DENTIN

HYBRIDIZATION
 Terminology
Adhesion or bonding- The forces or energies
between atoms or molecules at an interface that
hold two phases together.
Adherend- The surface or substrate that is
adhered.
Adhesive/ adherent/ bonding agent/ adhesive
system- A material that can join substances
together, resist separation, and transmit loads
across the bond.
 Terminology
Adhesive failure- The bond that fails at the
interface between the two substrates.
Cohesive failure- The bond fails with in one of
the substrates, but not at the interface.
 Potential Advantages
Microleakage reduction.
Postoperative sensitivity reduction.
Marginal staining reduction.
Reinforce weakened tooth structure.
Repair deteriorating or debonded restorations.
without additional loss of tooth structure.
Expands range of esthetic possibilities.
Minimizes removal of sound tooth structure.
 Indications
Replace carious and fractured tooth structure.
Fill erosion or abrasion defects in cervical
areas.
Correct unaesthetic shapes, positions,
dimensions, or shades. .
Cement crowns.
 Indications
Bond orthodontic brackets.
Treat dentinal hypersensitivity.
Repair of esthetic restorations.
Pit and fissure sealants.
Core build up foundations.
Post cementation.
Cementation of adhesive resin bridges.
Veneers.
Evolution of Bonding Adhesives
• 1960s and 1970s First and Second Generation

• Did not recommend dentin etching.

• Relied on adhesion to smear layer.
• Weak bond strength.
• 1980s Third Generation

• Acid etching of dentin.

• Separate primer.
• Increased bond strength.
 • Early 1990s Fourth Generation

• “Hybrid” layer of dentin and collagen.

• Better dentin seal.
• Concept of “wet bonding” introduced.
• Technique sensitive.
 • Mid 1990s Fifth Generation

• Combined primer and adhesive in one bottle.

• Maintained high bond strengths.
 • Late 1990s, Early 2000s Sixth Generation

• “Self-etching” primers.
• Reduced incidience of post-treatment sensitivity.
• Bond strengths lower than fourth- and fifth-
generations.
 • Late 2002 Seventh Generation

• “All-in-One”.
• Combines etching, priming and bonding.
• Single solution.
• Good bond strength and margin sealing.
• Van Meerbeek classification:

• Etch & Rinse adhesive system.

• Self etch adhesive system.
Classification of Current Adhesives

3 steps

primer
adhesive

GOLD
STANDAR
D
Total-Etch Adhesives Self-Etch Adhesives

Van Meerbeek et al. 2001 Adhesives and cements to promote preservation dentistry
Operative Dentistry Suppl. 6 119-144
 Total Etch (3 Steps)
• Total etch
– Smear layer removed
– Surface dentin
demineralized
• Primer (hydrophilic)
Primer
– Hybrid layer
• Adhesive (hydrophobic)
Adhesive
• Composite placementLimitations: resin
Too many steps
dentin moisture variable
Sensitivity reported
Classification of Current Adhesives

3 steps 2 steps

primer
adhesive Primer/
adhesive

GOLD
STANDAR
D Adhesives
Total-Etch Self-Etch Adhesives

Van Meerbeek et al. 2001 Adhesives and cements to promote preservation dentistry
Operative Dentistry Suppl. 6 119-144
Total Etch (2 steps)
• Total etch
– Smear layer removed
– Surface dentin
demineralized
• Primer/Adhesive
– Hydrophilic/hydrophobic
mixtures
– Hybrid layer
• Composite placement Primer/
Limitations: Adhesive
combo
dentin moisture variable
Sensitivity reported
Classification of Current Adhesives

3 steps 2 steps 2 steps 1 steps

primer Self-etch
adhesive Primer/ primer Self-etch
adhesive adhesive primer/
adhesive
GOLD
STANDAR
D Adhesives
Total-Etch Self-Etch Adhesives

Van Meerbeek et al. 2001 Adhesives and cements to promote preservation dentistry
Operative Dentistry Suppl. 6 119-144
 Self-Etching Adhesives
• Self Etching Primers
– Smear layer modified
– Surface dentin
demineralized
– Hybrid layer developed Etchant/
Primer/
Etchant/
Adhesive
• Adhesive Primer/
combo
Adhesive
• Composite placement combo
Lower sensitivity reported
Concerns about stability
Seal does not appear to be as good
 In etch & rinse adhesives;
Acidic solutions (i.e. 35%
phosphoric acid) are used to
demineralize the smear layer and the
underlying intact dentin to expose
the collagen network.
 Etch & rinse adhesive
• The incomplete impregnation of the exposed
collagen space by subsequent application of
bonding resin is due to imperfect resin monomer
infiltration. The discrepancy between the depth
of the collagen layer and resin infiltration creates
an exposed demineralized dentin zone under the
hybrid layer.

