Enamel and Dentin Adhesives

Kraig S. Vandewalle, Col, USAF, DC

Official Disclaimer
The opinions expressed in this presentation are those of the author and do not necessarily reflect the official position of the US Air Force or the Department of Defense (DOD). Devices or materials appearing in this presentation are used as examples of currently available products/technologies and do not imply an endorsement by the author and/or the USAF/DOD.

Overview
Principles of adhesion Principles of bonding Historical development Classifications Features Conclusions

Advantages of Adhesion
Help offset polymerization shrinkage
reduce marginal leakage
staining sensitivity caries

Adhesion
conservation of tooth structure internal splinting

Esthetic restorations

Indications for Adhesion

Direct resin composite restorations
caries, fractures, reshaping, masking

Bond all-ceramic restorations

veneers, inlays, onlays, crowns

Bond amalgam Resin-retained fixed-partial dentures

Indications for Adhesion

Pit and fissure sealants Orthodontic brackets Treat dentinal hypersensitivity Core build-ups Repair fractured porcelain and composite

Basic Mechanism of Adhesion

(resin-based) Exchange process
replacement of minerals
from hard tissue

by resin monomers
micromechanically interlocked

Primarily mechanical
retentive interlocking

Variations in Tooth Structure

Enamel
more predictable bonding
more homogeneous structure higher inorganic content higher surface energy

Dentin
less predictable bonding
higher variability higher organic content
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Enamel Composition
Primarily inorganic
hydroxyapatite
By volume

Organic 2% Water 12%

Inorganic 86% Van Meerbeek in: Summitt, Fund Oper Dent 2001

Enamel Bonding
Developed by Buonocore-1955 Etching
various acids
traditionally phosphoric acid

creates micropores
5 50 microns deep

increases surface energy increases wettability

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Surface Wetting
Tooth surface contamination
saliva, smear layer

Clean surface
increase surface energy decrease contact angle
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Enamel Bonding
Low-viscosity monomers
examples
Bis-GMA UDMA TEGDMA HEMA

Predictably high bond strengths

> 20 MPa
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Dentin Structure
Dentin composition Dentinal tubules Changes in dentin structure Smear layer Dentinal wetness

Dentin Composition
Inorganic 50% Organic 25%

By volume

Water 25%

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Dentinal Tubules
Radiate from pulp Largest near pulp
2.5 microns at pulp 0.8 microns at DEJ

Concentrated near pulp

45,000/mm2 at pulp 20,000/mm2 at DEJ
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Tubule Composition
Peritubular dentin
surrounds tubule hypermineralized

Intertubular dentin
between tubules less mineralized

Odontoblastic process Dentinal fluid

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Changes in Dentin Structure

Sclerotic
normal aging abrasion erosion

Hypermineralization Less receptive to bonding

Reparative
caries dental procedures
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Smear Layer
Produced by instrumentation Composition
cut dentin debris bacteria

Reduces dentin permeability

86%
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Smear Layer
Thickness
0.5 - 5.0 microns

Will not wash off Weak bond to tooth

2 3 MPa

Very soluble
weak acids
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Dentinal Wetness
Increases
dentinal depth removal of smear layer

Historically, more difficult to bond

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Dentin Bonding
Development
seven generations chronologic

Classification

Van Meerbeek in: Summitt, Fund Oper Dent 2001

First Generation
(1950-1970s) Hydrophobic monomers Very low bond strengths
2 to 3 MPa

First commercial dentinal adhesive

Cervident - SS White (1965)

claimed chemical bond to calcium

retention only 50% at 6 months

Class 5
Harris, J Prosthet Dent 1974

Second Generation
(late 70s to mid 80s) Phosphorous-ester monomers

enhanced surface wetting claimed chemical bond to calcium smear layer predominately intact

fear of etching dentin

Low bond strengths

5 to 6 MPa

Retention 70% at 1 year

Class 5
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Third Generation
(mid-80s) Mechanism of action
mildly acidic hydrophilic monomer modified/altered smear layer

Moderate bond strengths Improved short / long term success

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Fourth Generation
(early 1990s)
Multi-step
condition dentin
remove smear layer

primer adhesive

High bond strengths

Retention 98 to 100 % at 3 yrs
Class 5
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Fifth Generation
(late 1990s)
Attempt to simplify
reduce number of bottles
combined primer and adhesive

