NPG-GMA to hydroxyapatite via a metal ion (M)

The coupling agents utilize the concept of hydrophilic and hydrophobic groups i.e. it consist of a difunctional molecule one part of which enters into a chemical union with the tooth surface while the other attaches to resin10.

The coupling agents have basically the formula M-R-X M- Methacrylate group, which eventually becomes bound tooth resin by copolymerzation. X- represents a reactive group, which interacts with the tooth surface. The reactive groups are end groups. R-is the linking and spacing group. Spacing group must be able to provide the necessary flexibility to the coupling agent to enhance the potential for bonding of the reactive group. If the molecule is excessively rigid the

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Dentin Bonding Agents

ability of the reactive group to find a satisfactory conformational arrangement is jeopardized e.g.: Ethyl/oxypropyl

In N- phenyl, glycine glycidyl methacrylate a chelate bond is found between the N-phenylglycine group and the calcium of the tooth, while the methacrylate group becomes incorporated into the resin during polymerization. Another coupling agent which works by chelating with calcium is (4-META).

The monomer 4 methacryloyloxyethyl trimellitic anhydride (4-META)

Bond strength of these coupling agents can be increased by pretreatment with certain mordant ions such as ferric and aluminum ions in the form of aqueous solutions of their chlorides/oxalate salts. A strongly bound surface layer concentrated in ions capable of reacting with the chelating species is formed. Systems based on the combined use of mordant ions and coupling agents are now becoming available .The exact mechanism of role of these mordant ions is not known. But it is possible that the ionic solution is simply acting as weak acid, which solubilize and reprecipitate the dentin smear layer. In some case the acid may etch the dentin, opening up the dentinal tubules and encouraging mechanical attachment10.

A procedure, which can be classified as the multilayer system has been suggested. This system entails the treatment of the mechanically prepared cavity with a ferric oxalate solution and an acetone solution of NPG-GMA or

55

Dentin Bonding Agents

NTG- GMA. An acetone solution of PMDM (the reaction product of promellitic dianhydride and 2- hydroxy ethylmethacrylate) is placed and surface is air blown. Finally the composite restorative materials is inserted and polymerized.

The chemistry of such a treatment is based on the assumption that the treatment with ferric oxalate solution initiates several reactions with the smear layer, resulting in a porous layer cross-linked with metal ions. The layer constitutes insoluble iron phosphate and calcium oxalate attached to a continuous structure.

During treatment with NPG-GMA these monomer are bonded to iron ions by co-ordinative bonds. A continuos film is formed by polymerization of the methacrylate groups. NPG-GMA contains benzene ring rich in (pie) electrons. During treatment with PMDM monomer, this monomer is bonded to the NPG-GMA by complex or charge transfer complex formation.

The disadvantage of this system is discoloration due to reaction products of ferric oxalate. In tenure ferric oxalate has been replaced with aluminum oxalate.

Other coupling agents which primarily bond to the inorganic component of dentin contain reactive phosphate groups. The interfacial bond is

established through attractions between the negative charges of oxygen on the phosphate and the positively charged calcium at the dentin surface.

The bond strength to dentin produced by this type of adhesive is typically around 5MPa although it is not certain how durable this bond is in

56

Dentin Bonding Agents

moist environment. This R-O-P bond is thought to become hydrolyzed leading to a gradual reduction in strength. M-R-X here X=O-P. Coupling agents utilizing this concept of hydrophobic and hydrophilic groups are the monomers based on phosphates or phosphonates. The

hydrophilic phosphate group is thought to interact with the calcium ions of dentin.

An adhesive which is closely related to that mentioned before is a chloro substituted phosphate ester of BISGMA. Compound of this type can be formed by reaction between BIS-GMA and phosphorous oxychloride (POCL3). Bonding to tooth calcium may occur through chlorines having

partial negative charges. A more likely explanation of the mode of action is that the chlorophosphorus ester becomes rapidly hydrolyzed on contact with moisture on the dentin surface. Due to hydrolysis, HCL is liberated. Bond formation to calcium takes place as mentioned.

HCl -liberated may also play some part in bond formation by altering the structure of dentin including smear layer. Bond strength resulting from this type of coupling agent is about 3-5 MPa. But durability is adversely affected by hydrolysis.

A number of so called second generation adhesives in the market are based on monomers containing phosphate groups including Scotch bond (3M), Clearfil new bond (Kuraray) and Prisma Universal bond.

Clearfil new bond contains 2-methacryloxyethyl-phenyl phosphoric acid (MEP-P) reported to give adhesive strength of 5-6MPA.

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Dentin Bonding Agents

A product recently becoming commercially available depends on 2stage dentin treatment inorder to achieve adhesion. Two liquids are supplied. The first is an aqueous solution of HEMA and maleic acid. Both are

hydrophilic monomers which are able to make intimate contact with moist dentin.

The acid solubilizes the dentin smear layer and the soup of solubilized dentin, HEMA and maleic acid becomes firmly attached to the underlying dentin, helped by ability of maleic acid to interact with calcium. Second liquid consists of application of light activated resin, which consists of HEMA, and BIsGMA along with polymerization activators .The HEMA imparts some hydrophilic characters to the resin to ensure more intimate contact-than, which would be achieved with BIsGMA alone.

The adhesive system described so far work mainly through affinity for calcium ions.

All the above-mentioned adhesive systems form a more tenacious bond to enamel.

Some direct bonding between reactive groups in dentinal collagen and reactive groups in adhesive is possible. However the contribution from this type of bond is negligible compared to the bond formed with calcium.

The first bonding system for dentin that were reproducible enough to eliminate the need for mechanical retentive cavities began to be reported in the late 1970s. Nakabayashi et al reported the first system based on

methymethacrylate, tributyl borane as initiator and 4 META as bonding comonomer. 58

Dentin Bonding Agents

4-META/MMA- TBB resin system E.g.: Amalgabond and super bond D liner.

This system has a water-triggered polymerization. Methyl methacrylate is placed on the cut dentin surface with its smear layer intact. The monomer diffuses through the smear layer and into the dentin. The tributyl borane in presence of water (that is present on dentin surface) splits to butyl radicals, which graft on to the collagen molecules and initiate the polymerization reaction of the methyl methacrylate (chemical cure). The 4- META is a

methacryl-substituted mellitic anhydride, which is hydrolyzed to mellitic acid and chelates calcium. The chelation adds to binding between the growing methyl methacrylate chains, increasing both grafting and cross linking density of the final acrylic dentin composite layer.

The dentin and its smear layer are embedded in hydrophobic resin and can be bonded to by the curing composite restoratives materials by copolymerization. The bond is strong and resistant to hydrolysis. All these systems described are basically adhesive molecules with a potential for calcium bonding. It can be divided into 3 groups 1. Phosphate based adhesive M-R1-POYZ 2. Adhesive based on amino acid. M-R2-N2-R 3-COOH 3. Adhesives based on dicarboxylic acid M-R4- COOH COOH 59

Dentin Bonding Agents

All these case involve attraction between negative changes on the adhesive and positive changes on the tooth calcium ions.

Collagen bonding adhesive : Grafting to collagen : Some adhesive systems have been developed specifically with the aim of grafting to the organic collagenous component of dentin. Possible bonding sites of the collagen molecule include the hydroxyl, carboxyl and amino and amido groups. Removal of hydrogen from any of these groups allows combination with chemicals present in denting bonding agents. Compounds that have a capacity to react with one or more groups of collagen are isocyanates, carboxylic acid chlorides, carboxylic acid anhydrides and aldehydes.

One product relies on the addition reaction between the isocyanate groups and both the hydroxyl and the amine groups of collagen.

The adhesive is a low molecular weight polyurethane having excess of isocyanate groups. Bond strength to dentin about 4 MPA achieved through this is variable and depends on the presence of moisture on the dentin surface. Isocyanate groups undergo a rapid reaction with water.

Another commercial product depends on the reaction, which readily occurs between aldehyde groups and amine groups. The active components are glutaraldehyde and HEMA. Bonding involves a complex reaction in which aldehyde and amine groups react to from an adhesive link and the HEMA react with glutaraldehyde at dentin surface to give a polymerizable methacrylate group, which is attached to dentin and is capable of completing the adhesive

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Dentin Bonding Agents

link with restorative resin by co-polymerization. In order to produce optimal result it is necessary to remove the smear layer.

GLUMA system has been introduced based on this. Here an equimolar mixture of gluteraldehyde \HEMA is placed on dentin that has been cleansed of its smear layer by EDTA solution. The Gluteraldehyde\HEMA penetrates the tubules to depth greater than 300, m. There is some reaction between the hydroxyl groups and HEMA/ gluteraldehyde. The result is a dentin surface well wetted by a hydrophilic monomer. An intermediate unfilled resin is then placed on the treated surface, which forms a graded bridge between the hydrophilic HEMA and the hydrophobic composite resin. The reaction

basically as suggested by Munnksgaard is that of an amino group of EDTAdemineralised dentin collagen reacts forming covalent bonds. Other systems infiltrate the intact smear layer cross-linking it by reaction of the isocyanate groups with collagen. The smear layer is first deflated and dehydrated with acetone to maximize this reaction. The cross-linking extends to the very outer most part of the intact dentin but no further.

The isocyanate also bears a methacrylate group, which is capable of copolymerizing with composite resin. This is a very quick technique marred by the very rapid reaction of the isocyanate group which can cause the applicator brush to drag in the cavity. This system seals the dentin well provided the cut dentin is covered in an intact smear layer.

If the layer has been removed for any reason protection from acid attack is less in that area.

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PARAMETERS AFFECTING THE CLINICAL PERFORMANCE OF ADHESIVES


Dentine factors Tooth Patient Material

Dentine factors: Includes micro structural features of the dentine involved with local adhesion, smear layer, dentinal tubule density, size and length, dentin sclerosis. Smear layer is partially porous and it dramatically reduces the fluid flow from the underlying dentinal tubules. It acts as a biological band, aid in reducing postoperative sensitivity4.

Adhesion is affected by wetness of the dentine; this in turn is related to the density and size of dentinal tubules. Tubules density is greater near the pulp and tubules represent a much larger portion of the dentinal volume (or) around 28-volume% along the pulpal wall Vs 4 volume % at the DEJ. So this area has the greatest potential to immediately wet the cut dentinal surfaces. Bond strengths in deep dentine generally are lower because of the interference of moisture from tubules. Newer dentine bonding system including hydrophilic monomers that penetrate surface moisture and circumvent this problem.

Dentine Sclerosis : In response to caries, trauma (or) other stimuli, odontoblasts attempt to seal dentin by laying sown a bridge of peritubular hydroxyapatite crystals.

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These sclerotic changes associated with again may have an adverse effect o dentin bonding.

Tooth factors: a. Lesion size and shape. b. Enamel and dentine structure. c. Tooth flexure. d. Tooth location.

Shallow, saucer shaped lesions lack insufficient surface area for adequate retention, precludes sufficient bulk of restorative material to resist deflection. This type of restoration appears to be particularly vulnerable to dislodgement during tooth flexure. Eccentric forces on occlusal surface

generate a critical flexure resulting in stress concentration in bonded areas. These flexural forces appear capable of debonding cervical restorations, especially those without macro-mechanical retention4.

Tooth location: Created cervical restorations failure in mandibular teeth related to difficulties with moisture control; (or) due to greater propensity for tooth flexure to occur in mandibular teeth, this again could occur as the result of lingual inclination of the crown and the smaller cross sectional area of mandibular teeth in the cervical area.

Patient factors: History of bruxism(or) traumatic occlusion produces greater occlusal stresses on their teeth. Clinical studies observed that, there is a link between the presence of occlusal stress and loss of cervical restoration retention.

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Material Factors : Early improvements in dentin bonding agents had focused on developing chemical bonds to tooth structure. But currently micro-mechanical bonding is emphasized.

First generation DBA was designed for ionic bonding to hydroxyapatite (or) for covalent bonding to collagen. These materials were hydrophobic and were limited by the relative attachment strength of the smear layer to the underlying dentin. Bonding strength was about 2-6Mpa. New generation bonding agents procedures attempt to remove penetrate (or) solublize the smear layer and then wear the underlying dentin with resin monomers that are more hydrophilic. Bond strengths are decidedly improved by eliminating (or) penetrating the smear layer with mild organic acids. However the dentin may be extensively demineralized and weakened depending upon the concentration of acid and exposure time. Strong acids removed smear plugs and After dentin-

demineralized the intertubular dentin near the surface.

conditioning application of hydrophilic monomers penetrates the decalcified inter tubular dentine and embed 1-5 m of superficial dentine. zone, appears to be the primary site for dentinal adhesion4. This

transitional zone called Hybrid layer, interpenetration zone (or) interdiffusion

Bonding strength ranged from 12-22 MPa. Hydrophilic systems seem to keep the collagen network open while penetrating it. Also polymerization shrinkage, water absorption of the overlying composite restoration also influence bond strength. More cervical retention failures are associated with higher modules composite that include macro fillers and higher filler content. Where as macrofil composites with lower elastic modulus appear to flex in response to cervical deformation rather than debonding.

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STRUCTURE AND COMPOSITION OF ENAMEL AND DENTIN


Enamel : Enamel is the hardest of the mineralized tissues of the body. Enamel is formed by cells called ameloblasts, which originate from the embryonic germ layer known as ectoderm. Enamel covers the anatomical crown of the tooth. It is thickest over the cusp and thinnest at the base of the pits, fissures and the cervical region of the crown12.

Composition: Enamel composed of both inorganic and organic substances. 95% to 98% inorganic matter by weight. Hydroxyapatite, in the form of a crystalline lattice, is the largest mineral constituent and is present 90% to 92% by volume. Other minerals and trace elements are contained in smaller amounts. The remaining constituents of tooth enamel are an organic content of about 1% to 2% and a water contents of about 4% by weight, these total approximately 6% by volume. Various ions-strontium, magnesium, lead and fluoride, if present during enamel formation, may be incorporated into or adsorbed by the hydroxyapatite crystals. The bulk of organic material consists of tyrosine-rich amelogenin polypeptide (TRAP) peptite sequence lightly bound to the hydroxyapatite crystals as well as non-amelogenin protein. The organic

component of enamel is the protein enamelin. The distribution of enamelin between and on the crystals aids enamel permeability.

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Dentin Bonding Agents

Physical properties : The hardest substance of human body is enamel. Hardness may vary over the external tooth surface according to the location; also, it decreases inward, with hardness lowest at the DEJ. The density of enamel decreases from the surface to the DEJ. Enamel is a very brittle structure with a high elastic modulus and low tensile strength, which indicates a rigid structure.

The high inorganic content confers a translucent quality to the enamel with color being imparted by the dentin especially where enamel is thinnest at the cervical region. Developmental anomalies of maturation and consequences of carious attack produce localized changes in opacity, Specific gravity is 2.8.

Hardness-200-500 Knoop hardness range. Enamel is selectively permeable to certain ions and molecules, permitting both partial and complete penetration. Enamel permeability

decreases with age because of changes in the enamel matrix.

Enamel is soluble when exposed to an acid medium, but the dissolution is not uniform. Solubility of enamel increases from enamel surface to DEJ.

Acid etching of enamel surface produces an irregular and pitted surface with numerous microscopic undercuts by an uneven dissolution of enamel rod heads and tails. Composite or pit-and-fissure sealant is bonded to the enamel surface by resin tags formed in the acid- etched enamel rod structures. Therefore the structure of enamel can be an asset when it is subjected to purposeful and controlled acid dissolution of the enamel rods to provide this micro retention for composite or sealant.

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Microscopic structure of enamel : Human enamel is composed of rods that in transverse selection are shaped with a rounded head or body section and a tail section, which forms a repetitive series of interlocking prisms. The rounded head portion of each prism (5 m wide ) lies between the narrow tail portions (5 m long) of two adjacent prisms. The rounded head portion is oriented in the incisal or occlusal direction; the tail section is oriented cervical.

Enamel rods follow a wavy, spiraling course, producing an alternating arrangement for each group or layer or rods as they change direction in progressing from the dentin toward the enamel surface where they end a few micrometers short of tooth surface.

Rods follow a curving path through one third of the enamel next to the dentinoenamel junction. After that, the rods usually follow a more direct path through the remaining two third of enamel to the enamel surface. Other

microscopic structures also appear in enamel these include lamellae, which represent a localized increase in the size of rod sheath and may run both a short and long course.

Enamel tufts are hypomineralized structures of enamel rods and interrod substance that projects between adjacent groups of enamel rods from the dentinoenamel junction. Enamel Spindles are odontoblastic processes, which cross dentinoenamel junction into the enamel.

Enamel lamellae are thin, leaf like faults between enamel rod groups that extend from the enamel surface toward the dentinoenamel junction.

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The enamel surface itself is a micro morphologically and chemically complex region. An understanding of the micro morphological characteristics of the enamel and its biophysical and physiological properties has been significant in achieving interactions between it and dental biomaterials.

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DENTIN
Dentin forms the largest portion of the tooth structure extending almost the full length of the tooth. Externally dentin is covered by enamel on the anatomic crown and cementum on the anatomic root. Internally dentin forms the walls of the pulp cavity.

The dentin is laid down by Odontoblasts. The most recently formed layer of dentin is always on the pulpal surface. This unmineralized zone of dentin is immediately next to the cell bodies of the odontoblasts and is called predentin. The dentin forming the initial shape of the tooth is called primary dentin.

After the primary dentin is formed and the tooth has erupted dentin deposition continues at a reduced rate even without obvious external stimuli and the dentin is called as secondary dentin. In secondary dentin the tubules take a different directional pattern in contrast to primary dentin.

Reparative dentin (tertiary dentin) is formed by replacement odontoblasts (termed secondary odontoblasts) in response to moderate level irritants, such as attrition, abrasion, and erosion, trauma, moderate rate dentinal caries, and some operative procedures. It usually appears as a localized dentin deposit on the wall of the pulp cavity immediately sub adjacent to the area on the tooth that has received the injury.

When a moderate level of stimuli are applied to dentin the affected odontoblastic processes may die with associated odontoblasts. These areas of

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Dentin Bonding Agents

dentin are called dead tracts and extend from the external dentin surface to the pulp.