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 Etch & rinse adhesive
• The exposed collagen fibrils here underwent
structural deterioration due to hydrolytic
degradation, resulting in decreasing bond
strength.

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 Etch & rinse adhesive
• Also for etch-and-rinse systems, there are many
factors that affect sensitivity including: the
surface wetness of the acid etched dentin, acid
etching time, light irradiation time, thickness of
the bonding resin layer, consecutive coating
methods, and the method of air blowing for the
adhesive-coated dentin surface.

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 Self etch adhesives
• These problems can be overcomed with self etch
adhesives as the surface wetness of acid-etched
dentin can be theoretically eliminated because
there is no water rinsing or dentin moisture
retention. The fewer application steps of self-
etching adhesives are thought to require less
skill by the operator.
 Self etch adhesives
• Also for self-etching adhesives, the smear
layer is partially enveloped into the bond
structure, providing simultaneous
demineralization and infiltration during the
application of the acidic monomer, resulting
in formation of a hybrid layer.

• The incorporation of smear layer in the

hybrid layer result in less dentin sensitivity.

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 Dentine bonding processes
Conditioners such as acids or a calcium
chelator (EDTA) chemically alters the dentin
surface with the objective to remove or alter
the smear layer, demineralize the dentin
surface, and expose the microporous scaffold
of collagen fibrils.
The smear layer is defined as any debris,
calcific in nature, produced by reduction
or instrumentation of dentin, enamel,
cementum, or as a contaminant that
precludes interaction with the
underlying pure tooth tissue.

The smear layer may reduce dentin

permeability by as much as 86%.
• Scanning electron
micrograph of a smear
plug blocking the
entrance of a dentinal
tubule.
How to deal with the smear layer?
• Preservation: phosphonated esters of
bis-GMA.
• Modification: self etch adhesives
• Removal: basis of most modern DBAs,
often known as total etch, using
phosphoric acid then amphiphilic
monomer (HEMA) creates hybrid layer+
resin tags.
 Dentine bonding processes
• Phosphoric acid etch for 15s gives
– Smear layer removal
– Hydroxyapatite dissolution
• Drying causes
– Collagen collapse

Cross banded
• Priming gives

– Collagen rehydration
Hydrophilic wetting agents Primer does not plug
tubules
Compatible with dentin and resin
Bifunctional molecule
• Monomer penetration into tubules and
collagen provides
– Micromechanical adhesion on polymerization
– Tubule sealing
 Hybrid layer and resin tags

Cross section SEM

composite Resin must flow into•

Collagen – hybrid layer•

Tubules – branches especially•

dentine important for high bond strength
Dentin-Bonding
Interface
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WHY BONDING TO DENTIN
IS A CHALLENGE?
Challenges in dentin bonding

Changes in dentin
Smear layer
Internal and external dentinal wetness
Wetting of the adhesive
Polymerization contraction of restorative
resins
 Changes in dentin
Adhesion to enamel is much easier to
achieve than is adhesion to dentin.
Enamel has a homogenous structure
which contains primarily hydroxyapatite,
which has a high surface-free energy,
while dentin is composed of two distinct
substrates, hydroxyapatite and collagen
which has a low surface free energy.
 Compositon of Enamel and Dentin by
Weight and Volume
100 95
90 86
80 70
70
60 50 Inorganic
50 Organic
40 Water
30 2525
18
20 12 12
10 4 1 2
0
Enamel Dentin Enamel Dentin
Wt % Wt % Vol % Vol %
 BONDING TO MOIST VERSUS DRY DENTIN
SURFACES
• Complete drying of vital dentin is difficult to
achieve clinically.
• Most new adhesives combine hydrophilic and
hydrophobic monomers in the same bottle,
dissolved in an organic solvent such as ethanol
or acetone.
• Wet-bonding technique prevents the spatial
alterations (i.e. collagen collapse).
 BONDING TO MOIST VERSUS
DRY DENTIN SURFACES

• Excess water after rinsing the etching gel can be

removed with a damp cotton pellet, a disposable
brush, or a tissue paper without adversely affecting
bond strengths. Air drying is not recommended,

• The wet bonding technique enhance bond strengths

because water preserves the porosity of collagen
network available for monomer interdiffusion.

