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DENTIN BONDING AGENTS


         INDIAN DENTAL ACADEMY
      Leader in Continuing Dental Education

   
   
        www.indiandentalacademy.com
   
   ADHESION-        The mechanism that bonds two materials in intimate contact
    across an interface - Davidson (1996).




   Types of adhesion

   1.   Physical Bonding
   2.   Chemical Bonding
   3.   Mechanical Bonding


   1. PHYSICAL BONDING
    Physical bonding involves Vander walls forces or other electrostatic
    interactions that are relatively weak. It may be the only type of bonding if
    surfaces are smooth and chemically dissimilar.
   2. CHEMICAL BONDING
    Chemical bonding involves bonds between atoms formed across the interface
    from the adhesive to the adherend.          Because the materials are often
    dissimilar, the extent to which this bonding is possible is limited and the
    overall contribution to bond strength is normally quite low.
 
 3. MECHANICAL BONDING
Mechanical bonding is the result of an interface that involves undercuts and
  other irregularities that produce interlocking of the materials.
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   CHEMICAL ADHESION
                    Primary atomic bonds may be of three different
    types: 1) Ionic, 2) Covalent, and 3) Metallic.

    Ionic Bonds
   These primary bonds are of simple chemical type, resulting from
    the mutual attraction of positive and negative charges. The
    classic example being sodium chloride (Na+Cl-). Because the
    sodium atom contains one valance electron in its outer shell
    and the chlorine atom has 7 electrons in its outer shell, the
    transfer of the sodium valance electron to the chlorine atom
    results in the stable compound Νa+Cl−.
    Covalent Bonds
   In many chemical compounds, adjacent atoms share two
    valance electrons. The hydrogen molecule, H 2 is an example of
    covalent bonding. The single valence electron in each hydrogen
    atom is shared with the other combining atom, and the valence
    shells become stable.
    
   Metallic Bonds
   Certain atoms of a few crystals like gold can easily donate
    electrons from their shell and form a gas of free electrons. The
    contribution of free electrons to this could results in the
    formation www.indiandentalacademy.com
                of positive ions that can be neutralized by acquiring
    new valence electrons from adjacent atoms.
   Inter atomic Secondary Bonds
          In contrast with primary bonds, secondary bonds do not
    share electrons. Instead, variation among molecules or atomic
    groups induces polar forces that attract these molecules.
   a. Hydrogen Bonding
   In water molecule one oxygen atom is attached to two hydrogen
    atoms. These bonds are covalent because the oxygen and
    hydrogen atom share their electrons. As a consequence,
    electrons do not shield the protons of the hydrogen atoms
    pointing away from the oxygen atom efficiently. 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 water
    molecule mingles with other molecules the hydrogen portion of
    one molecule is attracted to the oxygen portion of its
    neighboring molecule, and hydrogen bridges are formed.
    
   Vander Walls 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 inter
    atomic forces are quite weak.
    
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ENAMEL ADHESION

   Buonocore- first proposed chemically treating enamel with acid solutions in
    1955. -H3PO4 creates micro-porosities in the enamel surface and enables
    bonding of resin to this surface via micro mechanical retention.

   Application time- 15 seconds

   The first bonding agents marketed for this technique were unfilled
    BISPHENOL A GLYCIDYL DIMETHACRYLATE (BIS GMA) resins.


   Enamel etching results in three different micro morphologic patterns.

   Type 1: The most common type involves preferential removal of the enamel
    prism cores, the prism peripheries remaining intact.
   Type 2: Etching pattern is the opposite of type 1 involving preferential
    removal of the peripheries with the cores being left intact.
   Type 3: Etching pattern contains areas, which resembles both type 1 and type
    2 along with some distinct areas where the pattern of etching appears to be
    unrelated to the enamel prism morphology.
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   Gwinnett     and    Buonocore    -use    of    lower    acid
    concentrations to prevent the formation of precipitates
    that could interfere with adhesion.
     Application of 50% phosphoric acid for 60 seconds
    -monocalcium phosphate monohydrate precipitate that
    can be rinsed off.
   concentrations below 27% may create a dicalcium
    phosphate monohydrate precipitate that cannot be easily
    removed and, consequently, may interface with adhesion.
        Other acids -maleic acid, citric acid, nitric acid and
    oxalic acid




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HYBRID LAYER
   HYBRID LAYER: (“adhesion interface”,
    “resin-dentin inter-diffusion zone”, inter
    penetration zone). is a “transitional zone of
    resin    reinforced    dentin    sandwiched
    between cured resin and the unaltered
    dentinal substrate” (Nakabayashi 1982).



   essential mechanism of adhesion -micro-
    mechanical & generated by monomer
    impregnation of the exposed collagen of
    demineralized superficial dentin.  
 