Sclerotic dentin results from aging or mild irritation and causes a change in the composition of the primary dentin. The peritubular dentin becomes wider, gradually filling the tubules with calcified material, progressing from the dentinoenamel junction pulpally. These areas are harder, denser, less

sensitive, and more protective to the pulp against subsequent irritations. Sclerosis resulting from aging is physiological dentin sclerosis and that resulting from a mild irritation is reactive dentin sclerosis. Reactive dentin sclerosis often can be seen radiographically in the form of more radiopaque area in the S-shape of the tubules. Eburnated dentin is a term referring to the outward portion of reactive sclerotic dentin where slow caries has destroyed formerly overlying tooth structure, leaving a hard, darkened, cleanable surface.

Structure : The dentin comprises of dentinal tubules, which are small canals that extend across the entire width of dentin, from dentinoenamel junction or dentinocemental junction to the pulp. Each tubule contains the cytoplasmic cell process (Tomes fiber) of an odontoblast. Each dentinal tubule lined with a layer of peritubular dentin, which is more mineralized than the surrounding intertubular dentin12.

The surface area of dentin is much larger at the dentinoenamel or dentinocemental junctions than it is on the pulp cavity side. Since the

odontoblasts form dentin progressing inward toward the pulp, the tubules are forced closed together. The number of tubules increases from 15,000 to

20,000/mm2 at the dentinoenamal junctions to 45000 to 65,000/mm2 at the pulp. The lumen of the tubules varies from the dentinoenamel junction to the 70

Dentin Bonding Agents

pulp surface as well. In coronal dentin, the average diameter of tubules at the dentinoenamal junction is 0.5 to 0.9m, but increase to 2 to 3m at the pulp.

The course of dentinal tubules is in a slight S-curve in the tooth crown, but the tubules are straighter in the incisal ridges, cusp and root areas. The ends of the tubules are perpendicular to the dentinoenamel junction and dentinocemental junctions. Along the tubule walls are small lateral openings called canaliculi. As the odontoblastic process proceeds from the cell in the pulp to the dentinoenamel junction lateral secondary branches extend into the canaliculi and appear to communicate with lateral extensions of adjacent odontoblastic processes. Near the dentinoenamel junction the tubules divide into several terminal branches, thus forming an inter communicating and anastomosing network.

Chemical composition : Composition of human dentin is approximately 75% inorganic material, 20% organic material, and 5% water and other materials. Dentin is less

mineralized than enamel but more mineralized than cementum or bone. The mineral content of dentin increases with age. The mineral phase is composed primarily of hydroxyapatite crystallites. The organic phase of dentin consists primarily of collagen.

The dentinal tubules are normally filled with odontoblastic processes and dentinal fluid, which makes it a difficult surface to bond to. Further the collagen fibers are usually type I collagen with traces of type IV collagen. They consist of carboxyl, amino and hydroxyl surface groups. The other noncollagenous constituents that can be found are dentin phosphoprotiens, sialoproteins and osteocalcins.

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Dentin Bonding Agents

Physical properties : Thickness of dentin varies with the age of the tooth. As age advances, the thickness is more than the younger age groups. Amount of dentin in primary teeth is half of that in corresponding permanent successor.

Depending on the depth of the preparation, the substrate surface can consist of widely varying proportion of intertubular dentin, peritubular dentin, secondary dentin and sclerotic dentin. Dentin is saturated with water and oxygen and water content again varies according to the type of dentin.

Resistance to fatigue : Collagen fibrils are generally distributed randomly in intertubular dentin but are oriented circumfererentially around tubules5. The more randomly the fibrils are distributed, the higher will be the probability that the growth of micro cracks will be retarded during function. If there is an intimate

association between resin and collagen fibrils, then that bond will undergo stress and strain under function and may exhibit fatigue over time. If there is no true bond, then both the resin and the collagen fibrils may experience fatigue separately over time.

Micro hardness: Pashley et al reported that the micro hardness of dentin fell when dentin was tested from superficial to deep regions. Using a modified atomic force microscope (AFM) Kinney et al demonstrated that the decrease in hardness with dentinal depth, reported by Pashley et al caused by a decrease in the stiffness of intertubular dentinal matrix14.

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Dentin Bonding Agents

Elasticity: Mineralized dentin is relatively stiff (modulus of elasticity of 14 to 19 GPa) and has an ultimate strength of 230 to 370 MPa (compressive) or 45 to 138 MPa (shear).

Following acid etching, the mineral phase of the dentinal surface and some noncollagenous proteins are solubilized and some of the proteins are extracted, exposing the collagen fibrils of the demineralized dentinal matrix. This produces a profound change in the physical properties of dentin

The demineralized dentinal matrix becomes very soft and elastic. The modulus of elasticity of wet demineralized dentinal matrix is only about 5MPa, which is more than 1,000 times lower than that of mineralized dentin. The clinical implication of this low stiffness is that the fibril network can easily collapse when air-dried, there by interfering with the uptake of adhesive monomers.

Permeability : Permeability refers to the ease with which a substance can move into or across a diffusion barrier. Two types of dentinal permeability must be considered. The movement of fluid with in dentinal tubules intratubular permeability is responsible for dentinal sensitivity or pain.

The diffusion of substances through tubules filled, with dentinal fluid to reach the pulp is another example of intratubular dentinal permeability.

The second important type of dentinal permeability is the diffusion of monomer into demineralized intertubular dentin. intertubular dentinal permeability. 73 This is referred to as

Dentin Bonding Agents

For hybrid layer formation, intertubular dentin must be demineralized to expose the collagen fibrils of the dentinal matrix and to create diffusion pathway for monomer infiltration. These fibrils are separated by spaces about 15 to 20m wide that was previously occupied by apatite crystallites. After the surface is acid etched and rinsed with water, these spaces are filled with water and are presumed to remain about 15 to 20m wide. It is through these spaces that adhesive monomer must diffuse if it is to infiltrate the demineralized dentinal matrix.

The movement of resin monomer into these long, continuous, interconnected, narrow channels, or pores is an example of intertubular permeability into demineralized dentin. The permeability of the substrate must be maintained as high as possible to obtain good monomer infiltration for hybridization of demineralized enamel and dentin.

The penetration of resin monomer into dentinal tubules to form hybridized resin tags to intratubular dentin is an example of intratubular dentinal permeability. Both types of dentinal permeability are important in dentin bonding

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Dentin Bonding Agents

ENAMEL BONDING SYSTEMS


Enamel bonding systems most often consist of an an unfilled or lightly filled liquid acrylic monomer mixture placed onto acid etched enamel.The monomer flows into the interstices between and within enamel rods14.

The most significant discovery in dentistry during the last three decades is that by Dr. Michael Buonocore in 1955, working in New York. He discovered that the bond strength between human enamel and acrylic resin could be tremendously enhanced by exposing the tooth to a mild acidic solution before applying resin to enamel surface.The effective etching was possible only due to the morphological characteristics of enamel. It is composed of bundles of rods, prisms, seeming to radiate from the center of the tooth towards the periphery. The area that surrounds these individual prisms and serves as mortar for them is known as the interprismatic enamel. It is a fortunate accident of nature that normally there is a difference between the resistance of enamel prisms and interprismatic enamel to acidic attack. Thus Dr. Buonocore discovered placing a weak acidic solution on the enamel surface causes a differential etch rate between the two areas. This results in an irregular and pitted surface. In addition to the presence of enamel prisms it has been discovered that the enamel prisms it has been discovered that the enamel contains approximately l%-2% space by volume. Although this means that the enamel is only minutely porous. These porosity also play a role in the bonding process. This results in augmentation of the bond strength achieved by differential etching.

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Dentin Bonding Agents

Etching Agents: 1. Phosphoric Acid: A concentration between 30%-50% with 37% being the

concentration most commonly provided.

2. Pvruvic acid: This may be a suitable alternative to phosphoric acid. But the stability of pyruvic acid solutions are not consistent.

3. An Alpha- ketocarboxvlic acid

Etching Pattern: Exposure of human enamel to conditioning solutions produces three basic etching patterns:

TYPE-I(Core Etching): This pattern is created when the center of the prisms rather than the

interprismatic enamel (i.e.) prism core material is preferentially removed leaving the prism peripheries relatively intact resulting in a honeycomb appearance. The average width of the craters usually found in this type of etching is 5 microns. This fact is of particular significance when selecting the luting agent for the bonding and fusing techniques. Any filler particle of greater diameter would simply not penetrate the enamel surface.

TYPE-H (Peripheral Etching): This type of etching results when the interprismatic enamel erodes more rapidly than the prism core i.e. the peripheral regions of the prisms are dissolved preferentially leaving the prism core relatively intact resulting in a cobblestone appearance15.

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TYPE-III ( Mixed patterns): This type of etching pattern results when the enamel being etched is composed of a homogenous mass instead of the more commonly found prismed structure.

Deciduous teeth often exhibit just a stratum in their outermost layer. Since the outer layer is homogenous in stiucture applying an acid etchant results only in a reduction of enamel bulk not the differential etch necessary for bonding. This type HI pattern can be troublesome for bonding because it does not allow the resin to grip the enamel. This area of prism less enamel are not confined to the deciduous teeth but also in the cervical two thirds of the crowns of molars and premolars. These zones are areas where the dentist hopes to achieve most of his bond strength , when using direct bonded retainers. This prism less enamel usually comprises only the outer 13-20 microns of the enamel. Applying the etchant not only roughens the outer surface but actually dissolves it, it is possible to etch past this prism less layer using the etchant itself. A 60 seconds application of 30% orthophosphoric acid results in a loss of 20microns in depth of histologic change. Once 20microns of enamel have been D removed from the surface the underlying structure usually exhibits one of the other three etching patterns. Thus the time needed to etch an area of enamel displaying prism less outer structure is considerably greater than an area of normal enamel. Etching pattern is not of clinical significance because the clinician cannot define the etching pattern by visual examination. They are not important to the resulting bond strength.

Advantages of etching: Etching results in tremendous increase in the surface energy which increases the wettability of the surface. Etching increases the surface area available for bonding. The improved mechanical bonding is responsible for the 77

Dentin Bonding Agents

high bond strength of 18 22MPa.This high bond strength is of simple micro mechanical retention. This can be explained by the fact once the enamel surface has been roughened by the etchant the enamel pores also become enlarged. Since these pores often interconnect their increase in size not only allows relatively larger resin molecules to penetrate the subsurface of the enamel but also allows these resin tags to interconnect. Stronger enamel bonding depends upon resin tags becoming interlocked with the surface irregularities created by etching. Resin tags which form between enamel peripheries are called MACROTAGS.

A much finer network of thousands of smaller tags from across the end of each rod where individual hydroxyapatite crystals have been dissolved leaving crypts outlined by residual organic material. These fine tags are called MICROTAGS. Microtags and macrotags are the basis of micro mechanical bonding. Micro tags are important because of their larger number and great surface of contact. The length of the macro tags are unimportant because the fracture occurs in the neck of the tags. Most macro tags are only 2-5 micrometer in length. Etching improves mechanical bonding between resin and enamel. This forms the basis of many innovative dental procedure such as resin bonded metal retainers porcelain laminate veneers and orthodontic brackets The etching improves marginal seal, which prevents marginal staining caused by interfacial leakage to a large extent. The improved mechanical bonding between resin and enamel. This forms the basis of many innovative dental procedure such as resin bonded metal retainers porcelain laminate veneers and orthodontic brackets. Thus etching improves marginal seal, which prevents marginal staining caused by interfacial leakage to a large extent.

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Dentin Bonding Agents

Enamel bonding agents : Enamel bonding systems most often consist of an an unfilled or lightly filled) liquid acrylic monomer mixture placed onto acid etched enamel12. The monomer flows into the interstices between and within enamel rods. Traditionally enamel bonding agents have been made by combining different methacrylates such as bis-GMA and TEGDMA to control viscosity. Because enamel can be kept fairly dry, these rather hydrophobic resin work well as long as they are restricted to enamel.

APPLICATION OF THE ACID ETCH TECHNIQUE: It is widely used for composite filling as a means of aiding retention and reducing or preventing micro leakage.

For class IV cavities the acid etch technique has replaced the gold inlay as the treatment of choice for restoring the tooth contours and function. In this example the use of an adhesive system allows the conservation of considerable quantities of tooth substance which would otherwise be lost in cavity preparation.

Bonding of resins using the acid etch technique has also been used as a means of strengthening or splinting teeth which have been weakened by cavity preparation. The teeth having a prepared cavity is weakened relative to an unprepared tooth. Under stress fracture being the most likely occurrence. Restoring with a non adhesive restoration has little beneficial effect on the strength of the tooth whereas the use of an adhesive material will strengthen the tooth and help to prevent cusp fracture.

PIT AND FISSURE SEALANTS: are now widely used for preventing pit and fissure caries. The success of fissure sealants depends on initial placement 79

Dentin Bonding Agents

condition and techniques. In order to get good resin tag formation the enamel must be properly etched and washed and thoroughly dried before the sealant is applied.

With the advent of acid etch technique resins are widely used for attaching orthodontic brackets. With the acid etch techniques composites are gaining popularity for attachment of bridges .e.g. Rochette bridge, Maryland bridge. The attachment of acrylic or porcelain labial veneers in order to improve the appearance of stained, discoloured misshapen.

BIOCOMPATABILITY; Pulpal tissue: No danger of pulpal irritation when it is placed over enamel. When they are placed over dentin or cemental tissues however there is danger of pulpal inflammation. The danger increases with the proximity of the acid to the pulp , the concentration of acid used and the duration of its application. Hence the etchant must be carefully placed when dentine or cementum may come into contact with the acid.

Gingival tissues : Damage to the gingival tissue is not a problem within the range of normal clinical technique. However gingival irritation occurs when gingival tissue is exposed to up to 50% orthophosphoric acid. Appearances are similar to that of aspirin bum.

To the tooth : The loss of fluoride rich surface enamel during prolonged etching may make the adjacent enamel more' usceptible to enamel decalcification as in orthodontics. 80

Dentin Bonding Agents

Clinically bonding to enamel should present a problem. However this does not mean that failure of enamel bonded restoration will not occur, since cohesive failure of the adhesive of the restoration can still take place. Equally, metallic or ceramic restorations can fail adhesion due to a lack of bonding between the resin and these restorative materials.

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Dentin Bonding Agents

SMEAR LAYERS
The observation that smear layers could occlude the tubular structure of dentin and bone was first made by Van Leeuwenhoek in 1677, although he did not call them smear layer. More recently dentinal smear layer was described by Boyde et al. The composition of the smear layer was demonstrated by Eick et al to consist of calcium and phosphate plus organic material containing sulfur, nitrogen and carbon. When observed under a SEM, it has a rough smeared appearance with obliterated tubule orifices. It is composed of

varying amounts of blood, saliva, bacteria, denatured collagen, and enamel and dentine particles.

The composition of the smear layer reflects the composition of the dentin from which it is formed. Thus the smear layer in] superficial normal

dentin may have a composition close to that of intertubular dentin whereas the composition of the smear layer in deep dentin would reflect its lesser degree of mineralization. Similarly smear layers created on caries affected and sclerotic cervical dentin has more Whitlockite just like this type of dentin where more Whitlock is present than normal dentin.

The smear layer acts like a natural bandage over the cut surface since it occludes many of the dentinal tubules with debris called smear plugs covered} by the smear layer. The thickness of the smear layer varies as a function of

whether the dentin is dry or wet during rotary instrumentation. The thickness is approximately 1-5 m. The morphology, thickness and composition of the

smear layer vary with the method used for cutting the surface, with coarse diamond abrasives used dry producing the thickest deposits.

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Dentin Bonding Agents

Smear layer (SEM 3, 950 x)

Smear layer has 2 phases : A solid phase - Made up of cutting debris. A liquid phase - Made up of tortuous fluid filled channels around the cutting debris.

There are two different opinions regarding smear layer treatment. Some believe that the smear layer acts as an affective, natural cavity liner that seals dentinal tubules and reduces permeability making the smear layer a clinical asset. Others argue that the smear layer interferes with the adhesion of restorative materials, serving as a focus for bacteria and bacterial toxins and therefore it should be removed. One study reported that the smear layer, which was firmly attached to the dentin initially, became loose and was largely replaced by bacteria and fluid within a few weeks.

In order to chemically attach a restorative system to tooth structure, one of the several options must be considered for the smear layer. For the currently

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Dentin Bonding Agents

available dentine bonding agents, the smear layer is managed in one of the five ways; No treatment at all: The smear layer is left in place without modification, and the dentin-bonding agent is applied directly to it. Dissolution of the smear layer: The dissolved smear layer plays a part in the chemical attachment of the dentin-bonding agent to dentin. The smear layer is removed: the dentine-bonding agent develops chemical attachment directly to intact dentin. It involves the modification of the smear layer. This process

theoretically improves the attachment of the smear layer to dentin. This means of smear layer treatment involves its removal and replacement with another mediating agents.

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Dentin Bonding Agents

DENTIN BONDING SYSTEMS


Dental Bonding System: The dental adhesive system consists of a conditioner (etchant), primer and bonding agent (adhesive).

Dentin bonding systems involve an unfilled (or lightly filled), liquid acrylic monomer mixture placed onto an acid-etched and primed dentin surface. The bonding primer depends on hydrophilic monomers, such as 2-hydroxyethy! methacrylate (2-HEMA or HEMA), to easily wet hydrophilic dentin surfaces that contain some moisture. Although primer and/or bonding agent may flow into dentinal tubules, the bond strength is primarily achieved by micromechanical bonding to the intertubular dentin (between tubules) along the cut dentin surface. Despite the fact that many dentin-bonding systems have been formulated to allow chemical reactions to take place with dentin, this has had little or no apparent contribution on the final bond strength. Generally, 90% or more of dentin bond strength is presumed to be due to mechanical bonding12.