Kanca J 1996
Collapse of etched dentin by air-drying.
 Sclerotic dentin
• Sclerotic dentin is hypermineralized and
impermeable.
• The tubules are filled with acid resistant
calcium phosphate crystals.
• Resin tags are short, blunt and funnel shaped
tags containing a core of mineral crystals.
• Self etching primers are ineffective on this
substrate.
 HOW TO BOND TO
SCLEROTIC DENTIN?

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• Extend the etching time.

• Extend tha cavity preparation beyond the

caries affected dentin to normal relatively
permeable dentin.

• Use of glass ionomer based adhesives to

benefit from the chemical adhesion potential
to this hypermineralized dentin.
 Internal and external
dentin wetness
Internal dentinal wetness occurs with
smear layer removal.

External dentinal wetness may occur

with humidity.
Dry versus moist dentin bonding
• Drying of acid etched dentin allows the
collagen fibers to collapse into a dense layer
that resists penetration of the primer resins.

• This means that the desired effect of etching

(increased permeability) is thus potentially
minimized.
• If too much water is present, the adhesive resin
may not be able to compete with water for the
collagen fiber surface, therby leaving voids.

• So it is recommended to keep the demineralized

dentin wet or visibly moist.

• The wet and dry bonding can be controlled by the

type of solvent utilized in the primer (acetone,
water or alcohol based primer).
Changes in dentin
Smear layer
Internal and external dentinal wetness
Wetting of the adhesive
Polymerization contraction of restorative
resins
The adhesive system must
sufficiently wet the solid surface,
have a viscosity that is low enough to
penetrate the microporosities, and
be able to displace air and moisture
during the bonding process.
.Wetting of a surface by a liquid is
characterized by the contact angle of a
droplet placed on the surface.
.Sufficient wetting of the adhesive will
only occur if its surface tension is less
than the surface energy of the
adherend.
Co n t ac t A n g le




 > 90o  < 90o

Su b s t rat e
 Challenges in dentin bonding

Changes in dentin
Smear layer
Internal and external dentinal wetness
Wetting of the adhesive
Polymerization contraction of restorative
resins
 Polymerization shrinkage
• Polymerization shrinkage of dental resin
composites is occur due to the fact that
monomer molecules are converted into a
polymer network.
• Polymerization shrinkage creates contraction
stresses in CR, internal stress and deformation
in tooth structure → resulting in poor
marginal adaptation, post operative pain, and
recurrent caries.
 Factors Responsible for Polymerization Shrinkage Stress

1. ↑ Filler content: ↓shrinkage ↑wear

resistance
2. Degree of conversion: reduction in final
degree of conversion lower the shrinkage
and contraction stress and lower the
mechanical properties of the material
3. Elastic Modulus: the higher the modulus the
higher the contraction stress
 Factors Responsible for Polymerization
Shrinkage Stress
4. Nature of the monomer: The monomer composition was
found to influence the rate of polymerization.
HEMA ↑rate of polymerization shrinkage
5. C-factor : An increased C-value leads to a decreased flow
capacity which causes a higher rate of shrinkage stress
development.
6. Water Sorption
→ hygroscopic expansion which compensate for
shrinkage.
→ deterioration of mechanical properties and
alteration of color stability
 Management of Shrinkage Stress
• Material modification to compensate
polymerization shrinkage
• Improvement in clinical application techniques.
• Improvement of adhesive system
• Modification in light curing techniques
 Material modification to compensate polymerization
shrinkage

• Decreasing the relative concentration of

resin phase
 Decreasing the relative concentration of resin phase

1. Nanofillers
2. Packable: high filler loaded
3. Compomer
4. Ceromers (Ceramic Optimized Polymers)
5. Ormocers Organically modified ceramics
6. Low shrinkage composite
7. Flowable Composites: hybrid with reduced filler
content.
8. Using indirect composite restorations
9. Glass-ionomer Cement
10. Light-curing and Self-curing Composites
 FACTORS THAT AFFECT LIGHT CURING OF COMPOSITE

• Time, intensity, temperature, light distance,

resin thickness, tooth structure, composite
shade, filler type, accelerator quantity, heat,
and room light.
Improvement in clinical application techniques

Placement Technique
Three main factors correspond to reduce
shrinkage stress: use of
• Small volume of material,
• Lower cavity configuration factor
• Minimal contact with the opposing cavity
walls during polymerization
Condon JR 2000
 Improvement in clinical application techniques

• Placement Technique
• Incremental application techniques:
Facio-lingual layering (vertical)
Gengivo-occlusal layering (horizontal)
Three-site Technique
• Wedge-shape Layering (oblique)
• Successive Cusp Build-up Technique
• Bulk Technique
• Centripetal Build-up
 Improvement of adhesive system

• Total etch adhesives.