 
 




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REQUIREMENTS OF A DENTIN BONDING AGENT


Bond strength:
 Biocompatibility of the material:
Long-term durability of the bond:.
Polymerization’s shrinkage:




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   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.

        Oil contamination of hand piece of Air Syringe

        Surface roughness of tooth surfaces

        Mechanical undercuts in tooth preparations

        Fluoride contents of teeth

                  www.indiandentalacademy.com
   Presence of plaque, calculus, extrinsic stains / debris

   Presence of bases or liners on prepared teeth

   Tooth dehydration.

   Constituents of temporary cements




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FACTORS AFFECTING ADHESION TO MINERALIZED
  I. Factors related to theTISSUES
                            adherent
   1. Physicochemical properties of dentin that complicate dentin
    adhesion
   2. The dentin smear layer and dentin permeability.
   3. Transformed dentin surface structure due to physiological
    and pathological processes.
    
   II. Factors Related to The Restorative Resins
   i.           Physical properties of adhesives.
   ii.         Polymerization contraction of restorative resins.
   iii.       Young’s modulus of elasticity.
   iv.         Initial polymerization site
   v.           The relaxation of contraction stress by hygroscopic
   expansion.
   vi.           Thermal expansion coefficient and thermal
    conductivity.
   vii.       Transmission of stress across the composite dentin
    interface.
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CLASSIFICATION ACCORDING TO GENERATIONS
    FIRST GENERATION DENTIN BONDING AGENTS

    -Buonocore 1956
    a glycerophosphoric acid dimethacrylate – containing resin would
     bond to acid etched dentin.
    bond -due to the interaction of this bifunctional resin molecule
     with the calcium ions of hydroxyapatitie, but immersion in water
     would greatly reduce this bond. Nine years later Bowen tried
     using N-Phenyl glycine and glycidyl methacrylate (NPG-GMA),
     which is a bifunctional molecule or coupling agent. This molecule
     had one end bonding to the dentin while the other bonds to the
     composite resin. The bond strengths of these system was however
     1-3 Mpa. The NPG-GMA also bonded to the dentin by chelation
     with calcium on the tooth surface.


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Materials
1.Glycerophosphoricacid dimethacrylate.
   2.   Cyanocrylate
   3.   N-Phenyl Glycine – Glycidyl Methacrylate Eg., CERVIDENT

   No commercial products are available from this generation. Intraoral hydrolysis
    of GPDM, polymerization problems of Cyanocrylate and instability of NPG-
    GMA precluded their use.

   DISADVANTAGES:
   1.    Poor bond to dentin familiar amalgam type retentive cavities
   2.    Used only for small class III and class V restorations where there was
    adequate enamel to which to bond.
   3.    Postoperative sensitivity in attempted posterior occlusal restorations.

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SECOND GENERATION DENTIN BONDING AGENTS

 1970- halo phosphorous esters of unfilled resins
   bisphenol-A glycidyl methacrylate (Bis-GMA),
    hydroxyethyl methacrylate (HEMA).
   bonded to dentin by an ionic bond to calcium by chloro
    phosphate groups.

   These were weak bonds but were an improvement over the first
    generation systems.





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   MATERIALS
   a.         Clearfil – A reaction product of 2 – HEMA and a phenyl
    phosphate ester. (Phenyl – p) was utilized. 1 – 3 Mpa.
   b.         Scotch Bond – Halo phosphorous ester of BIS – GMA. 1 –3
    Mpa.
   c. Prisma Universal Bond – 6.5 to 7.0 Mpa.
   d,. Dentin Adhesit – An adhesive system that utilizes a isocyanate onomer
    and 5% NaOcl as a conditioner – solubilize the dentin collagen.
 
   DISADVANTAGES
   1. Weak bond to dentin
   2. Mechanical retention form was still necessary since bond strength alone
    was inadequate.
   3. Margins on dentin were problematic since the low dentinal bond
    strengths permitted extensive marginal microleakage.
   4.Restoration failure occurred most commonly due to hydrolytic
    decomposition.


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THIRD GENERATION DENTIN BONDING AGENTS
   Acid etching of the dentin partially removes or modifies the smear layer

   Acid opens the dentin tubules partially and increases their permeability

   acid must be rinsed completely before application of the primer.
    The primer -hydrophilic resin monomers like hydroxyethyl trimellitate anhydride
    and bisphenol dimethacrylate (BDPM).

   The primers contain a hydrophilic group that infiltrates the dentin and the
    hydrophobic group that adheres to the resin.