Mechanical preparation of dentin leaves behind a highly distorted debris layer (smear layer) that coves the surface and conceals the underlying structures. Early dentin bonding systems were hydrophobic and were bonded directly to the dentin smear layer. Therefore macro shear bond strengths were found to be less than 6 MPa, because that is the strength of the bond of the smear layer to sound dentin. Initial dentin etching process removed the smear layer, but tended to over etch dentin. Bond strengths of 10 to 12 MPa were produced, and were not significantly increased until bonding systems were chemically modified to become more hydrophilic (18 to 20 MPa). Careful

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Dentin Bonding Agents

dentin etching produced micromechanical relief for bonding between tubules (intertubular dentin) without excessive demineralization of peritubular dentin. Coupled with hydrophilic primers, bond strengths increased to 22 to 35 MPa. The theoretic limit for dentin bonding system strength may actually be higher (80 to 100 Mpa) than that for enamel, because dentin is more resistant to shear fracture. The clinically important limit for dentin bonding is not yet known. However, because of the presence of more water in dentin than enamel, the clinical longevity of dentin bonding may not be as long as that of enamel. As portrayed in the priming action in dentin bonding systems is designed to penetrate through any remnant smear layer and into the intertubular dentin and to fill the spaces left by dissolved hydroxyapatite crystals. This allows acrylic monomers to form an interpenetrating network around dentin collagen. Once polymerized, this layer produces what Nakabayashi referred to as the hybrid zone (interdiffusion zone or interpenetration zone). Depending on the particular chemistry of a bonding system, the hybrid layer may vary from 0.1 to 5 m deep. If this decalcified dentin zone is not filled (bonded) by bonding system, it may as a weakened layer or zone contributing to fracture, in addition, the extent of the etching effect on the strength of the collagen fibers is not yet known, however these systems demonstrate that stronger dentin bonding is possible and portend a bright future for bonding systems.

The key ingredient for priming in many dentin-bonding systems is hydroxyethyl methacrylate (HEMA). This, molecule is an analog to methyl

methacrylate, except that an ethoxy ester group to make it hydrophilic replaces the pendant methyl ester. Importantly, it is relatively volatile and has some

tendency to produce mild sensitivity. Dentists and assistants should be aware that it is very mobile. , can diffuse through rubber gloves, and will cause skin dryness and cracking in many individuals. Therefore during the use of

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Dentin Bonding Agents

primers and bonding agents high-volume evacuation should be used to minimize HEMA vapor contact.

Bonding normally has been conducted in three steps (three-component systems). During the late 1990s,the number of stages (etching, priming, bonding) was reduced by combining the actions of various steps. Two component systems were devised that either employed etching with priming/bonding or etching/priming with bonding. In latter case, the term selfetching primer was used to describe the first component of the system. This is most often achieved by employing acidic monomers that dissolve or disrupt the smear layer, dissolve hydroxyapatite in the intertubular zone and tubules, and then polymerize to generate a hybrid zone. Despite the approach to designing

two-component system, they generally required significant solvent to cosolubilize the modifying material. Solvent levels among systems vary considerably but are generally in the range of 65% to 90% solvent. Choices for solvent systems, base on acetone or ethanol with water, do affect the wetting efficiency.

For bonding systems to efficiently produce a hybrid layer, it is extremely important to keep the dentin hydrated. Quite often, the rinsing and drying of dentin that follows tooth preparation or specific etching steps, results in dehydrated superficial layers of dentin. Etched dentin no longer contains hydroxyapatite crystals between collagen fibers. It consists only of the remaining collagen and water. Dehydration, whether intentional or not, causes the remaining collagen sponge to collapse with collagen molecules forming a mat and excluding monomers necessary for hybrid layer formation. Therefore etched dentin either must be kept moist or be intentionally rehydrated. Rehydration can be accomplished with a moist cotton pledget or applicator tip in contact with the surfaces for approximately 10 seconds or by the use of 87

Dentin Bonding Agents

rewetting agents. If dentin moisture is inadequate, then the hybrid layer will not form, and the bonding system will fail to seal and bond. It is suspected that in adequate precautions in this regard in many bonding instructions during the early 1990s may have contributed to the premature failure of many dentinbonding systems.

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Dentin Bonding Agents

CRITERIA FOR IDEAL DENTIN BONDING SYSTEM


Should provide an immediate permanent, high- strength bond to dentine3. Should have a bond strength to dentin similar to that to enamel Should be compatible with dental tissues Should minimize microleakage at the margins of restorations Should prevent, recurrent caries and marginal staining Should be easy to use and minimally technique sensitive Should a reasonable shelf life Should be compatible with a wide range of resins Use a resin of low film thickness (> 20mm) if the system is to be suitable for use with indirect restorations. Show no reduction in bond strength when applied to a moist surface, and Have no potential for sensitization of patients or operators

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Dentin Bonding Agents

CONDITIONING OF THE DENTIN SUBSTRATE


Conditioning of the dentin will be defined as any alteration of the dentin done after the creation of dentin cutting debris, termed the smear layer. The objective of dentin conditioning is to create a surface capable of micro mechanical and possible chemical bonding to a dentin-bonding agent.

The principle effects of conditioning of dentin may be classified as a. Physical changes b. Chemical changes

Physical changes are principally : Increases or decreases in the thickness and morphology of the smear layer. Changes in the shape of the dentinal tubules.

Chemical changes are principally : Modifications of the fraction of organic matter Decalcification of the inorganic portion.

Removal of the smear layer generally results in increase permeability of the dentin. The small particles comprising the smear layer have a large surfaceto volume ratio. The particles dissolve more easily than the intact dentin. If the smear layer and smear plugs within the tubules are lost, the exposed dentin becomes more permeable and sensitive. For clinical success, the conditioned dentin must be sealed to prevent sensitivity and to prevent the pathology associated with the increased permeability of the dentinal tubules16.

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Conditioning of dentin may be done by several means. Chemicals Acids. Calcium chelalors

Thermal Lasers

Mechanical Abrasion.

Acid conditioners : Mode of action of chemical conditioners : It has been suggested that mineralized collagen matrices have apatite crystallites arranged not only around collagen fibrils but also with in them, in the whole regions. Most of the apatites consist of Ca 10 (Po4) X2 where X can be carbonates, fluoride or hydroxyl ions. The major phosphate ion species is the non-protonated, trivalent form. This makes the apatite an excellent buffer for hydrogen ions. One can argue that intertubular dentin is solid buffer

material, because both apatite and collagen can take up hydrogen ions from acidic solutions, either as product of bacterial metabolism or therapeutically applied acidic conditions. As hydrogen ions are taken up by trivalent

phosphate the resulting protonated phosphate species no longer fit into the crystalline apatite lattice and hence the lattices disintegrate and dissolve into adjacent fluids. As the crystallites dissolve the underlying collagen fibrils

become accessible, these fibrils may also take up hydrogen ions. As acid conditioning proceeds into intertubular dentin the perifibril porosities previously occupied by apatite crystallites become filled with the liquid phase

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of the conditioner. The acidic conditioners demineralize dentin to a depth of at least 2-5 m16.

The factors that limit the depth of demineralization are: Type of acid Etching time Strength of the acid Buffering capacity of the dentin.

The depth of demineralization is limited in sclerotic cervical dentin because of either hypermineralization or formation of more acid resistant forms of calcium phosphate.

Effect of chemical conditioners : They remove the smear layer and expose a microporous scaffold of collagen fibrils thus increasing the microporosites of intertubular dentin. Because this collagen matrix is normally supported by the inorganic dentinal fraction, demineralization causes it to collapse. On intertubular dentin the exposed collagen fibrils are randomly oriented and are often covered by an amorphous phase with relatively few microporosities and variable thickness. Etchants thickened with silica leave residual silica particles deposited on the surface, but the silica does not appear to plug the intertubular micro porosities. Sometimes fibrous structures probably remnants of odontoblastic processes are pulled out of the tubules and smeared over the surface. With aggressive acid

etchants/ hypertonic acids the acid may tend to pull the collagen fibers away from the intact dentin/unaffected dentin leaving a sub micron 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

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Dentin Bonding Agents

mineralized peritubular dentin from the surrounding intertubular dentin. Alternatively the mineralized peritubular dentin may be completely dissolved to form a funnel shape.

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

The hydrogen ions from these acids diffuse into the dentin while etching. If one assumes that the self-diffusion co-efficient of hydrogen ions in free solution at room temperature is 1x106cm2/sec. One can calculate the distance that the hydrogen ions can diffuse into dentin as the square root of the product of the diffusion coefficient of hydrogen and time. Moreover the hydrogen ions dont diffuse as much as calculated as their diffusion is restricted by dentin. The surface reactions are violent as carbonate is

converted to carbon dioxide 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 products, that may limit further penetration of protons. Further the hypertonic solutions when osmotically draw the fluid from the dentin towards the surface could restrict the inward protein diffusion.

The removal of the smear layer and demineralization of the dentin matrix may facilitate bonding through a number of mechanisms.

They are Removal of loose smear layer debris and exposure of dentin matrix Exposure of collagen fibrils and their Epsilon-Amino groups which may catalyze HEMA polymerization.

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Exposure of intact collagen that serves as a scaffold for the creation of resin collagen hybrid layer

Phosphoric acid : It was the first dentin conditioner that was successfully used to remove the smear layer, etch the dentin and restore with adhesive composite resin by Fusayama and others. This helps in removing the surface dentin leaving a clean well defined etching pattern where the tubules are enlarged into funnel shape, phosphoric acid is the acid of choice currently for etching purpose. However controversy remains about the optimal concentration of H3 POH. The most widely used concentrations used in clinical practice exceed 30% H3 PO4. Chow and Brown demonstrated that the application of H3 PO4solutions greater than 27% resulted in the formation of monocalcium phosphate monohydrate, which is readily soluble and would be completely, washed away in the clinical situation. This is the product preferred because; if the reaction product is not completely removed after the etching procedure it may interfere with the bonding of composite resins to etched enamel surface. When H3 Po4, was used in concentration less than 27% dicalcium phosphate dihydrate was formed which is less stable. So it is not the desired concentration

Total etching with phosphoric acid : Phosphoric acid is generally acknowledged to be the preferred enamel etchant, especially in the presence of salivary pellicle or plaque. Fusayams pioneering research of total etching established the protocol for simultaneous etchings of dentin and enamel with phosphoric acid, followed by washing, drying, and application of an adhesive resin. This technique is being

successfully used by an ever-increasing number of clinicians worldwide. Perhaps this popularity has resulted from the realization that inadvertent 94

Dentin Bonding Agents

exposure of dentin to phosphoric acid is unavoidable. Use of dentin bonding agents that are successful with accidental or purposeful phosphoric acid etchings appear to be prudent. Kurarys original Clearfil new bond system accomplishes the total etch using 37% phosphoric acid for 60 seconds. Bisco system uses 10% phosphoric acid for 15 seconds in all etch techniques. A 10% solution appears to result in a slightly better bond strength than higher concentrations.

Other acid conditioners : Historically several acids have been researched as dentin etchants. These include hydrochloric, oxalic and pyruvic acid in addition to the betterknown acids such as phosphoric, citric and nitric. To put acids in perspective, it is perhaps best to compare their dissociation constants.

When an etchant is required dilution of a stronger than necessary acid may result in a better etching solution. The concentrated acid will uniformly strip a surface, while the dilution results in selective dissolution, termed etching. Acids with the lower Pkas tend to be used in a more dilute solution than those with higher Pkas.

Nitric acid : It is stronger than phosphoric acid Easily removes the smear layer Used in concentration of 2.5% causes funneling of the orifice of dentin to a depth of 5mm in 40 seconds. Nitric acid conditioners are highly adhesive and provide good tubule seals. e.g. Tenure, Mirage Bond, Restobond 3.

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Citric acid : 10% citric acid is used for the purpose of removing the smear layer. It has been reported by Nakabayashi (1989) that such treatment tends to lower the porosity or permeability of the demineralised surface, possibly by denaturing the collagen. 10% citric acid and 3% ferric chloride combination was developed by Nakabayashi, found to be effective smear layer remover. This combination was found to be particularly effective for methacrylate based adhesives containing 4-META (4- methacryloxyethyl trimellitate anhydride)

Ferric ions appear to be necessary since the citric acid alone yields poor results with this system. e.g. Super-bond

The higher bond strength of 4 methacryloxyethyl trimellitic anhydride/ methyl methacrylate- tetra butyl borane oxidized ( 4 META/ MMA- TBB) products conditioned by 10% citric acid and 3% ferric chlorides solution can also be achieved by substituting cupric chloride for ferric ions Another combination etchant is 10% citric acid with 20% calcium chloride. combination result in improved bond strength. This

This high concentrate of

calcium may stabilize collagen during surface etching. It also decreases the extent of the demineralization of hydroxyapatite by a common ion effect. The depth of decalcification is about 8 microns compared to the phosphoric acid etching, which results in 16-micron depth of decalcification. . Eg. Clearfil Liner Bond.

The tubules do not open into a funnel shape.

Hydroxyapatite is

removed from intertubular and peritubular dentin, resulting in exposed collagenous structure in the intertubular dentin.

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Pyruvic acid : Pyruvic acid and pyruvic acid buffered with glycine have been reported to satisfactorily acid etch both enamel and dentin (Asmussen and Munksgaard, 1988). When using the gluma bonding system Glycine was used to adjust the pH and perhaps to facilitate polymerization reactions.

Dissociation constants of some acids used on tooth etching and conditioning :

Acid Hydrochloric Nitric Maleic Phosphoric Citric Oxalic

PKa 1.4 1.4 1.8 2.1 3.1 4.1

CHELATORS : Chelators are used to remove the smear layer with out decalcification or significant physical changes to the underlying substrate as opposed to the strong acid etchants.

EDTA : The best-known chelating conditioner is ethylene diamine tetracetic acid (EDTA) adjusted to a pH of about 7.4. It was developed for use in the Gluma system.

While the smear layer is removed, no significant concavity is formed, and the funnel shape change associated with phosphoric acid not evident. 97

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The smear plugs in the dentinal tubules are not fully removed by 30 seconds application of the conditioner. Inokoshi and others data indicate that the Gluma system also results in a significant hybrid layer. The system uses both glutraldehyde and HEMA in a primer that is applied after the EDTA conditioner removes the smear layer.

Maleic acid (e.g. Scotch bond 2); Denthesive ( Heraeus Kulzer Inc) Irvine, CA 92718) also results in removal of the smear layer when used as a primer in combination with HEMA in a scrubbing action on the dentin. The generally reported bond strengths with this system compare favorably with other bonding system that have thicker hybrid layers. This observation

suggests that the thickness of the hybrid layer may not have much effect on dentin bond strength.

Lasers : Hard tissues lasers in dentistry are an emerging technology. A pulsed Nd: YAG laser will not disturbs the pulp, even when the approach is a close as 1mm. Heat is dissipated between the 10 to 30 pulses per second. The

mechanism of dentin removal is microscopic explosions caused by the thermal transients while most research has been conducted on dry dentin, the laser will operate on dentin immersed in saliva or water. The carbonized, black sort that results is easily washed off with water. The lased surface results in

desensitized dentin, presumably by occlusion of the open and permeable dentinal tubules. Microorganisms and organic debris are eliminated from the lased surfaces. The laser decreases the organic fraction and increases the inorganic fraction of the dentin surface.

Lasing of the dentin has the potential to increase the bond strength of the current dentin bonding agents. Its effect on the bond strength of Scotch 98

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bond 2 was recently presented by white and others .

The bond strength

increased about 60% compared to the control smear-layered dentin, presumably by increasing the bondable inorganic fraction of the dentin surface. The laser may create micromechanical retention, which is an analogue to the effect seen on laser-etched enamel.

Micro abrasion : Modification of dentin by micro abrasion with aluminum oxide removes healthy as well as diseased dentin and results in a smear layer. The abrasion action, of aluminum oxide depends on the particle size as well as on the velocity. Particle 0.5 microns or less in diameter do not affect the enamel except to cleanse it. The 0.5-micron or larger particles create a smear on the dentin and increase the surface area. The smear layer might be used to

enhance the bond strengths of smear-mediated dentin bonding agents.

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PRIMERS
Major advances have been achieved by the introduction of primers, which promote wetting of the dentin with the bonding agent, and penetration of the bonding agent into the dentin. Primer monomers are amphiphilic i.e. they contain hydrophilic groups (e.g. -OH, -COOH) for better compatibility of the resin monomers with the moist dentin, and hydrophobic methacrylate groups for the co-polymerization with the bonding resin. Nakabayashi and Pashley summarized the function of dentin primers to be "to maintain or recover the porosity of the demineralized dentin".

Primers are monomers dissolved in solvents such as water, acetone/alcohol and are applied to the etched/conditioned dentin substrate but are not rinsed off. Organic solvents aid in displacing water, expanding or reexpanding the collagen network and thus promoting the infiltration of the monomer into the submicron or nanometer sized spaces within the collagen fiber network12.

The first dentin bonding mechanism that gave reliable, high bond strengths, reported by Nakabayashi et al was based on the use of 4META/Methyl Methacrylate-tri-n-butyl borane (MMA-TBB) resin and 3% ferric chloride in 10% citric acid as a conditioner.

Effective primers contain monomers with hydrophilic properties that have an affinity for the exposed collagen fibril arrangement and hydrophobic properties for copolymerization with adhesive resins. The objective of this step is to transform the hydrophilic dentin surface into a hydrophobic and spongy state. Besides 2-hydroethyl methacrylate HEMA, primers contain other

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monomers, such as NTG-GMA, PMDM, BPDM and PENTA. More recent primers also include a chemical/photopolymerization initiator so that these monomers can be polymerized in situ. In prime and bond and Bisco one step dental adhesive they combine the priming and bonding step.

Bonding can be carried out by applying primer to a collapsed matrix followed by application of bonding agent or else a bonding agent may be directly applied to a noncollapsed demineralised dentin as these substrates have high permeability to monomers, thereby permitting hybrid layer formation without the intermediary step of primer application. In bonding systems in which the acidic conditioner permits the demineralized dentin to collapse when air dried, a primer is required to reexpand the collagen fibril network and restore the permeability of the demineralized intertubular dentinal matrix.

There are at least 2 possible explanations for the major shrinkage of the demineralized dentinal meshwork when it is air dried.