High bond strengths

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Sixth Generation
(late 1990s) Combined conditioner and primer
moderate bond strengths

Combined conditioner, primer and adhesive

lower bond strengths

Van Meerbeek, Oper Dent 2003 Click here for abstract

Seventh Generation
(most recent) All-in-one adhesives
combined conditioner, primer and adhesive one-step

No mixing Low bond strengths

Van Meerbeek, Oper Dent 2003 Click here for abstract

Currently Available Generations

Fourth Generation
Three-step Etch & rinse

Fifth Generation
Two-step Etch & rinse

Sixth Generation
Two-step Self-etch One-step Self-etch
mix

Seventh Generation
One-step Self-etch
no mix

Classification of Newer Systems

Interaction with tooth surface Number of clinical application steps 1) Etch & rinse (i.e., total-etch) 2) Self-etch 3) Resin-modified glass ionomer
Van Meerbeek, Oper Dent 2003 Click here for abstract

Adhesive Categories
Etch & Rinse
Three-Step
conditioner, primer, adhesive

Two-Step
conditioner, (primer & adhesive)

Self-Etch
Two-Step
(conditioner & primer), adhesive

One-Step
(conditioner & primer & adhesive)

Glass Ionomer
Two-Step
conditioner, resin-modified glass-ionomer mixture

Etch & Rinse (Three-Step)

Conditioner Primer Adhesive resin Examples
Scotchbond Multi-Purpose Optibond FL

Conditioner
Chemical alteration of surface
acids

phosphoric, citric, maleic, nitric

Removes dentinal smear layer

exposes collagen fibrils

Simultaneous enamel etch Rinse

keep moist
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Primer
Hydrophilic monomers
dissolved in acetone, alcohol, or water

Displaces water Promotes infiltration into collagen Lightly air dry

drive off solvents, water

Transforms hydrophilic to hydrophobic

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Primer
Bifunctional monomer
Link
hydrophilic collagen hydrophobic resin

Example
HEMA

CH3 H2C=C-C-O-CH2-CH2-OH O

Adhesive Resin
Unfilled or lightly-filled monomers
equivalent to enamel bonding Bis-GMA, UDMA, TEGDMA

Stabilize the hybrid layer

fills up remaining pores

Resin tags Links primer to composite resin

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Hybrid Layer
Conditioner demineralizes dentin Interdiffused with low-viscosity monomer
displaces water bifunctional

Resin mechanically interlocks collagen

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Etch & Rinse (Two-Step)

Conditioner Combined primer and adhesive
higher technique sensitivity
higher solvent-to-monomer ratio
risk of applying too thin

apply multiple layers

Examples
Single Bond Optibond Solo Plus Prime & Bond NT
Hashimoto, Oper Dent 2004 Click here for abstract

Pros/Cons of Etch & Rinse

Separate acid etch
good enamel etch pattern

Potential to over-etch dentin

except sclerotic dentin

Post-conditioning rinse necessary

sensitive to level of dentin wetness

Multiple long-term clinical studies available

Van Meerbeek, Oper Dent 2003 Click here for abstract

Dentin Wetness
Etch & Rinse

After conditioning dentin

dentin must be wet
prevent collagen collapse

Too little water

collagen collapse

Ineffective resin penetration Leads to nanoleakage

Sano, Oper Dent 1995 Click here for abstract

Wet Bonding
Acetone and ethanol based primers
displace remaining water carry monomers into collagen gently air-dried
leaving monomers behind

Examples
One-Step Prime & Bond NT
Kanca, Quintessence Int 1992 Click here for abstract

Effect of Dentin Wetness

One-Step (Bisco)
16 14 12 10 8 6 4 2 0 moist dry 1 sec dry 5 secs dry 5 secs + rewet Bond Strength (MPa)

Perdigao, Am J Dent 1998 Click here for abstract

Overwet Phenomena
Too much water
not completely displaced

Phase separation
blister and globule formation

Tay, Dent Mater 1996 Click here for abstract

Disadvantages to Wet Bonding

Cannot check for enamel frosted etch Technique sensitivity
not too wet or too dry

Solvents evaporate from bottle

may reduce monomer penetration

Van Meerbeek in: Summitt, Fund Oper Dent 2001

Dry Bonding
Water-based primers
effective on wet or dry dentin
self-rewetting effect re-expand collapsed collagen