• Self etch technique.
• Glass ionomer based adhesives.
 Modification in light curing techniques

• 1. Continuous curing techniques

• 2. Discontinuous curing techniques
 Modification in light curing techniques

1. Continuous curing techniques

• Uniform continuous cure: light of constant intensity is
applied to a composite for a specific period of time.
• Step cure; composite is first cured at low energy, and
then stepped up to high energy, each for a set duration.
• Ramp cure: light is initially applied at low intensity and
gradually increased over time to high intensity.
• High-energy pulse cure: uses a brief (10 second) pulse of
extremely high energy (1000–2800 mW per cm2).
 Modification in light curing techniques
2. Discontinuous curing techniques
soft-cure technique, a low intensity or soft light is used to
initiate a slow polymerization that allows a composite resin to
flow from the free (unbound) restoration surface toward the
(bound) tooth structure.

• Pulse-delay cure
A single pulse of light is applied to a restoration, followed by a
pause and then by a second pulse cure of greater intensity
and longer duration. It is best thought of as an interrupted
step increase
 HOW TO IMPROVE
BONDING TO DENTIN?

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The hydrolysis of bared collagen greatly affects the long-
term bond stability of total-etch adhesive systems, the
reason of this collagen hydrolysis may be the effects of
saliva or oral bacteria. Also self-destruction of Collagen
has been found in the human dentin matrix by the
matrix metalloproteinase enzymes.
• Enhancement of the dentin bonding can be
done either by improving the physical
properties of the bonding agent, or by
modifying the dentin substrate to act as a
foundation for the subsequent applied
adhesive restoration.
Modification of the dentin substrate can be
carried out through:
 The use of proteolytic agents on acid etched dentin,
known as dentin deproteinization.

 The use of cross linking agents.

Both aimed to eliminate the negative consequences

related to the organic content of the dentinal substrate.

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 DEPROTEINIZATION
• The use of deproteinizing solutions (NaOCl or
collagenase) alters dentin surface
ultramorphology by dissolving the exposed
collagen fibrils. Their action promotes the
exposure of a lateral runway network and
amplifies the dentin tubules, rendering dentin
similar to etched enamel, which is a favorable
characteristic for adhesion. This surface has
shown multiple irregularities, with good
mechanical retention of the adhesive in modified
dentin substratum (Gisele et al, 2006).
• The dissolution of organic tissues by sodium
hypochlorite solutions is based on the action of
chloride over the proteins, forming chloramines,
which are soluble in water. Thus it alters the
configuration or removes the organic
components of dentin; especially, the collagen
fibrils.
Pratic et al, attributed the improvement
in the bond strength to the formation of
a reverse hybrid layer.

They found that collagen fibrils were

completely removed from the acid
etched surface by NaOCl treatment. The
diameter and size of the dentinal tubules
and the number of the lateral branches
of the tubules were increased following
NaOCl treatment and also the resin tags
were larger.
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 Cross linkers
Recently new approaches have been
introduced for reinforcement of the
collagen fibrils including the application of
crosslinking agent, which is claimed to
improve the mechanical stability and
reduce the biodegradation rates of
collagen network .
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 Examples of crosslinking agents:

Grape seed extract

Chlorohexidine
Gluteraldehyde

Grape seed extract as a crosslinking agent has

been reported to be a low toxicity compound that
can induce exogenous crosslinks. It has the ability
to interact with collagen and affect the mechanical
properties of dentin. It is composed mainly of
proanthocyanidin, a naturally occurring
crosslinking agent.
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 Four mechanisms for interaction between
proanthocyanidin and proteins have been
postulated including covalent interactions, ionic

interactions, hydrogen bonding interactions,

or hydrophobic interactions. The primary
mechanism of collagen stabilization with
proanthocyanidin is the formation of hydrogen
bonding between the protein amide carbonyl and
the phenolic hydroxyl.
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 It has been reported that pretreating the
demineralized dentin by PA-based agents was
effective to increase the mechanical properties
of dentin matrix, enhance the resin–dentin
microtensile bond strength (mTBS) and
decrease the enzymatic degradation compared
to the non-treated dentin.

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Thank you