   The dentin primers usually used in these third generation systems may be 6%
    phosphate penta-acrylate (PENTA); 30 percent HEMA and 64% ethanol. After the
    application of the primer the unfilled resin adhesive is applied.

   In most of these systems, the phosphate primer modifies the smear layer by
    softening it after penetration and it cures forming a hard surface. The adhesive is
    then applied attaching the cured primer to the composite resin. However bonding
    was not very successful because the resins did not penetrate the smear layer and
    the smear layer was very weak.
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-        XR bonding system
   -   Gluma bonding system
   -   Tenure dentin bonding system
   -   4 META
   -   Phenyl-P
   -   Mirage bond
   Super bond



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FOURTH GENERATION DENTIN BONDING AGENTS
   complete removal of the smear layer




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FIFTH GENERATION DENTIN BONDING AGENTS
   reducing the bonding steps

   The fifth generation consists of two different types of adhesive
    materials.
   -     The so called “one bottle system”.
   -     Self etching primer bonding systems.
   Indications:
   •           Direct composite restoration.
   •           Indirect bonding.
   •           Root desensitization
    



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   Chemistry:
   •           HEMA, BisGMA, dimethacrylates, and patented polyalkenoic
    acid copolymer.
   •         Technique:
   •          Etch enamel and dentin for 15 seconds.
   •          Using a fully saturated brush tip, apply 2 consecutive coats of
    Single Bond.
   •          Dry for 2-5 seconds.
   Light-Cure for 10 seconds
     Water and ethanol




                   www.indiandentalacademy.com
SIXTH  GENERATION                          DENTIN   BONDING
AGENTS
   proper bond to enamel and dentin
    used only one solution.
   1.   Compartment 1 : Containing
    methacrylate phosphoric acid esters,
    photo initiators and stabilizers.
   2. Compartment 2 : contains water,
    complex fluoride and stabilizers.
   3.   Compartment 3 has a micro
    brush.




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CLASSIFICATIONS                                                     OF
MODERN ADHESIVES
     
    Classified based on number of clinical application steps and
     interaction with tooth substrate.
     
1.   Total etch adhesives
    [E + P,A]                     a) Two step etch adhesives
    [E + P + A]                   b) Three step etch adhesives
2.   Self etch adhesives
    [E + P, A]                        a)    Two step self etch
     adhesives
    [E + P + A] = [C,P,A]       b) One Step self etch adhesives
     


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Dentin boning agents /certified fixed orthodontic courses by Indian dental academy