Collagen of etched dentin by air drying

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The passive theory assumes that the demineralized collagen fibril network is floating/suspended in water. Each fibril is separated from the other by a water filled space which occupies the space that was previously occupied by apatite crystallites. As the water supported collagen network is air dried, the amount of water separating the fibrils disappears as the water evaporates and the collagen fibrils come closer together in all three dimensions. This results in a passive collapse of the collagen network. . The result is a loss of space between the fibrils. The addition of water rapidly reverses these events causing passive reexpansion (i.e. floating) of the collapsed network. Gwinett also suggested that the surface tension forces operating at the air collagen network interface might be responsible for the collapse. As the collagen molecules come closer together, they may interact by forming hydrogen bonds as well as interacting electrostatically and hydrophobically.

Reexpansion of the Collagen Network: If water or an aqueous primer is added to dried dentin, the water reverses all of these events, water molecules would hydrogen bond with collagen peptides, breaking intermolecular hydrogen bonds. Sugizakis SEM and TEM observations showed that the collagen fibrils are closer together in collapsed dentin than when the matrix reexpands. He thought that the reexpansion of the collagen meshwork was the result of HEMA/hydrophilic primers, although more recent work indicates that it might have been the water content of the primers that was responsible for reexpansion.

Kanca and Gwinnett recommended that etched dentin should not be dried before application of the bonding primer.

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Moist Bonding: When the etched dentin is excessively dried after rinsing off the etchant, the collagen network will collapse and the microchannels opened by the removal of the apatite crystal will be closed. In order to avoid the collapse of the collagen network, a moist (wet) bonding procedure has been proposed in which the primer is applied to the moist or even wet dentin where the perifibrillar spaces are kept open with water.

A review of literature has shown that moist bonding is only essential for particular bonding systems with a low water content of primer such as AllBond 2. The primer of All Bond 2 contains acetone as solvent with only 5% of water, In contrast primers with water content of 20% or more (eg. Optibond FL, Scotchbond Multipurpose) are able to reexpand the collapsed collagen due to their intrinsic rewetting capacity. Acetone based primer adhesives (eg. Prime and Bond 2.1, One-step) have shown higher bond strengths and reduced microleakage when a moist bonding protocol is followed.

In conclusion moist bonding is only mandatory in bonding systems with minimal water content of the primer/primer-adhesives, while water based primers/primer adhesives have shown to be less sensitive to variations in the moisture of the etched dentin surface. Tay et al concluded that the term bonding to moist or wet dentin should not be loosely interpreted and must be clearly defined and the presence of water in acetone-based primers may be sufficient to rewet briefly desiccated dentin.

Research has demonstrated that moist bonding increases the bond strengths of many bonding systems. However the water present in between the fibrils should be displaced completely as if too much water is present, the resin

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monomers may not be able to successfully compete for the collagen fibril surface thereby leaving voids.

Water Based Primers : The first approach to creating a hybrid layer in wet dentin is the use of water-soluble primers containing HEMA. Examples of this type of primer are Scotchbond 2 nd Scotchbond Multi-purpose. After application of the waterHEMA mixture,the surface is air dried to evaporate the water. As the water concentration falls, the HEMA concentration rises, until theoretically there should be near zero water and 100% HEMA on the surface. Water has a much higher vapor pressure than does HEMA. In fact at atmospheric pressure HEMA can be regarded as almost volatile. This permits its retention as its solvent, water is evaporated during air drying.

Use of Water Miscible Primer Solvents : The second method of creating hybrid layers in this category of bonding is to sequentially acid etch, rinse; leave moist or dry, prime and then bond. The HEMA will be in 2 types ; 1) 35% HEMA in water, 2) 13% Polyalkonic acid copolymer in 50% HEMA. The problems with moist bonding is to determine how moist is moist. The dry condition is easily recognized and achieved but when does a moist condition become overwet. This is complicated by the fact that the intrinsic wetness of dentin varies from about 1% in superficial to about 22% in deep dentin. The consequences of applying acetone-based primers to overwet dentin have been described by Tay et al using All Bond 2, BISCO; those authors found that small globules formed within dentinal tubules. These were formed when the first one or 2 layers of primer were applied. That is in the tubules filled with dentinal fluid there was too much waters available to dilute the acetone with the result that the monomer came out of the solution. As more globules formed, they accumulated on the walls of the tubules, 104

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reducing the permeability of the tubules, permitting successive primer applications to dehydrate the tubules enough to from normal resin tags.

If excessive extrinsic water is left on the surface prior to application of the All Bond 2 primer, the primers tend to bridge the excess water droplets to from a tiny blister. This prevents resin tag formation in those tubules beneath the water droplet, clinically if the clinician sees a rough texture on the primed surface that might be caused by this phenomenon, he or she can destroy those droplets with the tip of a brush, which can be used to add more primer. The danger is that this may occur somewhere in a complex cavity design that is not easily visualized. This may result in an unbonded region, which could change its dimensions under thermal/occlusal stress and produce sufficient fluid shifts to cause dentinal sensitivity . It may also permit the concentration of stresses that may lead to bond failure in that portion of the restoration. Thus overdrying/overwetting of dentin can have undesirable effects.

The goal of priming is to replace all of the water/acetone monomer mixtures in the interfibrillar spaces with polymerizable monomers. Maciel et al demonstrated that 100% acetone, ethanol and HEMA all cause a time dependent stiffening of demineralized dentinal matrix. Once stiffened the matrix cannot collapse thus allowing efficient hybrid layer formation.

The primer should be either water or water miscible agent. The commonly used solvents are;

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Acetone Highly volatile evaporates quickly Excellent water-Chaser Strong drying agent (risk of overdrying dentin) Storage and dispense problems Ethanol (water) Excellent penetration capability Good compromise in respect of evaporation Good surface energy for wetting exposed collagen fibril network Water Good penetration capability Enables self-etching capability of acid monomers Evaporates slowly consequently more difficult to remove Remaining water may hamper resin penetration/polymerization

Application of primer to Smear Layer covered Dentin followed by bonding Agent: Bonding to the smear layer covered dentin was not very successful before 1990 as the resins did not penetrate through the smear layer and the smear layer was very weak. This led most manufacturers to use acidic conditioners. However the resulting soft collagen rich surface can collapse and interfere with monomer infiltration. So in order to prevent this and to simplify the number of bonding steps Watanabe developed a new bonding system which was an aqueous solution of 20% Phenyl-P in 30% HEMA. This self etching and self priming system provided important new information on smear layer as bonding substrates. The ideal self-etching, self priming bonding system is one that can penetrate 2.0 m of smear layer and engage underlying dentin to a depth of 1 mm. However as smear layers are made up of dentin they

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have a significant buffer capacity and tend to buffer the acidity of the acidic monomer used as a self etching agent. This property in addition to the tight packing of smear layer particles limit the penetration of monomer to about 2.0 m.So Toida et al advised the removal of smear by a separate etching step to produce more reliable and durable bonds.

Steps for effective priming : Microscopic examination of attachments produced by primer has shown deficiencies like ; 1) 2) 3) Incomplete surface coverage Incomplete interfibrillar saturation within the hybrid zone Incomplete penetration to the full depth of demineralized dentin.

One method of improving surface coverage and diffusion of the primer is by the application of multiple coats. A 2nd coat of primer has shown to increase the shear bond strength significantly. The surface of dentin should not be overdryed or overwet. The etching time should not exceed the time recommended by the manufacturers.

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HYBRID LAYER
Dentin hybrid layer is a transitional zone of resin reinforced dentin sandwiched between cured resin and the unaltered substrate (Nakabayashi). The essential mechanism of adhesion for current dentin bonding systems to the dentin substrate is described as micro mechanical and is generated by monomer impregnation of the exposed collagen of demineralised superficial dentin. The hybrid layer thus formed is a mixture of dentinal components and cured resin at the molecular level. The synonyms are adhesion interface, resin-dentin interdiffusion zone, and interpenetration zone5.

Hybrid layer

The formation of hybrid zone depends on several factors in general they are

i.

Type of the conditioners

ii. Depth of the cavity- hybrid layer appeared to be thinner at the deeper part of the dentin compared with the middle and the superficial parts.In the superficial dentin most of the hybrid layer is composed of hybridized intertubular dentin with only occasional resin tag penetrating

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into the tubules. In deep dentin the tubules are so numerous and so large that there is little intertubular dentinal matrix so these is less amount of hybridized intertubular dentin and large resin tags are seen.

iii. iv v.

Permeability of the dentin surface It depends on the conditioning priming pretreatment Diffusability and wettability of the monomer resins.

In order to obtain an intimate association between the resin monomers and collagen fibrils the primer and bonding agents must be able to wet the collagen fibrils. If the fibril is enveloped by water, the monomer must be able to successfully compete with water for the fibril surface. But monomer

penetrating is just one part, as after penetration the monomer must polymerize right there in situ. An adhesive system that has been demonstrated to have good bonds is 4-META in methylmethacrylate (MMA-TBB). The HEMA bonds to either the calcium or iron precipitates. Further the polymerization takes place by the unique initiator in a butyl borane in conjunction with O 2 and H2O as co catalysts. So the polymerization is initiated once polymerized the resin formed not only entangles and envelops collagen but also encapsulates hydroxyapatite.

The characteristics necessary for the formation of hybrid layer Substrate must be suitably prepared by smear layer and smear plug removal. The dentinal peptides including collagen must not be denatured when the dentin is decalcified because the denatured collagen shrinks or collapses quite easily, decreasing the porosity and penetrability of protein molecule.

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The bonding resin must include monomer with both hydrophilic and hydrophobic groups that can penetrate the dentin and combine with it.

One of the critical factors is a suitable monomer mixture which diffuses and impregnates into the demineralised dentin, thus stabilizing the dentin matrix. Once the adhesive monomer has penetrated into the demineralized substrate to its full extent, it must be made to polymerize in situ at the full penetration depth it has achieved, with minimal shrink back.

The catalyst must allow polymerization in the presence of oxygen and water. This is accomplished by the unique initiator tri-n-butyl borane in conjunction with two co-catalysts, viz., oxygen and water. These co-catalysts are abundantly available on dentinal surfaces and within its subsurface and tubules and comprise a significant portion of dentin. The polymerization

reaction is initiated once the catalyst comes in contact with water and oxygen. Polymerization shrinkage of dental monomers is always towards the initiation points of the reaction. Therefore, the shrinkage of the forming resin is in the optimal direction towards the substrate .

SEM and TEM Examination of the ultra structure of resin dentin interdiffusion zone : By Van Meerbeck et al, both SEM and TEM confirmed the presence of the resin-dentin interdiffusion zone as the junction between the deep unaltered dentin structure and the restorative resin.

Within the interdifussion zone, three sub layers were identified by TEM with characteristic ultra structure and staining they are, An upper layer, with diffuse black staining containing few structural features. No separation between the interdiffusion zone and the adhesive 110

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resin is apparent. Small inorganic microfiller particles were deposited on top of the interdiffusion zone, and only the smaller sized particles could be found in deeper layer. Underneath this zone, partially altered collagen fibrils were closely packed, mostly running parallel with the interface and perpendicular to the dentinal tubules. Their outline was electron dense forming tunnel like structures. At the base of the upper layer, several stained

projections were found to interdiffuse between sectioned collagen fibrils. Finally, the third dense layer, containing hydroxyapatite crystals, demarcating the superficially demineralised dentin layer from the deeper unaltered dentin. Resin diffusion into the decalcified dentin surface layer was evident, but diminished with depth, presumably reducing deeper resin impregnation into the interfibrillar spaces.

The hybrid layer, as a microscopic structure, is very difficult to evaluate, as has been described earlier. Under some bonding conditions, the demineralized layer is not completely infiltrated by resin. Micro leakage might take place.

Micro leakage is the diffusion of a substance into a fluid filled gap or defect between filling materials and tooth structure. This is usually seen to occur via 3 routes. With in or via the smear layer Between the smear layer and cavity varnish or cement. Between the cavity varnish or cement and the restorative material. This occurs when the forces of polymerization contraction exceed dentin bond strength leading to the formation of a gap.

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Leakage from the margin of the restoration deep into the hybrid layer via interconnected defects, porosities and flaws that exist is termed nanoleakage. The clinical significance of nanoleakage is unclear.

Reverse Hybrid Layer : The acid etched surface of dentin is further subjected to treatment with NaOCl. This results in dissolution of the collagen fibrils, which are exposed. Further the use of self-etching primers results in superficial etching of the surface. Here the hybrid layer is surrounded by more of inorganic material unlike the normal hybrid layer where the collagen fibers are encapsulated by resin, and so this layer thus formed is termed reverse hybrid layer or soft tissue hybrid layer). Dentin bonding agent when comes in contact with pulp forms this.

Three types of ultra morphological features have been described as resulting from this hybridization process: 1. Shag carpet appearance: Here there's loose organization of collagen fibrils that are directed towards the adhesive resin and often unraveled into their microfibrils1.

This feature is seen when the dentin surface after being acid etched is actively scrubbed with an acidic primer solution.

Because of the combined mechanical / chemical action of rubbing the acid etched dentin with an acidic primer (or P/A combination) which probably dissolves additional mineral while fluffing and separating the entangled collagen at the surface. This promotes infiltration of monomers into the loosened collagen scaffold by a kind of massaging effect.

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2. Tubule wall hybridization: Here there is extension of hybrid layer into the tubule wall area. Resin tag formation in the opened tubule is surrounded by a hybridized tubule orifice wall which is thought to favourable in hermetically scaling the pulp dentinal complex. This may be particularly effective when the bond fails either at the top or the bottom of the hybrid layer, which are considered weak links in the micro mechanical attachment.

3. Lateral tubule hybridization: There is a formation of tiny hybrid layer into the walls of the lateral tubule branches. This micro version of hybrid layer typically surrounds a central core of resin called a micro resin tag.

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CLASSIFICATION OF DENTIN BONDING AGENTS


a) b) According to composition According to type of primers or combined primer\adhesive resin According to mode of action c) d) e) b) f) g) h) i) According to bond strength According to mode of curing According to number of clinical steps According to generation Adhesive system with stress bearing potential Adhesive system that include fluoride Classification based on adhesion strategies (VanMeebeck) According to smear layer modified/removed/ dissolved

ACCORDING TO CHEMICAL COMPOSITION: Polyurethanes Polyacrylic acids Organic phosphonates Mellitic anhydride and methyl methacrylate (4- META) Hydroxyethyl methacrylate+Glutraldehyde(HEMA+GA) Ferric oxalate +NPG-GMA (N-phenyl glycine and glycidyl methacrylate)+PMDM(Pyromellitic dianhydride and 2 HEMA)

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According to type of solvent of primers or combined primer\adhesive resin1 :


Acetone Acetone water ABC Enhanced (Chameleon) AQ Bond Acetone ethanol All-Bond 2 Excite (Vivadent) Ethanol Ethanol water Gluma Comfort Bond (Kulzer) EG Bond (sun Medical) Reactmer (shofu) Optibond Solo plus (kerr) Gluma One Bond (Kulzer) Tenure Quik (Den-Mat) PQ1 (ultradent) Permaquik (ultradent) Clearfil SE Bond (Kuraray) One step (BISCO) Quadrant Unibond (cavex) Permagen (ultradent) Prime&Bond NT (Dentsply) Solid Bond (Kulzer) Solist (DMG) Scotchbond 1 (3M) Syntac sprint Fuji Bond LC (Vivadent) (GC) One-coat Bond (coltene) Prompt L. Pop 1.2 (ESPE) Stae (SDI) Scotchbond multi-purpose (3M) Tenure Quik F (Den-Mat) Syntac Single EBS (ESPE) Denthesive II (kulzar) Optibond FL ART Bond (kerr) (Coltene) Amalgambond plus (parkerr) Water

(sun Medical (BISCO)

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According to mode of action (Eick et al) : 1. Those that bond with calcium ion-based on phosphate esters of BISGAMA and its modifications bond with calcium ion in the smear layer and dentin surface. The smear layer is therefore left intact. Eg: Scotch bond/and Bondlite.

2. Those that bond with amine or hydroxyl groups-based on isocyanate or aldehyde. They bond with amine or hydroxyl groups of organic component of dentin. Hence the smear layer has to be removed and dentin surface decalcified to expose the collagen fibers. Eg. Gluma

3. Those that bond with reprecipitated smear layer-Dentin bonding system in this category require partial removal and modification of smear layer. Bonding is possibly by mechanical entanglement with collagen fibrils on dentin surface Eg: Scotchbond 2 and Tenure.

According to bond strength : Category I : Included dentinal adhesives, which produce shear bond strength of 5-7 Mpa Eg; Dentin Adhesit Scotch bond dual cure Gluma The failures occurred at the interface or in the resin adhesives

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Category II : Included the experimental and commercial products derived from Bowens work with ferric and aluminum oxalates and have produced shear bond strength between 8-14 Mpa eg;Tenure Mirage Bond

Category III : Included dentinal adhesives , which produced shear bond strength values of about 17 20 Mpa Eg; Super bond Scotch bond 2 Scotch bond Multipurpose All bond

According to their mode of curing: Chemical cure Eg;Amalgam bond plus Light cure Eg; One bond Gluma comfort bond Dual cure Eg;Clearfil liner bond 2v Prime and bond NT

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According to number of steps needed to complete the bonding process17: Three-step or conventional system Two step systems Single bottle systems Self etching primer `One-bottle or All in one systems. `Three-step or conventional systems : This group represents those materials that have separate etching, priming and adhesive steps. Still widely used and have been shown to provide reliable bonding. The greatest problem with this group would seem to be that three district steps are needed, they are more technique sensitive. `Two-step systems : This group has two subgroups: The first includes those systems that have a separate etch and have combined the priming and bonding steps. These systems are often referred to as `single bottle systems. Although one step has been eliminated, the great problem is ensuring good infiltration of the primingbond into demineralized dentin.

The Other subgroup combines the etching and priming steps together and are referred to as self etching `primers. Have ability to etch the enamel to a greater extent to ensure a good seal. The problem of technique sensitivity have been significantly reduced with these systems compared with conventional and `single-bottle systems.

The self-etching priming agent does not have to be washed off the dentin, therefore eliminating the need to maintain the dentin in a moist state. The method of demineralization of these materials is by the use of an acidic 118

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resin that etches and infiltrates the dentin simultaneously. The dentin is an excellent buffer, so the acidity of the self-etching primer is rapidly reduced and after polymerization is neutralized. `One-bottle or `All-in-one systems : This is the simplest of all dentin-bonding systems. They combine all steps into one process. Their mode of demineralization is identical to that of the self-etching priming materials, but the bonding resin is also incorporated. These systems also have the problem of not etching the enamel as effectively as phosphoric acid. These systems are the newest and have no long-term clinical data to demonstrate their effectiveness.

ACCORDING TO GENERATIONS : First Generation Dentin Bonding Agents : Buoncore et al in 1956 reported that glycerophosphoric acid dimethacrylate (GPDM) could bond to hydrochloric acid- etched dentinal surfaces. This bond was believed to be due to the interaction of this

bifunctional resin mole cule with the calcium ions of hydroxyapalete, but immersion in water would greatly reduce this bond. Nine years lates Bowen tried using N- phenyl glycine and glycidyl methacrylate (NPG) which is a bifunctional molecule or coupling agent. This molecule has one end bonding to the dentin while the other end bonds to the composite resin. The NPG-GMA) also bonded to the dentin by chelation with calcium on the tooth surface. Among the first generation of bonding agents used were. 1. Glycerophosphoric acid dimethacrylate 2. Cyanoacrylate 3. NPG- GMA The First commercial system of this type is Cervident, S.S. white

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Disadvantage : 1. Poor adhesion to dentin 2. Bond strength of 2.87 Mpa 3. Hydrolysis of GPA-DMA in oral environment 4. Difficulty in bulk polymerization of cyanoacrylates

Second Generation : In the late 1970s, the second generation systems were introduced. Majority of these incorporated halophosphorous esters of unfilled resins such as bisphenol A-glycidyl methacrylate or BIs-GMA or hydroxyl ethyl methyacrylate( HEMA). The mechanism by which these second generates systems bonded to dentin was postulated to be through an ionic bond to calcium by Chlorophosphate group. These were weak bonds but they were a significant improvement over the first generation systems.

The bonding mechanism involves a surface wetting phenomenon as well as ionic interaction between the phosphate groups and dentinal calcium. The second generation bonding system required a smear layer intact to create. This was to create a ca+ rich layer where the phosphate can combine with ca+.

Limitations : 1. The phosphate bond to dentin was not strong enough to resist the hydrolysis resulting form water 1mmession. This hydrolysis resulting form either saliva exposure or moisture form the dentin itself, could result in composite resin debonding from dentin and causing micro leakage.

The dentin was not etched in these early bonding system, much of the adhesion was due to bonding to this smear layer and this resulted in bond strength to dentin that were weak and unreliable. 120

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Eg: Clearfil, Scotch Bond, Bond Lite (sybron/kerr) bonding agent

J&J

Dentin

Invitro bond strength of these materials were reported to be 5 to 6 MPa. The bond however hydrolyze over time in the oral environment which attributed & their poor clinical success.

Dentin Adhesit (Vivadent) comprising of isocyanate monomer is also generally considered a second generation bonding agent.

Third generation adhesives : The third generation of dentin adhesives was based on the use of an acid group to react with ca2+ ion and a methacrylate group to co polymerize with unfilled resin that was applied before placement of the composite restorative material.

The first and second generation of adhesives achieved low bond strengths partly because of failures within smear layer or between smear layer and underlying dentin.

Smear layer had a negative influence on the performance of adhesive systems. To overcome this, third generation dentin bonding agents were introduced which differed from early materials in that an additional step was employed to either modify or remove the smear layer before the application of actual adhesive.

The third generation adhesive procedures for bonding dentin involved two approaches.

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Modification of the smear layer to improve its properties or Removal of smear layer without disturbing the plug that occluded the dentinal tubules.

Third generation bonding procedure generally involved four steps : Application of dentin conditioner, which is a type of acid, used to alter or remove the smear layer. Application of the primer (dentin bonding agent) Application of the adhesive, typically an unfilled resin. Placement of resin based composite.

Dental conditioner is an acidic solution that removes the smear layer and is rinsed off after application. The primer solution usually contains an adhesion promoter in a solvent such as water ethanol or acetone. These are applied to the surface and dried, presumably leaving the adhesion promoter on the dentin with its hydrophobic groups exposed to create a favorable surface for the bonding agent.

Removal of the smear layer by the use of acids or chelating agents reduces the availability of calcium ions for interaction with chelating surfaceactive co monomers, such as NPG-GMA. Bowen et al, in 1982, tried to supplement the calcium ion by applying an acidic solution of 6.8% ferric oxalate to dentin as an acidic conditioner or cleanser. An insoluble precipitate of calcium oxalates and ferric phosphates was formed on the surface, the precipitate was also expected to seal the dentinal tubules and protect the pulp. The subsequent application of an acetone solution of pyromellitic acid diethylmethacrylate (PMDM) mixed with NPG-GMA or its alternatives, Ntolylglycine glycidyl methacrylate. (NTG-GMA) improved bonding level of

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clinical significance. Ferric oxalate sometimes causes black interfacial staining, and was replaced by aluminum oxalate. This technique gave bond strength of about 15MPa to both enamel and dentin. Tenure was the first commercial oxalate bonding system, which utilized phosphoric acid in conjunction with aluminum oxalate and nitric acid as a dental conditioner.

Extensive research in Japan has demonstrated favorable effect of 4META on bonding to dentin. 4-META contains both hydrophobic and hydrophilic chemical groups. With this system, dentin is etched with an aqueous solution of 10% citric acid and 3% ferric chloride, followed by the application of an aqueous solution OF 35% HEMA And a self curing adhesive resin containing 4-META, methyl methacrylate (MMA) and TBB, the last as polymerization initiator. Based on this technology, adhesive system, such a C&B Metabond, Super Bond D-Liner, and Amalgam-bond plus are commercially available.

Mirage bond: utilized enamel and dentin conditioner of NPG (N- phenyl glycine )+2.5% nitric acid followed by application of PMDM. Dentin bonding strength achieved was 10.9 1.2 Mpa.

Gluma Bonding system : In 1984, a new bonding agent Gluma was developed It utilizes 0.5 M EDTA (ethylene diamine tetra acetic acid) at an approximately neutral pH to remove the smear layer and free collagen from embedding apatite.

The second step is treatment with an aqueous solution of 35% HEMA and 5% glultraldehyde. The bonding reaction involves attack of the aldehyde

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on the amino groups of collagen. The resulting complex is able to react with the hydroxy group of methacrylate monomer, which then bonds to the resin. Gluma could provide 15 MPa bond strength.

Scotch bond 2 dentin bonding system : The Scotch bond 2 has two components.The primer, Scotch prep (3M) an aqueous solution of 23% maleic acid and 55%HEMA . Bonding agent consists of hydrophilic monomer-HEMA(32.5%)hydrophobic monomerBISGMA (62.5%) and photoinitiator. The scotch bond 2 dentin bonding system to receive provisional and later, full acceptance from the American dental Association in 1987. The result was preservation of a modified smear layer with slight demineralization of the underlying intertubular dentin surface.

Prisma Universal Bond 2 : The main material has two components: Dentin primer HEMA, PENTA Adhesive TEGDMA, Urethane dimethacrylate, PENTA, Gluteraldehyde. ethanol,

The phosphate group containing monomer (PENTA) differs in functionality of acrylate groups as well as in the balance of hydrophilic and hydrophobic parts of the molecule.

In this system the smear layer is intact and the dentin primer applied helps in saturating the smear layer with monomer. As a result these is no thorough penetration of the adhesive resin only a few resin tag are seen in areas initially covered by a locally very them or permeable smear layer.

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In the adhesive, urethane dimethacrylate helps in generating better hydrogen bonds than BISGMA.

Prisma Universal Bond 3 : The only difference between the Prsima universal bond 2 and this is that there is an increased amount of gluteraldehyde in the adhesive.

Disadvantage of third generation bonding systems : Time consuming Technique sensitive

Fourth Generation dentin bonding agents : Although the smear layer acts as a diffusion barrier that decreases the permeability of dentin, it must be removed so that resin can be bonded to the underlying dentin substrate. Based on that consideration, fourth generation dentin adhesives were introduced for use on acid-etched dentin. Recently removal of the smear layer via acid etching has led to significant improvement in bond strengths.

In 1982 Nakabayashi and his colleagues reported the formation of hybrid layer resulting from the polymerized methacrylate and dentin.

The use of total etch is one of the main characteristics of the fourth generation bonding. The total etch technique permits the etching of enamel and dentin simultaneously using phosphoric acid for 15 to 20 seconds. The surface must be left moist to inorder to avoid collagen collapse. The application of hydrophilic primer can infiltrate the exposed collagen network forming the hybrid layer. Unfortunately moist dentin is not easily defined clinically and hence the bonds may not be ideal if the dentin is excessively wet /dried. The 125

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formation of resin tags and adhesive lateral branches complete the bonding mechanism between the adhesive material and etched dentin substrate.

Fourth generation adhesives are basically composed of An acid etching gel that is rinsed off A solution of primers that are reactive hydrophilic monomers in ethanol, acetone, and/or water; and An unfilled or filled fluid-bonding agent

The latter generally contains hydrophobic monomers such as bisphenol glycidyl methacrylate (BIS-GMA), frequently combined with hydrophilic molecules such as HEMA12.

The application of acid to dentin results in partial or total removal of smear layer and demineralization of the underlying dentin. Besides

demineralizing intertubular and peritubular dentin, acids open the dentin tubules and exposes dense filigree of collagen fibers.

Thus increasing the micro porosity of the intertubular dentin. Dentin is demineralized up to 7.5m. depending on the type of acid, application time and concentration.

Alteration in the mineral content of the substrate also change the surface free tension and the substrate must have a high energy of dentin. The adhesive system must have a low surface free energy for adequate interfacial contact. Substrates are characterized as having low or high surface energy. Of those materials used in dentistry, hydroxyapatite and glass-ionmer cement filler particles are high-energy substrates. Collagen and composite have low energy surfaces. Consequently, dentin consists of two distinct substrates, one of high126

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surface energy (hydroxyapatite) and one of low surface energy (collagen). Thus, after etching with acidic agents, the dense web of exposed collagen is a low-surface energy substrate. Infact, there is a correlation between the ability of an adhesive to spread on the dentin surface and the concentration of calcium on that same surface. An increase in the critical surface tension of dentin by surface-active components (primers) is highly desirable in this case, since a direct correlation between surface energy of dentin and shear bond strengths has been demonstrated.

When primer and bonding resin are applied to etched dentin, they penetrate the intertubular dentin, forming a resin-dentin intertubular dentin, forming a resin-dentin interdiffusion zone orhybrid layer. They also

penetrate and polymerize in the open dentinal tubules, forming resin tags.

Examples: All bond 2 (Bisco) Scotch Bond multipurpose (3M) Prime and Bond (Probond, dentsply) Solid Bond (kulzer) Optibond (sybron/kerr) Permaquick (ultradent) Imperiva bond (Shofu).

All Bond-2 : Uses an etchant of 35% phosphoric acid on dentin and enamel followed by the application of hydrophilic primer (primer A) containing 2% NTG GMA (N TOLYGLYcine- glycidyl methacrylate) and primer B- 16% BPDM (biphenyl dimethacrylate) in ethanol or acetone. Subsequently, an unfilled

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resin containing BIS GMA and HEMA is applied. Mean bond strength for thus system is seen to be 21.47.8MPa

Scotch bond multipurpose: Uses 10% maleic acid to etch both enamel and dentin. Primer is an aqueous solution of HEMA and poly alkenoate copolymers. The adhesive resin is a BIS GMA containing HEMA and photo initiators.

The bond strength achieved was 21.0 MPa with wet dentin and 18.0 MPa with dry dentin. Panavia 21 (kuraray) also utilizes a primer containing MDP, HEMA and 5 NMSA. It does not require a separate conditioning step. Adhesive monomer is the phosphoric acid ester of MDP. MDP has a potential towards providing long-term bond strength to metal and silanated porcelain. The material is strongly oxygen inhibiting so the manufacturer provides a gel to prevent oxygen coming in contact with it. Bond strengths with the system have been observed to be 211.5 Mpa

Amalgam Bond : Conditioner 10% citric acid 3% ferric chloride Primer Adhesive HEMA with water 4 META MMA TBB

Other fourth generation bonding system include Imperva Bond (Shofu), solid Bond (Kulzer), Opti Bond c & B, Metabond, etc. Mean shear bond strength achieved with this generation of agents is 17-24 MPa. 128

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Advantages of this concept of bonding agent : Reduced technique sensitivity Similar bond strengths to enamel and dentin No reduction in bond strength when applied to moist surface or under conditions of high humidity. Some systems can bond to mineralized tissue as well as metal, amalgam, porcelain and indirect composite restorations.

Fifth generation dentin bonding agents : Because of the complexity and number of steps or compounds involved with the fourth-generation systems, researches and manufacturers have worked to develop simpler adhesive systems. The objective has been to achieve

similar or improved bonding and sealing to that provided by the fourth generation materials, but to do it with fewer bottles and/or in less time18.

Uses a one-component resin is, after conditioning of enamel and dentin the steps of priming and bonding are combined so that bonding is achieved with a one-component formula. These systems have generally been reported to as One component systems. This technique also referred to as One coat, one bond and one cure technology.

These materials consist of hydrophilic and hydrophobic resin simultaneously dissolved in solvents like alcohol or acetone, displacing water and achieving an intimate contact to dentinal structures.

These materials also generally rely on residual moisture in the dentin and hydrophilic water chasing compositions to effect resin penetration into the 129

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dentin. Given the relatively high percentage of solvent, these formulations may be less forgiving to small changes in the dentin moisture content and may also require multiple application of primer/adhesive combination for successful bonding.

The fifth generation consists of two different types of adhesive materials. The so called one bottle systems Self etching primer bonding systems

One bottle system : These systems combined the primer and adhesives into one solution to be applied after etching enamel and dentin simultaneously with 35 to 37 percent phosphoric acid for 15 to 20 sec. These bonding systems create a mechanical interlocking with etched dentin by means of resin tags, adhesive lateral branches and hybrid layer formation and show high bond strength values both to etched enamel and dentin18.

The three step bonding procedures usually take up to 2 minutes. Hence the so-called one bottle systems. (Eg. Excite, Gluma one bond, one coat bond, Optibond Solo, Prime and Bond NT, Single bond, Solobond M, Syntac Sprint). It has been further seen that primer adhesive with incorporated filler particles (eg Optibond Solo) have higher bond strengths than unfilled products. When evaluating the marginal adaptation of class V restoration invitro most threestep systems showed more gap formation. This could be attributed to amore complete hybridization of the dentin in three-step smear layer removing bonding systems.

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Self Etching primer : Watanabe and Nakabayashi developed a self etching primer that was an aqueous solution of 20 percent Phenyl-P in 30 percent HEMA for bonding to enamel and dentin simultaneously. The combination of etching and priming steps reduce the working time, eliminate the washing out of the acidic gel and also eliminate the risk of collagen collapse. However, the self-etching primer solution also has some disadvantages. Like the solution must be refreshed continuously because its liquid formulation cannot be controlled where it is placed and often residual smear layer remained in between adhesive material and dentin. Also the effectiveness of self etching primer systems on properly etching the enamel was less predictable than the result obtained with phosphoric acid gel. Toida advised the removal of the smear layer by a separate etching step before bonding would produce a more reliable and durable bond to dentin.

Bond strength test did not demonstrate significant differences between one bottle systems and self etching primer bonding systems. Leakage tests showed that the seal achieved at the enamel margins with one bottle system is superior to that resulting from self etching primer.

Sixth Generation dentin bonding agents: To improve bond strength and to make manipulation easy this generation of adhesives has been tried.The sixth generation bonding systems are characterized by the possibility to achieve a proper bond to enamel and dentin using only one solution. The first evaluation of these systems showed sufficient bond to conditioned dentin while bond to enamel was less effective. This may be due to the fact that the sixth generation systems are composed of an acidic solution that cannot be kept in place, must be refreshed continuously and have a PK that is not enough to properly etch enamel. 131

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Self conditioning primer : (Eg. Clearfil liner bond 2, Resulcin Aqua Prime+ Monobond) when used there is no need of etching, rinsing and drying. In vitro studies have shown that the efficacy of clearfil liner bond 2 when used on unaltered dentin is comparable to the 3 step systems.

Recently a water based agent has been introduced which combines the functions of the conditioner, the primer and the adhesive in a so called selfconditioning primer-adhesive/condiprimer-adhesive (Etchand Prime 3.0). The active solution is mixed from two components resulting in the formation of an acidic (self conditioning) monomer which superficially etches dentin and enamel. The dentin bond medicated by this bonding agent seems to be

adequate. However the etching pattern of enamel appears to be less retentive than that produced by phosphoric acid etching.

Eg. Prompt L Pop: This has 3 compartments: Compartment 1 : Containing methacrylated phosphoric acid esters, photointiators and stabilizers. Compartment 2 : Contains water, complex fluoride and stabilizers. Compartment 3 : has a microbrush.

The blister is activated by squeezing compartment 1, thereby releasing its content into compartment 2. The mixing ratio is 4:1 and the freshly mixed solution is released on the microbrush into compartment 3.

On applying this on dentin the smear layer will be dissolved. Then the dimineralized dentin is loaded with prompt L pop monomers leading to the formation of a hybrid layer.

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Dentin might trigger inflammatory pulpal responses. Based on these concerns, acids were believed to be contraindicated for direct application of dentin and the total etch technique did not gain acceptance in Europe or the United states. However, newer adhesive systems) the fourth and fifth generation materials described in the previous section) based on the total etch philosophy have proved successful in vitro and vivo. Clinical retention rates have been reported to be very close to 100% compared with a second generation-adhesive system having retention rates in the 50% rates in 50% range. Laboratory bond strength usually vary from 17 MPa to 30 MPa, which are very close to the values obtained on enamel.