  • 1. DENTIN BONDING AGENTS INDIAN DENTAL ACADEMY Leader in Continuing Dental Education     www.indiandentalacademy.com  
  • 2. ADHESION- The mechanism that bonds two materials in intimate contact across an interface - Davidson (1996).  Types of adhesion  1. Physical Bonding  2. Chemical Bonding  3. Mechanical Bonding  1. PHYSICAL BONDING Physical bonding involves Vander walls forces or other electrostatic interactions that are relatively weak. It may be the only type of bonding if surfaces are smooth and chemically dissimilar.  2. CHEMICAL BONDING Chemical bonding involves bonds between atoms formed across the interface from the adhesive to the adherend. Because the materials are often dissimilar, the extent to which this bonding is possible is limited and the overall contribution to bond strength is normally quite low.    3. MECHANICAL BONDING Mechanical bonding is the result of an interface that involves undercuts and other irregularities that produce interlocking of the materials. www.indiandentalacademy.com  
  • 3. CHEMICAL ADHESION  Primary atomic bonds may be of three different types: 1) Ionic, 2) Covalent, and 3) Metallic.  Ionic Bonds  These primary bonds are of simple chemical type, resulting from the mutual attraction of positive and negative charges. The classic example being sodium chloride (Na+Cl-). Because the sodium atom contains one valance electron in its outer shell and the chlorine atom has 7 electrons in its outer shell, the transfer of the sodium valance electron to the chlorine atom results in the stable compound Νa+Cl−.  Covalent Bonds  In many chemical compounds, adjacent atoms share two valance electrons. The hydrogen molecule, H 2 is an example of covalent bonding. The single valence electron in each hydrogen atom is shared with the other combining atom, and the valence shells become stable.     Metallic Bonds  Certain atoms of a few crystals like gold can easily donate electrons from their shell and form a gas of free electrons. The contribution of free electrons to this could results in the formation www.indiandentalacademy.com of positive ions that can be neutralized by acquiring new valence electrons from adjacent atoms.
  • 4. Inter atomic Secondary Bonds  In contrast with primary bonds, secondary bonds do not share electrons. Instead, variation among molecules or atomic groups induces polar forces that attract these molecules.  a. Hydrogen Bonding  In water molecule one oxygen atom is attached to two hydrogen atoms. These bonds are covalent because the oxygen and hydrogen atom share their electrons. As a consequence, electrons do not shield the protons of the hydrogen atoms pointing away from the oxygen atom efficiently. 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 water molecule mingles with other molecules the hydrogen portion of one molecule is attracted to the oxygen portion of its neighboring molecule, and hydrogen bridges are formed.     Vander Walls 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 inter atomic forces are quite weak.    www.indiandentalacademy.com
  • 5. ENAMEL ADHESION  Buonocore- first proposed chemically treating enamel with acid solutions in 1955. -H3PO4 creates micro-porosities in the enamel surface and enables bonding of resin to this surface via micro mechanical retention.  Application time- 15 seconds  The first bonding agents marketed for this technique were unfilled BISPHENOL A GLYCIDYL DIMETHACRYLATE (BIS GMA) resins.  Enamel etching results in three different micro morphologic patterns.  Type 1: The most common type involves preferential removal of the enamel prism cores, the prism peripheries remaining intact.  Type 2: Etching pattern is the opposite of type 1 involving preferential removal of the peripheries with the cores being left intact.  Type 3: Etching pattern contains areas, which resembles both type 1 and type 2 along with some distinct areas where the pattern of etching appears to be unrelated to the enamel prism morphology. www.indiandentalacademy.com
  • 6. Gwinnett and Buonocore -use of lower acid concentrations to prevent the formation of precipitates that could interfere with adhesion.  Application of 50% phosphoric acid for 60 seconds -monocalcium phosphate monohydrate precipitate that can be rinsed off.  concentrations below 27% may create a dicalcium phosphate monohydrate precipitate that cannot be easily removed and, consequently, may interface with adhesion.  Other acids -maleic acid, citric acid, nitric acid and oxalic acid www.indiandentalacademy.com
  • 7. HYBRID LAYER  HYBRID LAYER: (“adhesion interface”, “resin-dentin inter-diffusion zone”, inter penetration zone). is a “transitional zone of resin reinforced dentin sandwiched between cured resin and the unaltered dentinal substrate” (Nakabayashi 1982).  essential mechanism of adhesion -micro- mechanical & generated by monomer impregnation of the exposed collagen of demineralized superficial dentin.         www.indiandentalacademy.com
  • 8. REQUIREMENTS OF A DENTIN BONDING AGENT Bond strength: Biocompatibility of the material: Long-term durability of the bond:. Polymerization’s shrinkage: www.indiandentalacademy.com
  • 9. 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. Oil contamination of hand piece of Air Syringe Surface roughness of tooth surfaces Mechanical undercuts in tooth preparations Fluoride contents of teeth www.indiandentalacademy.com
  • 10. Presence of plaque, calculus, extrinsic stains / debris  Presence of bases or liners on prepared teeth  Tooth dehydration.  Constituents of temporary cements www.indiandentalacademy.com