Seventh Generation: A new simplified adhesive system has been introduced that is the first representative of the 7th generation of adhesive materials. The 7th generation simplifies the multitude of 6th generation materials into a single component single bottle system19.

i bond (Heraeus Kulzer), the first no-mix, self etching, self priming, single bottle adhesive represents the most current formulation of dentinal adhesives on the market. It eliminates the uncertainty of mixing, and thus, any resulting technique sensitivity. It also eliminates the etching step, and by accomplishing the priming and the bonding of dental surfaces simultaneously, simplifies the adhesive procedure tremendously. This is a true, one-step, one bottle system for the complete etching and bonding of both enamel and dentin surfaces.

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Advantages: Excellent bonding strength to dentin (18-25Mpa) Similar adhesion to both prepared and unprepared enamel. Contains a desensitizing agent based up on Gluma. Can be used effectively for both direct and indirect composite restorations. Adheres well to ceramic and metal. Single bottle product. Insensitive to amount of residual moisture on surface of preparation. The bond strength to both dentin and enamel are essentially the same, regardless of the moisture or lack of moisture on the prepared surfaces. The shear bond strength of i Bond to dentin is relatively unaffected by the type of curing light used to polymerize the material, whether halogen, LED or plasma Arc. Adhesive systems with stress-absorbing potential4 : Product name Systems that provide a practical-filled adhesive resin Clearfil liner bond Clearfil liner bond 2 Fuji bond LC Imperva FL-Bond (Fluorobond) Optibond Optibond FL Optibond solo Permaquik Solid Bond Kuraray, Osaka, Japan Kuraray GC, Tokyo, Japan Shofu, Kyoto, Japan Kerr, Glendora, CA, USA Kerr Kerr Ultradent, South Jordan, UT, USA Heraeus Kulzer, Wehrheim, Germany Manufacturer

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Adhesive systems that include fluoride with caries protective and remineralization potential4 : Product Name Clearfil liner Bond2 Fuji bond LC Imperva Fl-Bond (Fluorobond) Opti Bond OptiBond FL Optibond solo Permaquik Prime&Bond 2.1 Solid Bond Syntax Single component Syntax Sprint Tenure Quik Kuraray GC, Tokyo; Japan Shofu, Kyoto, Japan Kerr, Glendora, Ca, USA Kerr Kerr Ultradent, south jordan, UT, USA Detrey-Dentsply, Konstanz, Germany Heraeus Kulzer, Wehrheim, Germany Vivadent, Schaan, Lictenstein Vivadent, Den-mat, Santa Maria, CA, USA Manufacturer

Classification based on adhesion strategies (VanMeerbeck and others)20 Total etch adhesives. 3 step 2 step Self etch adhesives 2 step 1 step Resin modified glass ionomer adhesives

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Dentin Bonding Agents

Total etch adhesive systems: Total etch adhesives involve a separate etch and rinse phase. Simultaneous application of an acid to enamel and dentin, known as the totaletch technique, is the most common strategy of dentin bonding. The total-etch technique was initiated in Japan by phosphoric acid etching of dentin before the application of a phosphate ester type of bonding agent. In spite of the obvious penetration of this early adhesive into the dentinal tubules, the application of phosphoric acid on dentin did not result in a significant improvement in bond strength, possibly because of the hydrophobic nature of phosphonated resin. In addition, in the mid-1970, some researches had hypothesized that the application of acids to dentin might trigger inflammatoy pulpal response.

Two step total etch adhesives combine the primer and adhesive resin in to one application. The underlying mechanism of adhesion of dentin is alike for the three and two step total etch adhesives. The dentin smear layer produced during cavity preparation is removed by the etch-and-rinse phase, which concurrently results in a 3-5m deep demineralization of dentin surface collagen fibrils are nearly completely uncovered from hydroxyapatite and form a micro retentive network for micro-mechanical interlocking, of monomer

The etch and rinse technique is still the most effective approach to achieving efficient and stable bonding to enamel and basically requires two steps. Selective dissolution of hydroxyapatite crystals through etching is followed by insitu polymerization of resin that is readily absorbed capillary attraction within the created etch pits, there by enveloping individually exposed hydroxyapatite crystals. Two types of resin tags interlock with in the etch pits. Macro-tags fill the space surrounded the enamel prism while

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numerous micro tags result from resin infiltration polymerization with in the tiny etch pits at the cores of the etched enamel prisms.

At dentin, this phosphoric acid treatment exposes a microporous network of collagen that is nearly totally deprived of hydroxyapatite.

TEM and chemical surface analysis by energy dispersive X-ray spectroscopy (EDXS) and X-ray photoelectron spectroscopy (XPS) have conformed that nearly all calcium phosphates were removed at least became under detection limit. As a result, the primary bonding mechanism of etch and rinse adhesives to dentin is primarily diffusion based and depends on hybridization or infiltration of resin with in the exposed collagen fibril scaffold. True chemical bonding is rather unlikely, because the functional groups of monomers may have only weak affinity to the hydroxyapatite depleted collagen.

Bonding of resin to dentin, using a total etch technique

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Three Step Total-Etch Adhesives Product ABC Enhanced Aelitebond All bond 2 Amalgambond plus Clearfil liner bond2-4 Dentastic Denthesive EBS EBS Multi Gluma Bonding System Gluma CPS Imperva Bond (total-etch) Mirage Bond OptiBond (total-etch) OptiBond FL (total-etch) PAAMA2 Permagen Permaquik Quadrant UniBond Restobond 3 Scotchbond Multi-Purpose Sctochbond Multi-Purpose Plus Solid Bond Super-Bond D Liner Tenure S Manufacturer Chameleon, Kansas city, KA, USA BISCO Bisco Parkell Kurary Pulpendt Hereaus-Kulzer ESPE ESPE Bayer Bayer Shofu Chameleon Kerr Kerr Southern Dental industries Ultradent Ultradent Canvex Holland, Haarlem, Netherlands, Lee Pharmaceuticals, South El Monte, CA,VS 3M 3M Heraeus-Kulzer Sun Medical Den- Mat

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Plus- minus balance of three-step total etch adhesives1. Plus Minus concentrated phosphoric acid etchants ) Time consuming three step application procedure In vitro and in-vivo effectiveness and dentin proven Post conditioning rinse phase required surface rubber Separate application of conditioner , Risk of over - etching dentin (highly primer and adhesive resin Lower technique sensitivity

of adhesion to enamel (time consuming and risk on contamination dam ) when not using

Best bond to enamel

Sensitive to overwet or overdry dentin surface conditions Weak monomer collagen interaction (which may lead to nano leakage and early bond degradation

Most effective and consistent results

Possibility for practice filled adhesive (shock absorber) Two step total etch1 : One concern in two step total etch is a risk of getting a thin hybrid layer. Monomers should be sufficiently supplied not only to saturate the exposed collagen fibril network, but also to establish a satisfactorily thick resin layer on top of the hybrid layer. Such a distinct resin layer must be regarded as a flexible, intermediate shock absorber. In light of an elastic bonding concept, it is expected that this shock absorber may help to protect the adhesive joint against early failure caused by the shrinking composite cured on top. Therefore when using one bottle adhesives, it is recommended to apply multiple layers to ensure a sufficiently, think resin film on top of the hybrid layer. They are particularly necessary when using primer / adhesive resin 139

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combination with high acetone content. The so called nanofiller added is certain one bottle adhesives (Prime & Bond NT) may also help to establish a uniform resin film that stabilizes the hybrid layer . After priming the surface should appear glossy with out dryspot, the clinical indication that resin was adequately and sufficiently applied.

Brand name Manufacture Two Step Total Etch Adhesives -One Bottle Adhesives Bond 1 Jeneric/Pentron, Wallingford, CT, USA Dentastic Uno Pulpdent, Watertown, MA, USA Dentastic Duo Pulpdent Easy Bond Parkell, Farmingadale, NY, USA Excite2 Vivadent Gluma 2000 Bayer, Leverkusen, Germany Gluma One Bond Hereaus-Kulzer Gluma Comfort Bond Hereaus-Kulzer One Coat Bond Coltene One Step Bisco, Schaumburg, IL, USA Optibond SOLO Kerr Optibond solo plus Kerr Prime & Bond 2.1 Dentsply Prime &Bond 2.1 Dual Cure Dentsply 2 Prime & Bond NT Dentsply Prime & Bond NT Dual Cure Dentsply PQ1 Ultradent, South Jordan, UT, USA Scotchbond 1 (single Bond) Cooley& Cooley, Houston, TX, USA Snapbond DMG Solist Voco, Cuxhaven, Germany Solobond M Southern Dental Industries, Stae Victoria,Austraia Syntac Single-Component Vivadent Syntac Sprint Vivadent Tenure Quik with Fluoride Dent-Mat, Santa Maria, CA, USA.

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Plus Minus Balance of Two Step Total Etch Adhesives1 Plus Basic features of three steps systems simpler application procedure by reduction with 1 step Possibility for single-dose Packaging Consistent and stable composition Controlled solvent evaporation Hygienic application Possibility for particle-filled adhesive Effects of total-etch technique (shock-absorber) Risk of over etching dentin Post-conditioning rinse phase required sensitive to degree of dentin wetness Weak monomer-collagen interaction Insufficient long-term clinical results Minus Not substantially faster application (multiple layers) More technique- sensitive (multiple layers) Risk of too thin bonding layer (no glossy film, no shock absorber, insufficiently polymerizable due to oxygen inhibition)

Self etching primers : The first system based on this philosophy included acidic etchants with low concentration than the traditional 30-40%. Phosphoric acid. Some studies have indicated that low concentration etchants (such as 2.5% nitric, 10% citric), 10% phosphoric, or 10% maleic) are as effective as 30% to 40% phosphoric acid when applied to enamel for 15 seconds. However other studies have shown that such low concentration acids have lower enamel bond 141

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strengths than conventional 30% to 40% phosphoric acid, when the traditional frosted enamel surface often is not apparent after the application of weaker acids. Under SEM enamel etched with 10% maleic acid or with 10%

phosphoric acid for 15 seconds does not acquire the etching pattern characteristic of enamel etched with 30-40% phosphoric acid for 15 to 30 seconds.

More recently another type of acidic conditions, the self-etching primers (SEPs), was introduced in Japan. These acidic primers include a phosphonated resin molecule that performs two functions simultaneously-etching and priming of dentin and enamel. Unlike conventional etchants, self-etching

primers are not rinsed off. The bonding mechanisms of self etching primers is based on the simultaneous etching and priming of enamel and dentin without rinsing, forming a continuum in the substrate and incorporating smear plug into the resin tags.

In addition to simplifying the bonding technique, the elimination of rinsing and drying steps reduces the possibility of over wetting or over drying, which can have a negative influence in adhesion. However, the sealing of enamel margins in vivo may be compromised because a perfect marginal integrity is not achieved.

Based on the use of non- rinse acidic monomers that simultaneously condition and prime dentin and enamel. The concept of self- etch primers was introduced with Scotch bond 2 in the early 90.s.. However this system was

advocated only to be applied on dentin alone, and therefore required a selective enamel etching step.

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The current self etch adhesive provide monomer formulations for simultaneous conditioning and priming of both enamel and dentin.

Bonding to dentin using a self etching primer

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Two step self etch adhesive1

Product Clearfill Liner Bond 2 Clearfill Liner Bond 2v Clearfill SE Imperva FL-Bond NRC & Prime&Bond NT OptiBond (no-etch) OptiBond FL (no-etch) Sustel (F2000) Unifil BOND Coltene ART bond Denthesive 11 Ecusit Primer-Mono Imperva bond (no etch) Scotchbond 2 Solid Bond3 Superlux Universalbond 2 Syntac XR-Bond

Manufacturer Kuraray Kuraray Kuraray Shofu Dentsply Kerr, Orange, CA, USA Kerr 3M GC Coltene, Alstatten, Switserland Hereaus-kulzer, Wehrheim, Germany DMG Shofu 3M Hereaus-Kulzer DMG Vivadent Kerr

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One step self etch (all in- one adhesives)1

Product AQ Bond-Touch & Bond Etch&Prime 3.0 One-up Bond F Prompt L-Pop Xeno CF Bond

Manufacture Sun Medical, Kyoto, Japan Degussa, Hanau, Germany Tokuyama, Tokyo, Japan ESPE Sankin, Otahara, Japan

Self etch adhesives subdivided depending on their pH and etching potential1 Mild (pH=2) Clearfil Liner Bond 2V (Kuraray) Strong (pH1) Non-Rinse Conditioner & Prime & Bond NT (Dentsply) Clearfil SE Bond (Kuraray) F2000 Primer/adhesive (3M) Imperva FL-Bond (Shofu) Mac-Bond II (Tokuyama) One-up Bond F (Tokuyama) Experimental PQ/Universal (Uttradent) Unifil Bond (GC) Prompt L- Pop (ESPE) Vivadent adhesive experiment self-etch

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Mild self etch adhesives : Mild self etch system has a pH of around 2 and demineralize dentin only to a depth of 1 m. This superficial demineralization occurs only partially, keeping residual hydroxyapatite still attached to collagen. The bonding mechanism of mild self etch adhesives to dentin based on hybridization , with the difference that only submicron hybrid layers are formed and resin tag formation is less pronounced .

The preservation of hydroxyapatite with in the submicron hybrid layer may serve as a receptor for additional chemical bonding. Carboxylic acid based monomers 4-META (4-methacryloxyethyl trimellitic-acid ) and phosphate based monomers, such as Phenyl p (2 methacryloxyethyl phenyl hydrogen phosphate) and 10 MDP(10-methacryloxydecyl dihydrogen

phosphate) have a chemical bonding to calcium of residual hydroxyapatite .

Thus two - fold bonding mechanism may be advantageous in terms of restoration longevity. It cornprises a micro- mechanical bonding component that may provide resistance to acute debonding stress. The additional monomer \ hydroxyapatite around collagen interaction on a molecular level may result in bonds that better resist hydrolytic degradation

process, and these may help keep the restoration margins sealed for longer periods. Weak self etching effect is mandatory inorder to 1. 2. 3. Deal with smear layers resulting from cavity preparation. Achieve micro mechanical interlocking with in etch pits at enamel Achieve micro mechanical interlocking through hybridization at dentin

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Strong self etch adhesive : Have a pH 1 or below. Thus high acidity results in rather deep demineralization effects. At enamel, the resulting acid etch pattern resembles a phosphoric acid treatment following an etch & resins approach. At dentin, collagen is exposed and nearly all hydroxyapatite is dissolved. The bonding mechanism of strong- self-etch adhesives is primary diffusion-based, similar to etch & rinse approach.

Advantages: Simplify the bonding process by eliminating steps Eliminate some of the technique sensitive of total etch system Since etch/ rinse phase is eliminated, the issue of wet bonding is of no relevance. The risk on incomplete resin infiltration of the exposed collagen fibril scaffold with resin up to the same depth of demineralization. Intermediary strong two step self- etch adhesives : pH is about 1.5 Most typical is the two fold build up of the dentinal hybrid layer with a complete demineralized top layer and a partially deminaralized base. Following a Intermediary strong self- etch approach , the deepest region of the hybrid layer up to a maximum of 1m still contains hydroxyapatite , by which the transition of the hybrid layer to the underlying unaffected dentin is more gradual.

Based on acidity the one step self etch adhesive i-Bond are Xeno III must also categorized as intermediary strong self-etch adhesives.

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Plus-Minus Balance of Self-Etch Adhesives1 Plus Simultaneous demineralization and resin-infiltration No post-conditioning rising Minus Insufficient long-term clinical research Adhesion potential to enamel needs yet to be clinically proven Not sensitive to diverse dentinwetness conditions Time-saving application procedure Low technique-sensitivity Possibility for Single-dose packaging Consistent and stable compositon Controlled stable composition Hygienic application Possibility for particle-filled adhesive (shock-absorber) Adequate monomer-collagen interaction Effective dentin desensitizer

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According to smear layer modified / removed / dissolved : The most common classification of adhesives is based on the time of their release on the dental market. Classification in generation lacks scientific basis and thus does not allow the adhesives to be categorized on objective criteria. A more logical classification of adhesives would be based on the number of clinical application steps and, more importantly, on their interaction with the dentinal substrate.

Three adhesion strategies, distinguished by how they interact with the smear layer are currently in use with modern dentin adhesive systems.

One strategy aims to modify the smear layer and incorporate it in the bonding process : One and two-step smear layer-modifying adhesives can be

distinguished, as they either provide only an adhesive resin or, successively, a primer and an adhesive resin or successively, a primer and an adhesive resin.

The second strategy completely removes the smear layer and concurrently demineralizes the underlying dentinal surface : The system using this strategy can be further subdivided into two- and three-step smear layer- removing adhesives, depending on whether they have a combined or separate application of primer and adhesive.

The third adhesion strategy is a combination of these two : This system dissolves the smear layer rather than removing it and simultaneously demineralizes the underlying dentinal surface, but only superficially. This category can also be subdivided into one- and two-step smear layer-dissolving adhesives.

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Smear layer-Modifying Adhesives : Dentin adhesives that modify the smear layer are based on the concept that the smear layer provides a natural barrier to the pulp, protecting it against bacterial invasion and limiting the outflow of pulpal fluid that might impair bonding efficiency. Efficient wetting and in situ polymerization of monomer infiltrated into the smear layer are expected to reinforce the bonding of the smear layer to the underlying dentinal surface, forming a micro mechanical and perhaps chemical bonds to underlying dentin. Clinically, these systems require selective etching of enamel in a separate step. Most typical in this group are the primers that are applied before the application of polyacid-modified resin composites or compomers.

The interaction of these adhesion with dentin is very superficial, with only a limited penetration of resin into the dentinal surface . This shallow interaction of the adhesive system with dentin, without any collagen fibril exposure, confirms the weak acidity of these smear layer-modifying primers. The dentinal tubules commonly remain plugged by smear debris. One step smear layer modifying system4 Product Name Manufacture

Hytac OSB (in combination with Hytar) ESPE,Seefeld,Germany Pertac Universal Bond Prime & Bond 2.1(no-etch,in Combination with Dyract) Solist(in combination with luxat) Tokuso Light Bond (one step) DMG, Hamburg, Germany Tokuyama Japan Soda, Tokuyama, ESPE Caulk, Konstanz, Germany

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Two step smear layer modifying systems4

Product name

Manufacturer

Optec Universal Bonding System Jeneric/Pentron, Wallingford, CT, USA Pentra Bond II Pro BOND Tokuso Light Bond ( two Step) Tripton Jeneric /Pentron Caulk, Konstanz, Germany Tokuyama soda, Tokuyama, Japan ICI, Macclesfield, UK

Smear layer-Removing Adhesives : Most of todays adhesive systems opt for a complete removal of the smear layer, using a total-etch concept. Their mechanism is principally based on the combined effect of hybridization and formation of resin tags . These systems are applied in three consecutive steps and subsequently categorized as three steps smear layer-removing adhesives. Even when applied to sclerotic dentin, the relatively aggressive phosphoric acid etching procedure results in the formation of a loosely organized hybrid layer.

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Three step smear layer removing systems4 Product name ABC enhanced Aelitebond All-Bond Amalgambond plus Clearfil liner Bond Dentastic Denthesive EBS Gluma Bonding System Gluma CPS Imperva Bond (total-etch) Mirage Bond OptiBond (total-etch) Opti Bond FL (total-etch) PAAMA2 Manufacture Chameleon, kansas city, KS, USA. Bisco, itasca, IL, USA Bisco Parkell, Farmingade, NY, USA Kurary, Osaka, Japan Pulpdent, Watertown, MA, USA Heraeus Kulzer, wehrheim, Germany ESPE, Seefeld, Germany Bayer, Laverkusen, Germany Bayer Shofu, Kyoto, Japan Chameleon Kerr, Glendora, CA, USA Kerr, Southern Dental industries, Victoria, Australia Permagen Permaquik Restobond 3 Ultradent, South Jordan, UT, USA Ultradent Lee pharmaceuticals,south Ei Monte, CA, USA Scotchbond Multi-Purpose Scotchbond Multi-Purpose Plus Solid Bond Super-Bond D Liner Tenure S 3M. St. Paul, MN, USA 3M, St, Paul, MN, USA Heraeus Kulzer Sun Medical, Kyoto, Japan Den-Mat, Santa Maria, CA. USA

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Two step smear layer removing systems4

Product name One-step Fuji Bond LC Gluma 2000 Optibond solo Prime & Bond 2.0 (total etch) Scotchbond 1 (Single bond) Solist Syntac Single-Component Syntac Sprint Tenure Quik

Manufacturer Bisco, Itasca, IL, USA GC, Tokyo, Japan Bayer, Leverkusen, Germany Kerr, Glendora, CA, USA Caulk, Konstanz, Germany 3M, St. Paul, MN, USA DMG, Hamburg, Germany Vivadent, Schaan, Liechtenstein Vivadent Den-Mat, Santa Maria, CA, USA

Smear layer dissolving adhesives : A simplified application procedure is also a feature of the smear layerdissolving adhesives or self etching adhesives, which use slightly acidic primer or so called self etching primers. These primers practically demineralize the smear layer and the underlying dentin surface without removing the dissolved smear layer remnants or unplugging the tubule orifices.

The current two-step smear layer-dissolving adhesives provide selfetching primers for simultaneous conditioning and priming of both enamel and dentin. Simplification of the clinical application procedure is obtained not only by reduction of application steps, but by omission of a post conditioning rinsing phase. These condiprimers are only air dispersed with out rinsing. As a supplementary advantage, the controversy of post conditioning drying or keeping the dentin moist, as in a wet bonding technique is avoided. The actual

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rationale behind these systems is to superficially demineralize dentin and so simultaneously penetrate it to the depth of demineralization with monomer that can be polymerized in situ. Two step smear layer dissolving systems4

Product name Clearfil Liner Bond 2 Coltene ART bond DenthesiveII Etch & Prime 3.0 Ecusit Primer-Mono Imperva FL-Bond (no etch) Imperva FL-Bond (Fluorobond) Optibond ( no-etch) OptiBond FL (no-etch) Scotchbond2 Superlux Universalbond 2 Syntac XR-Bond

Manufacturer Kuraray, Osaka, Japan Coltene, Altstatten, Switzerland Heraeus Kulzer, Wehrheim, germany Degussa, Hanau, Germany DMG,Hamburg,Germany Shofo, Kyoto, Japan Shofo, Kyoto, Japan Kerr, Gledora, CA, USA Kerr, 3M, St. Paul, MN, USA DMG, Hamburg, Germany Vivadent, Schaan, Liechtensein Kerr

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Bonding generations table19 Bonding generation 7th Characteristics Bond strength to dentin Single component Desensitizing Self etching Self priming No mixing Moisture independent Bonds to metal Little or no sensitivity 6th Multi component Multi step Self etching Self priming Hybridization No mixing Little sensitivity 5th Single component Moist bonding Hybridization No mixing Little sensitivity 20-24 MPa Gluma Comfort Bond Prime & Bond NT single Bond Excite One step Bond1 1 18-23MPa Prompt-LPop SE Bond Liner II Bond 2-3 18-25MPa iBOND 1 Examples Components

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4th

Hydridization Total etch Little sensitivity

17-25MPa

All bond II Pro Bond Scotchbond MP Tenure Bond it Syntac

2-5

3rd

2 component primer 8-15 MPa and adhesive system Bonds to metal Reduced sensitivity

Prisma Universal Bond Scotchbond II Tenure Gluma X-R Bond

2-3

2nd

Weak adhesives requiring retentive preparations Prone to water degradation

2-8 MPa

Bond Lite Scotch bond Dentin Adhesit

1st

Very Weak Bond to dentin

2 MPa

Cervident Cosmic Bond

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AMALGAM BONDING SYSTEMS


Amalgam bonding systems may be used to seal underlying tooth structure and bond amalgam to enamel and dentin. They require dual characteristics to achieve optimal wetting. Amalgam is strongly hydrophobic, whereas enamel and dentin are hydrophilic. Therefore the bonding system must be modified with a wetting agent that has the capacity to wet either hydrophobic or hydrophilic surfaces. Typical dentin bonding systems may be used, but special 4-methyloxy ethyl trimellitic anhydride (4-META) based systems are used frequently. This monomer molecule contains both hydrophobic and hydrophilic ends12.

Macro shear bond strengths for joining amalgam to dentin are relatively low (2 to 6 Mpa). Although good bonding occurs to tooth structure, micromechanical bonding at the interface of the amalgam with bonding system is poor. Most debonding occurs by fracture along this interface. Since no chemical bonding occurs at this interface, it is important to develop micromechanical bonding. To accomplish this, the bonding system is applied in much thicker layers, so that amalgam being condensed against the resin adhesive layer will force fluid components of the amalgam to squeeze into the unset bonding adhesive layer and produce micromechanical laminations of the two materials. Thicker bonding agent films can be produced by adding thickening agents to the unset bonding materials or by applying many applications of bonding material.

The primary advantages for amalgam bonding agents in most clinical situations are the dentin sealing and improved resistance form, but the increase in retention form is not significant. Adhesion of amalgam to tooth structure is

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not necessary in clinical circumstances when satisfactory retention and resistance forms of tooth preparation already exist. Primary indication for amalgam bonding is when weakened tooth structure remains and bonding may improve the overall resistance form of the restored tooth.

Sealing amalgam preparations is the sole purpose for bonding, and then an alternative is the use of dentin sealers. The earliest version of such a system (Gluma 2, Bayer Dental Products) was actually the primer component of a dentin bonding system. Since the introduction of that product, several others have been developed that are essentially primer monomers and/or polymers dissolved in solvent that penetrate the surfaces of the preparation and dry or are cured as a polymer film. The action of this film is very similar to that of varnish, except the film has much better wetting characteristics and produces a completely impervious layer. The film actually covers enamel as well as dentin but is still categorized as a dentin sealer. Because the same material may be used over open dentin tubules on exposed root surfaces to eliminate fluid flow and desensitize dentin, dentin sealers are also known as dentin desensitizers. However, an expansive list of other products also may be called dentin desensitizers, but they are not routinely used to seal dentin under amalgam restorations.

Bonding systems used below insulating restorations, such as composite, do not utilize traditional liners and bases except when the tooth excavation is extremely close to the pulp (RDT<0.5 mm). In that case, a traditional calcium hydroxide liner is used for pulpal medication, to stimulate reparative dentin.

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PULPAL CONSIDERATIONS OF ADHESIVE MATERIALS


It has been suggested that conditioning agents (etching agents used on dentins) should be Isotonic to avoid osmotic pressure charger in dentinal tubules Of neutral pH or at least between PH 5.5 and PH. 8.0 Nontoxic to dentin, pulp and gingival tissue, Compatible with the chemistry of the materials it will contact. Water soluble and easily removed Unable to deplete the enamel or dentin chemically Able to enhance the surface chemically in preparation for bonding.

Many dentin-conditioning agents have pH values much lower than 5.5.Acids can challenge pulp vitality and they can harm the pulp if they contact it. The smear layer and tubular plug (smear unit) and peritubular dentin (sclerotic dentin) can be rapidly dissolved by strong acidic conditioning agents when applied for excessive time intervals20.

The concentration of an acid reaching the pulp tissue is determined by how much penetrates through dentinal tubules and reacts along the way with hydroxyapatite and proteins contained with in the tubules. The solute

concentration of an acid is reduced over distance such that at relatively large thickness (>1.0mm) the concentration of a substance is relatively low by the time it reaches pulp surface. As the remaining dentin thickness decreases, there is less reduction of solute concentration, causing a higher concentration at the pulpal surface as the diffusing solutes reach the end of the tubules. Cytotoxic effects with in the pulp tissues can be caused by low pH, hypertonic, 159

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and hypotonic concentrations (abnormal osmolatity) or chemical interferences with vital biochemical reactions.

The pulp of younger virgin tooth with wide open dentinal tubules to begin with is more susceptible to the toxic components of dental materials and responds with a more intense inflammatory response than does an older tooth which over the years has produced a considerable amount of sclerotic dentin and reparative dentin that protect the pulp with. (a) Sclerosis of dentin either as a natural process of aging or induced by the irritation from caries, attrition, abrasion and erosion, and (b) Reparative dentin formation, induced by the above factor and also by tooth cutting and restorative procedures.

Some investigators recommend that the smear layer be removed with various acids to optimize the bonding of restorative materials to dentin, while others feel it can be left but modified, since its presence reduces the permeability of dentin.

Many authors utilizing either phosphoric acid or citric acid as conditioning agents found them to be too destructive, since they removed the smear unit, opened and widened (funneled) dentinal tubules, and increased the severity of the pulpal responses to materials placed subsequently.

Technique factors must be taken into consideration : When evaluating whether an etching technique is good or bad, one must remember that subtle changes in techniques and methods can cause important changes in results, and that the following factor must be taken into consideration.

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Type of acid, concentration, time interval; of application. Active (rubbing, scrubbing) or passive (soaking) application Whether the etching was applied as a solution or as drops . Cavity preparations or just exposed superficial dentin Consideration of remaining dentin thickness (RDT) Presence or absence of sclerotic dentin and reparative dentin. Age of the patient and species and age of experimental animal. Pulpal responses to subsequent type of restoration; Condensation of amalgam Self cured composite resin, placed under pressure. Visible- light cured composite resin placed incrementally, and Pulpal response to a fresh mix of a restorative material or to a cured disc of the material in question placed in a leaching solution to measure the release of H+.

Shortening of application time of conditioning agents : In 1977 Brannstrom and Nordenvall noted no demonstrable differences between dentinal surfaces etched for 15 seconds or two minutes and recommended shorter etching times.

Brannstrom felt that the degree of chemical action depended on the duration of its application. Removal of the smear layer from both enamel and dentin was accomplished rapidly in five to ten seconds of exposure to a weak acid and five seconds of 37% H 3Po4applied to dentin was quite adequate to produce necessary changes. But the same agent that may remove the smear layer in five seconds can cause considerable decalcification if left in place for 30 seconds, and produce pulpal damage if left for 60 seconds (Mount, 1990).

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Pulpal responses to bonding agents : Bonding agents of themselves do not appear to be toxic. As far back as 1975 it appeared that bonding agents helped reduce the expected pulpal responses induced by the subsequent placement of toxic composite resins.

Gluma bonding technique also provided immediate bactericidal and long term (90 days) bacteriostatic action.

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CLINICAL APPLICATIONS OF DENTIN BONDING AGENTS


Bonding of directly placed resin based restorative materials. Bonding of ceramic restorations. Bonding of amalgam restorations. Re-attachment of fractured tooth fragments. Pulp capping. Desensitization of sensitive cervical dentin or cementum. Adhesive luting of bridgework. Repair of porcelain and metal ceramic restoration. Desensitization: Dentin hypersensitivity is a common clinical condition that is difficult to treat because the treatment outcome is not consistently successful. Hydrodynamic theory explains dentin hypersensitivity.

Patients may complain of discomfort when teeth are subjected to temperature changes, osmotic gradients such as those caused by sweet or salty foods, or even tactile stimuli. The cervical area of tooth is the most common site. Cervical hypersensitivity may be caused not only by chemical erosion, but also by mechanical abrasion or even occlusal stresses.

Theories about the transmission of pain stimuli in dentin sensitivity suggest that pain be amplified when the dentinal tubules are open to the oral cavity. The relationship between dentin hypersensitivity and the patency of dentin tubules in vivo has been established and occlusion of the tubules seems to decrease that sensitivity. It also has been suggested that the incorrect 163

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manipulation of some adhesives materials, namely those with acetone, may actually trigger postoperative sensitivity.

Clinicians have used many materials and techniques to treat dentin hypersensitivity, including specific dentifrices, co2 laser irradiation, dentin adhesives, antibacterial agents, aldehydes, resin suspensions, fluoride rinses, fluoride varnishes, calcium phosphate, potassium nitrate, and oxalates.

The use of dentin adhesives to treat hypersensitive root surface has gained popularity over the last few years. Reduction in sensitivity may result from formation of resin tags and a hybrid layer when a dentin adhesive is used. The precipitation of proteins from the dentinal fluid in the tubules may also account for the efficacy of desensitizing solutions.

The primers of multibottle adhesive system All-Bond 2 (Bisco) have a desensitizing effect, even without consistent resin tag formation.

In a clinical study using the primer of the original Gluma adhesive system (an aqueous solution of 5% gultaraldehyde and 35% HEMA, currently marked as Gluma Desensitizer), the desensitizing solution was applied to crown preparations. The author concluded that Gluma primer reduced dentin sensitivity through a protein denaturation process with concomitant changes in dentin permeability.

Adhesive Amalgam restoration : Marginal discoloration, recurrent caries lesions, and postoperative sensitivity are the most frequent consequences of the penetration of oral fluids and bacteria through gaps at the dentin resin interface towards the pulp.

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Delayed interfacial marginal leakage occurs at the amalgampreparation interface. Corrosion products from amalgam seal the interface after a few months, however, this process may take more than 6 months for copper rich amalgam alloys.

To overcome the inevitable marginal micro leakage, dentin adhesive systems have been used both under mercury-based amalgam restorations and under gallium-based amalgam restorations. The use of adhesive systems

beneath amalgam restorations reduces or prevents marginal leakage both in vivo and in vitro and improves marginal integrity of the restoration when compared to the use of a copal varnish. Additionally, dentin adhesives reinforce the amalgam restoration margins, making the cavosurface angle less susceptible to acidic demineralization in vitro.

Several laboratory and clinical studies have shown that dentin adhesive systems such as All-Bond 2 (Bisco), Amalgam bond plus (Parkell), Panavia (kuraray) and Scotch bond Multipurpose plus (3M) can be used to bond amalgam restorations. The attachment mechanism between the adhesive and the amalgam is not full understood, but it may be micromechanical entanglement of the uncured adhesive material with the settings amalgam mix during condensation of the amalgam.

This bonding mechanism actually may depend on the type of amalgam used, for example spherical amalgam alloys critically have higher bond strength than dispersed phase or admixed amalgam alloy.

Recent studies have demonstrated that some current adhesive systems provide bond strength in range of 10 to 14 MPa. As a safety precaution,

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primary mechanical retention features are still recommended when an adhesive system is used with amalgam.

Some studies also suggest that the use of dual- cured filled liners may be beneficial for bonding amalgam to dentin. The additional adhesive liner may provide an increased retention to adhesive amalgam restorations, therefore allowing for preparations with lower demand for additional retention features such as dove tails, slots, holes or even pins, Moreover marginal leakage has been shown to decrease when thick dual cured or self cured liners are used.

Another advantage from the use the of dentin adhesives under amalgam restoration is that the residual tooth structure becomes more resistant to fracture.

Light curing of resin from the external tooth surface after condensing the amalgam into the preparation recently has been evaluated in vitro for three dual-cured adhesive system. The rationale behind the use of light curing through the tooth walls was that some dual cured adhesives might not be able to polymerize completely underneath the amalgam restoration.

Dentin adhesive systems also are used to bond fresh amalgam to existing amalgam restorations in repair procedures. The prognosis of this type of procedure is unpredictable and can be unsuccessful. The interfacial failure between fresh amalgam and old amalgam may be result of lack of micro mechanical retention in the old amalgam restoration surface. dentin adhesive systems are not recommended for amalgam repair. Therefore

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Indirect Adhesive restorations : Current dentin adhesive systems are considered as universal adhesives because they bond to various substrates besides dentin. Recent developments in adhesion technology have led to new indications for bonding to the tooth structure, such as indirect composite and ceramic restorations (Crowns, inlays, onlays, and veneers). The use of a universal adhesive system in conjunction with resin cement provides durable bonding indirect restorations to tooth structure.

Ceramic restorations (with the exception of aluminous core porcelains such as In-ceram high strength ceramic) must be etched internally with 6% to 10% hydrofluoric acid (HF) for to 2 minutes to create retentive micro porosities.