  • 11. FACTORS AFFECTING ADHESION TO MINERALIZED  I. Factors related to theTISSUES adherent  1. Physicochemical properties of dentin that complicate dentin adhesion  2. The dentin smear layer and dentin permeability.  3. Transformed dentin surface structure due to physiological and pathological processes.     II. Factors Related to The Restorative Resins  i. Physical properties of adhesives.  ii. Polymerization contraction of restorative resins.  iii. Young’s modulus of elasticity.  iv. Initial polymerization site  v. The relaxation of contraction stress by hygroscopic  expansion.  vi. Thermal expansion coefficient and thermal conductivity.  vii. Transmission of stress across the composite dentin interface. www.indiandentalacademy.com
  • 12. CLASSIFICATION ACCORDING TO GENERATIONS  FIRST GENERATION DENTIN BONDING AGENTS  -Buonocore 1956  a glycerophosphoric acid dimethacrylate – containing resin would bond to acid etched dentin.  bond -due to the interaction of this bifunctional resin molecule with the calcium ions of hydroxyapatitie, but immersion in water would greatly reduce this bond. Nine years later Bowen tried using N-Phenyl glycine and glycidyl methacrylate (NPG-GMA), which is a bifunctional molecule or coupling agent. This molecule had one end bonding to the dentin while the other bonds to the composite resin. The bond strengths of these system was however 1-3 Mpa. The NPG-GMA also bonded to the dentin by chelation with calcium on the tooth surface. www.indiandentalacademy.com
  • 13. Materials 1.Glycerophosphoricacid dimethacrylate.  2. Cyanocrylate  3. N-Phenyl Glycine – Glycidyl Methacrylate Eg., CERVIDENT  No commercial products are available from this generation. Intraoral hydrolysis of GPDM, polymerization problems of Cyanocrylate and instability of NPG- GMA precluded their use.  DISADVANTAGES:  1. Poor bond to dentin familiar amalgam type retentive cavities  2. Used only for small class III and class V restorations where there was adequate enamel to which to bond.  3. Postoperative sensitivity in attempted posterior occlusal restorations. www.indiandentalacademy.com
  • 14. SECOND GENERATION DENTIN BONDING AGENTS  1970- halo phosphorous esters of unfilled resins  bisphenol-A glycidyl methacrylate (Bis-GMA),  hydroxyethyl methacrylate (HEMA).  bonded to dentin by an ionic bond to calcium by chloro phosphate groups.  These were weak bonds but were an improvement over the first generation systems.  www.indiandentalacademy.com
  • 15. MATERIALS  a. Clearfil – A reaction product of 2 – HEMA and a phenyl phosphate ester. (Phenyl – p) was utilized. 1 – 3 Mpa.  b. Scotch Bond – Halo phosphorous ester of BIS – GMA. 1 –3 Mpa.  c. Prisma Universal Bond – 6.5 to 7.0 Mpa.  d,. Dentin Adhesit – An adhesive system that utilizes a isocyanate onomer and 5% NaOcl as a conditioner – solubilize the dentin collagen.    DISADVANTAGES  1. Weak bond to dentin  2. Mechanical retention form was still necessary since bond strength alone was inadequate.  3. Margins on dentin were problematic since the low dentinal bond strengths permitted extensive marginal microleakage.  4.Restoration failure occurred most commonly due to hydrolytic decomposition. www.indiandentalacademy.com
  • 16. THIRD GENERATION DENTIN BONDING AGENTS  Acid etching of the dentin partially removes or modifies the smear layer  Acid opens the dentin tubules partially and increases their permeability  acid must be rinsed completely before application of the primer.  The primer -hydrophilic resin monomers like hydroxyethyl trimellitate anhydride and bisphenol dimethacrylate (BDPM).  The primers contain a hydrophilic group that infiltrates the dentin and the hydrophobic group that adheres to the resin.  The dentin primers usually used in these third generation systems may be 6% phosphate penta-acrylate (PENTA); 30 percent HEMA and 64% ethanol. After the application of the primer the unfilled resin adhesive is applied.  In most of these systems, the phosphate primer modifies the smear layer by softening it after penetration and it cures forming a hard surface. The adhesive is then applied attaching the cured primer to the composite resin. However bonding was not very successful because the resins did not penetrate the smear layer and the smear layer was very weak. www.indiandentalacademy.com
  • 17. - XR bonding system  - Gluma bonding system  - Tenure dentin bonding system  - 4 META  - Phenyl-P  - Mirage bond  Super bond www.indiandentalacademy.com
  • 18. FOURTH GENERATION DENTIN BONDING AGENTS  complete removal of the smear layer www.indiandentalacademy.com
  • 19. FIFTH GENERATION DENTIN BONDING AGENTS  reducing the bonding steps  The fifth generation consists of two different types of adhesive materials.  - The so called “one bottle system”.  - Self etching primer bonding systems.  Indications:  • Direct composite restoration.  • Indirect bonding.  • Root desensitization    www.indiandentalacademy.com
  • 20. Chemistry:  • HEMA, BisGMA, dimethacrylates, and patented polyalkenoic acid copolymer.  • Technique:  • Etch enamel and dentin for 15 seconds.  • Using a fully saturated brush tip, apply 2 consecutive coats of Single Bond.  • Dry for 2-5 seconds.  Light-Cure for 10 seconds  Water and ethanol www.indiandentalacademy.com
  • 21. SIXTH GENERATION DENTIN BONDING AGENTS  proper bond to enamel and dentin used only one solution.  1. Compartment 1 : Containing methacrylate phosphoric acid esters, photo initiators and stabilizers.  2. Compartment 2 : contains water, complex fluoride and stabilizers.  3. Compartment 3 has a micro brush. www.indiandentalacademy.com
  • 22. CLASSIFICATIONS OF MODERN ADHESIVES     Classified based on number of clinical application steps and interaction with tooth substrate.    1. Total etch adhesives  [E + P,A] a) Two step etch adhesives  [E + P + A] b) Three step etch adhesives 2. Self etch adhesives  [E + P, A] a) Two step self etch adhesives  [E + P + A] = [C,P,A] b) One Step self etch adhesives    www.indiandentalacademy.com
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