HF must be rinsed off carefully with running water for at least 2 minutes. Some clinicians use sandblasting with aluminum oxide particles in the internal surface of the restorations. After rinsing off the HF and drying with an air syringe, a silane-coupling agent is applied on the etched porcelain surface and air-dried. The coupling agent acts as a primer because it modifies the surface characteristics of etched porcelain. Because etched porcelain is an inorganic substrate, the coupling agents make this surface more receptive to organic materials, the adhesive system and composite resin cement. The use of silanes may actually increase the bond between the composite and porcelain in the range of 25%. Indirect composite restorations may be bonded to etched

dental substrates using a universal adhesive system and a resin luting cement. One of the great advantages of indirect composite restorations is that polymerization shrinkage occurs outside the mouth.

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Additionally, the degree of monomer conversion is higher for indirect resin-based restorations. However, this increased level of double bond

conversion results in only a small amount of monomer double bonds on the internal surface of the indirect composite restoration therefore decreasing the potential for bonding with the adhesive system and with the composite luting cement. To overcome this unsuitable bonding surface, the composite maybe treated with surface activators to reestablish the surface energy. [Composite Activator (Bisco), Activator-Art Glass (Heraeus kulzer)]. Another alternative is sandblasting the bonding surface of indirect restoration to expose an internal area where more double bonds may be present. HF is contraindicated for treating indirect composites because it softens some composite materials.

Porcelain and Ceramic Repair systems : Fractured regions on porcelain-fused-to-metal or all-ceramic

restorations may be repaired by etching the surface with hydrofluoric (HF) acid, silanating the etched ceramic material, applying bonding agent, and adding composite to replace the missing material. This is not a long-term solution to the problem but does provide an immediate alternative rather than complete replacement of the original restoration. Wetting of ceramic materials by bonding materials is different than for dentin and may not work well with all bonding systems. If the substrate being repaired includes exposed metal alloy on a portion of a porcelain-fused-to-metal restoration, then the metal should be sandblasted and etched to enhance retention.

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DENTIN BONDING AGENTS FOR PULP CAPPING : The direct pulp-capping technique with adhesive system has recently been advocated with mixed evidences of clinical success from vital pulp therapy performed in the teeth of animals. The apparent clinical/radiographical success of pulp therapy and the results from vital pulp capping performed in animals teeth are also compared to clinical conditions and results obtained form pulp capping procedures performed in mechanically exposed sound human pulps.

For vital pulp capping to be successful, the tooth should be asymptomatic or have minimal symptoms and the bleeding must be controlled. This control may be achieved by washing the area with sterile saline and drying it with either paper points or cotton pellets,

For vital pulp capping by total etch procedure, hemostasis must be obtained. The exposure site is then covered with a non-setting calcium hydroxide paste (e.g., Pulpdent, Pulpdent Corp. of America, Brookline, Mass.) and the cavity preparation completed. Following disinfection of the cavity, the enamel and dentin are etched with 32% phosphoric acid for 15 seconds. The acid and calcium hydroxide are rinsed off and the preparation is lightly dried. The entire preparation, including enamel, dentin and pulpal tissue , is treated with a dentin bonding system. Fourth-generation system with a separate primer and adhesive is recommended, as little research has been published to date on the fifth-generation dentin bonding systems. Following placement of several layers of the hydrophilic primer, a thin layer of the adhesive resin is painted onto the enamel, dentin and pulpal tissue and light cured. A second layer of unfilled resin is applied, and a thin layer of resin-modified glass ionomer is also applied over and around the exposure site to mechanically protect the perforation from intrusion of the restorative material during packing or 169

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condensation. These layers are also light cured. The restoration is subsequently completed in conventional fashion.
Pulp exposure

Total etch technique

Hemostasis

Disinfect cavity

Etch

Primers

Adhesive

Resin modified glass ionomer

Restoration

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In a study performed in primate teeth, Akimoto et al. showed that Clearfil liner bond 2 permitted the differentiation of new pulpal cells that stratified, polarized (reoriented), and laid down a dentinal bridge. These

histological findings may support the use of those materials for placement on pulp exposures. It has also been reported that possible failures of pulp capping therapy with adhesive systems may be due to poor hemorrhage control, material placement and incomplete polymerization. The results observed with animal teeth capped with adhesive systems are different from those in which similar vital pulp therapy has been performed in human teeth.

Recent studies performed in human teeth have demonstrated that following application of an adhesive system to pulpal wounds, the materials delayed pulpal healing, resulting in lack of dentin bridge formation, even 60 days after the pulp capping procedure. The pulp exposure site showed a persistent inflammatory response evidenced by macrophages and giant cells.

Gwinnett and Tay recently demonstrated the features of the pulpal responses following application of all bond 2 to acid- conditioned human pulp tissue. The authors reported an irreversible injury to the odontoblasts closest to the site of cavity preparations that resulted in a death of these cells. In some specimens, the presence of these particles appeared to have triggered a foreign body response, characterized by the presence of a mononuclear infiltrate as well as the appearance of multinuclear giant cells. The persistence of

unresolved chronic inflammation wan associated with the lack of calcified bridge formation in these specimens.

Following application of Clearfil Liner bond 2 to mechanically exposed human pulps a large number of macrophages and giant cells were notable

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features of the pulp tissue capped with clearfil liner bond 2. The materials were evaluated at 4.30, between 90 and 300 days.

In studies performed in human teeth, the histological findings has no direct correlation with clinical observations. Patients who had their pulps capped with adhesive systems reported no clinical discomfort during the experiments. In contrast, the histopathological analysis of the teeth showed intense inflammatory responses in the short term and persistent inflammatory reactions close to the resin pulp capping in the long-term. Periapical lesions were not detected even along-term evaluation (360 days in primary teeth or between 60 and 300 days in permanent teeth. These observations have confirmed that clinical and radiographic evidence alone cannot support the introduction of any new pulp therapy.

The results obtained from in vivo animal studies; in which various adhesive systems were applied to mechanically exposed pulps cannot be directly extrapolated to human clinical conditions.

Clinical and radiographic evaluations of teeth submitted to various pulp therapies do not indicate the biocompatibility of dental materials or support pulp capping techniques.

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LIST OF GUIDELINES TO ENSURE CLINICAL SUCCESS


1. Use proper isolation : Hydrophilic bonding systems may tolerate saliva contamination to certain degree but evidence for such tolerance remains minimal so proper isolation is necessary.

2. Bond to enamel : Whenever a restoration is bond to dentin the adjacent enamel should be etched. Enamel etching is a very reliable method of bonding resins to tooth structure.

3. Roughen sclerotic dentin : Bonded restoration are most likely to fail when bonded to sclerotic dentin. Light roughening with diamond or carbide bur may provide more micromechanical locking.

4. Use mechanical retention it supplements retention :

5. Leave dentin moist after etching : Virtually all present day dentin adhesives bond to dentin that is moist. Systems containing acetone primers are well suited for bonding to wet surfaces. General rule dentin should not be dessicated. If dessicated or if dentin is dried to check enamel etch. It should be remoistened to improve bond strength. However pooled moisture should not be allowed to remain on tooth as excess

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water can dilute the material and reduce it effectiveness. A glistening hydrated surface is that referred appearance.

6. Apply and dry primers correctly : They should be applied in adequate quantity some require multiple coats or longer application times. Also solvents must be driven off completely with compressed air before the bonding agent or composite is applied. It is reported that adhesion may be compromised if acetone is not evaporated properly.

7. Do not over thin the bonding resin : Application of me resin bonding agent is the simplest steps in the 3 step bonding procedure. If it is excessively or aggressively air thinned, oxygen inhibition prevents complete polymerization and result sin low bonding strength. Thinning of bonding agent by a dry brush is better than thinning with air blast.

8. Use flexible restorative system : Flexible restorative system (Microfilled composites) or "Stress breaking liners" (filled bonding relines) may improve the quality of bonded restoration by compensation for stresses generated by polymerization shrinkage and tooth flexure.

9. Fill incrementally : Decrease overall polymerization shrinkage.

10. Delay finishing : Bond strength is increased after 24 hours so a brief delay in finishing may help preserve the integrity of delicate margins.

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11. Rebond margins : Because it is assumed that gap may occur in atleast some marginal areas. The margins are re-etched and sealed with special low viscosity resin.

12. Follow directions : Reputable manufacturers have specific protocols for application of their bonding systems.

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CONCLUSION
Advances in adhesive dental technology have radically changed restorative dentistry. The acid etch technique for enamel bonding led to the development of revolutionary restorative, preventive and esthetic treatment methods. More recently developments in resin/dentin bonding have moved adhesive dentistry at an even higher level. But it is necessary that these materials must be used properly to optimize their clinical performance.

Dentine adhesive systems have created a new era in the field of dentistry. Owing to its property of adherence to the tooth structure by both micromechanical and chemical means, it finds a wide range of application in various fields. It has lead to the most desired form of treatment needs, i.e. the conservation of tooth structure, which is the ultimate goal of conservative dentistry. Although, it was initially considered as a time consuming procedure, with the introduction of the sixth and seventh generation dentine adhesive system, the technique of dentine bonding has reduced to a single step. Finally, the responsibility lies in the hands of the clinician to make the appropriate use of its superior qualities. Yet, various clinical studies have to be carried out to prove its long term efficacy.

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REFERENCES
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12. Sturdevant C.M, Theodore M. Roberson, Herald O.Heymann, Edward J. Swift; the art science of operative dentistry. Fundamental concepts of enamel and dental adhesion 235-268. 13. John Gwinnett: Structure and composition of enamel: Operative dentistry supplement 5,1992. 10-17. 14. Garyson W. Marshall. : Dentin microstructure and characterization, Quintessence International: 1993(9) 606-617. 15. Edward J. Swift, Jorge Perdigio, Harold 0. Heymann: Bonding to enamel and dentin: A brief history and state of the art, Quintessence International 1995, vol 26. No.2. 16. Raymond L Bertolotti: Conditioning of the dentin substrate. Operative dentistry supplement 5, 1992. 17. M.J. Tyas, M.F Burrow. Adhesive restorative materials: a review; Australian Dental Journal 2004: 49 (30:112-121. 18. Gerarad Kugel, Marco Ferrari: The science of bonding: From first to sixth Generation; JADA 2000 vol 131, June 2000. 19. Dr. George Freedman and Dr Karl Leinfelder; 7th generation adhesive systems: Famdent practical dentistry handbook 2003 vol 3 April-June. 20. B. Van Meer beek, J. De Munck, Y. Yoshida, S. Inoure, P. Lambrechts. Adhesion to enamel and dentin. Current status and future challenges. Operative dentistry 2003, 28-3, 215-235. 21. Harold R Stanley; Pulpal consideration of adhesive materials; Operative dentistry supplement 5,1992. 22. J.R. Holtan, G.P. Nystron, R.A. Phelps, TB Anderson, W.S. Becker, Influence of different etchants and etching times on shear bond strength; Operative dentistry, 1995, 20,94-99. 23. Franklin R. Try, David. H.Pashley: Aggressiveness of contemporary selfetching systems: depth of penetration beyond dentin smear layer layers, Dental materials 17 (2001) 296-308. 178

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24. C.Prati, S. Chersoni, D.H. Pashley, Effect of removal of surface collagen fibrils on resin- dentin bonding, Dental materials 15 (1999) 323-331. 25. Johan Blomlof et al; Acid conditioning combined with single-component and two component dentin-bonding agents: Quintessence international 2001; 32:711-715. 26. PT Triolo et al; Shear bond strengths of composite to dentin using six dental adhesive systems: Operative dentistry 1995,20,46-50. 27. M Miyazaki, J A Platt, H. Onose, B.K. Moore; Influence of dentin primer application methods on dentin bond strength, Operative dentistry, 1996,21,167-172. 28. Slavoljub Zivkovic: Quality assessment of marginal sealing using seven dentin adhesive systems: Quintessence international 2000; 31:423-429. 29. Bruno T. Rosa, Jorge Perdigao, Bond Strengths of non-rinsing adhesives, Quintessence International 2000,31:353-358. 30. Y Shimada et al, Bond strength of two adhesive systems to primary and permanent enamel: Operative dentistry 2002,27,403-409. 31. Y. Shimada et al; Shear bond strength of current adhesive systems to enamel, dentin and dentin- enamel junction region; Operative dentistry, 2003, 28-5,585-590. 32. M. Tanumiharja, M.F. Burrow, MJ. Tyas: Microtensile bond strengths of seven dentin adhesive systems, Dental materials 16 (2000) 180-187. 33. GC Lopes et al; Dentin bonding effect of degree of mineralization and acid etching time: Operative dentistry, 2003, 28-4, 429-439. 34. Amer Abu-Hanna, Valeria U. Gordan and Ivar Mjor; The effect of variation in etching times on dentin bonding; General dentistry 2003, 2833. 35. George Eliads, Georgios Palaghias, George Vougiouklakis; Effect of acidic conditioners on dentin morphology, molecular composition and collagen conformation in situ, Dental materials 1997,13, 24-33.

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36. M Hashimoto et al: The effect of hybrid layer thickness on bond strength: demineralised dentin zone of the hybrid layer, Dental materials 16 (2000) 406-411. 37. Jorge Perdigao, J C. Ramos, Paul Lambrechts, In vitro interfacial relationship between human dentin and one-bottle dentin adhesives, Dental materials 1997:13, 218-227. 38. H. Li, M.F. Burrow, M.J. Tyas: Nanoleakage patterns of four dentin bonding systems, Dental materials 16(2000) 48-56. 39. David H Pashley, Franklin R Tay: Aggressiveness of contemporary self etching adhesives: etching effects on unground enamel: dental materials 17 (2001)277-283. 40. Frankenberger, J Perdigao, B T Rosa, M Lopes: No-bottle Vs multibottle dentin adhesives a Microtensile bond strength and morphological study: Dental materials 17 (2001) 373-380. 41. Richard B.T Price, Gordon C. Hall: In vitro comparison of 10-minute versus 24-hour shear bond strengths of six dentin-bonding systems, Quintessence Int 1999; 30:122-134. 42. Murat Turkun, Sebnem Turkun, Atakan Kalender: Effect of cavity disinfectants on the sealing ability of non-rinsing dentin- bonding resins; Quintessence international 204; 35; 469-476. 43. Hagay Slutzky, Shlono Matalon, Ervin I, Weiss; Antibacterial surface properties of polymerized single bottle bonding agents: Quintessence international 2004; 35; 275-279. 44. Esra Can Say et al; In vitro effect of cavity disinfectants or the bond strengths of dentin bonding systems; Quintessence International 2004; 35; 56-60. 45. Sigurdur O. Eiriksson et al; effects of Saliva contamination on resinresin bond strength, Dental materials (2004) 20, 37-44.

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46. Sigurdur O. Erriksson et al; Effects of blood contamination on resinresin bond strength, Dental materials (2004) 20, 184-190. 47. G. Schmalz, Z. Erguca and K-A. Hiller Effect of dentin on the antibacterial activity of dentin bonding agents: Journal of endodontics vol. 32, No5. 2004. 48. Arlin Kiremitci, Filiz Yalcin, Saadet Gokalp; Bonding to enamel and dentin using self-etching adhesive systems; Quintessence international 2004, 35: 367-370. 49. Maria Carolina Guilherme, Erhardf et al: In vitro influence of carisolv on shear bond strengths of dentin bonding agents: Quintessence international 2004; 35: 801-805. 50. Jorge Perdigao et al; Effect of calcium removal on dentin bond strengths; Quintessence International 2001; 32: 142-146. 51. Lorenzo Breschi et al; High resolution SEM evaluation of dentin etched with maleic and citric acid, Dental materials 18 (2002)26-35. 52. Atila Stephan Atac, Zafer C.Chehreli, and Burcin Sener; Antibacterial activity of fifth-generation dentin bonding system, Journal of endodontics Vol. 27, No 12, 2001. 53. G. Eliades, G. Vougiouklakis, G. Palaghias: Heterogeneous distributions of single-bottle adhesive monomers in the resin- dentin interdiffusion zone: dental materials 17 (2001) 277-283. 54. P.N.R. Pereira et al: Effect of intrinsic wetness and regional difference on dentin bond strengths, Dental materials 15 (1999) 46-53. 55. K. Miyasaka, N. Nakabayashi; Combination of EDTA conditioner and phenyl-P/HEMA self-etching primer for bonding to dentin, Dental materials 15 (1999) 153-157. 56. M. Miyazaki, K Tsubota, H Onose, K. Hinoura: Influence of adhesive application duration on dentin bond strength of single-application bonding systems; Operative dentistry 2002, 27,278-283. 181

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57. Sofia S.A. Oliveira et al, The influence of the dentin smear layer on adhesion, a self etching primer Vs a total-etch system Dental materials 19 (2003) 758-767. 58. Bora Ozturk and Fusun Ozer; Effect of NaOCl on bond strengths of bonding agents to pulp chamber lateral walls. Journal of endodontics vol. 30, no5, 2004.

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ABBREVIATIONS USED
bis-GMA BPDM DMA DMAEMA GPDM HAMA HEMA HPMA MA 10-MDP 4-MET 4-META MMA MMEM MPDM NPG NPG-GMA NTG-GMA PENTA Phenyl-P PMDM TBB TEG-DMA TEG-GMA UDMA Bisphenol glycidyl methacrylate Biphenyl dimethacrylate Dimethacrylate Dimethylaminoethyl methacrylate Glycerophosphoric acid dimethacrylate Hydroxyalkyl methacrylate 2- Hydroxyethyl methacrylate Hydroxypropyl methacrylate Methacrylate 10- Methacryloyloxy decyl dihydrogenphosphate 4- Methacryloxyethyl trimellitic acid 4- Methacryloxyethyl trimellitate anhydride Methyl methacrylate Mono- methacryloyloxyethylmaleate Methacryl propane diol monophosphate N- Phenylglycine N- Phenylglycine glycidyl methacrylate N- Tolylglycine glycidyl methacrylate Dipentaerythritol penta acrylate monophosphate 2- Methacryloxy ethyl phenyl hydrogen phosphate Pyromellitic acid diethylmethacrylate Tri-n-butyl borane Triethylene glycol dimethacrylate Triethylene glycol-glycidyl methacrylate Urethane dimethacrylate

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