Permits check of frosted enamel Examples

Scotchbond Multi-Purpose Optibond
Van Meerbeek in: Summitt, Fund Oper Dent 2001

Class V Clinical Studies

Etch & Rinse Three-Step Scotchbond MP (3M ESPE)
100% retention at 3 yrs
Van Meerbeek, Quint Int 1996

98-100% retention at 3 yrs

Trevino, J Dent Res 1996

100% retention at 2 yrs

Alhadny, Am J Dent 1996

Class V Clinical Studies

Etch & Rinse Two-Step Optibond Solo (Kerr)
93.3% retention at 3 yrs
Swift, JADA 2001

Prime & Bond 2.1 (Caulk)

89.4% retention at 3 yrs
Swift, JADA 2001

Laboratory Study
Three-Step vs Two-Step Etch & Rinse
Shear Bond Strength
30 25 20
Two-Step Three-Step

MPa

15 10 5 0 Opti Opti FL Solo+ Single Bond MP + Excite Syntac

Pecora, J Prosthet Dent 2002 Click here for abstract

Laboratory Study
Three-step vs Two-step Etch & Rinse
Microtensile Bond Strength

60 50 40 uTBS 30 20 10 0

24 hr 4 yr Single Bond Scotchbond Optibond MP Solo Optibond FL

De Munck, J Dent Res 2003 Click here for abstract

Adhesive Categories
Etch & Rinse
Three-Step
conditioner, primer, adhesive

Two-Step
conditioner, (primer & adhesive)

Self-Etch
Two-Step
(conditioner & primer), adhesive

One-Step
(conditioner & primer & adhesive)

Glass Ionomer
Two-Step
conditioner, resin-modified glass-ionomer mixture

Self-Etch Components
Acidic monomers
MDP Di-HEMA-Phosphate MA 154 Phenyl-P MAC-10 4-MET(A) BisGMA UDMA TEGDMA GDMA HEMA usually water based

Crosslinking monomers
Solvent

Self-Etch (Two-Step)
Combined conditioner and primer Adhesive resin Examples
Clearfil SE AdheSE

Click here for table of self-etching adhesives

Self-Etch (One-Step)
Combined
conditioner primer adhesive

Examples
Prompt L-Pop One-up Bond F Touch and Bond iBond Xeno III
Click here for table of self-etching adhesives

Pros/Cons of Self-Etch
Good dentin conditioning
simultaneous infiltration
depth of demineralization

Possible reduction in post-op sensitivity?? No post-conditioning rinse

not sensitive to level of dentin wetness

Reduced application time

Hara, Am J Dent 1999

Clinical Studies
(Post-Operative Sensitivity) Class 1 or 2 composite restorations
Clearfil SE
self-etch

Prime & Bond NT

etch & rinse

Tested for post-op sensitivity No difference

Baseline, 2 weeks, 6 weeks, 6 months
Perdigao, JADA 2003 Click here for abstract

Baseline, 2 weeks
Perdigao, Quint Int 2004 Click here for abstract

80

Seconds

100

120

20
Self-Etch

40

60

Application Time

Source: USAF DECS N=3

Pr om pt LPo Xe p n O ne o I II -u p B on C le d ar fil SE A dh eS E iB on d Ex c Si ng ite Pr im le e& Bo n B on d d N T Ty ria n O PQ pt ib 1 Sc on d ot ch So lo bo nd M P

Etch&Rinse

Pros/Cons of Self-Etch
Limited clinical indications Limited clinical data Relatively lower bond strengths Many require refrigeration

Van Meerbeek, Oper Dent 2003 Click here for abstract

Shear Bond Strength to Dentin

Etch&Rinse

50 40
MPa

Self-Etch

30 20 10 0
Clearfil PBNT PQ1 Excite 1-Up AdheSE Xeno III Tyrian iBond Prompt SE Bond L-Pop Source: USAF DECS Horizontal lines connect nonsig diff at 0.05 level N=10

Class V Clinical Studies

Self-Etch Two-Step Clearfil SE Bond (Kuraray)
100% retention at 2 yrs
Peumans, J Dent Res abstr #0911

93% retention at 2 yrs

Turkun, J Dent 2003

Class V Clinical Studies

Self-Etch One-Step Prompt L-Pop (3M ESPE)
65% retention at 1 yr
Brackett, Oper Dent 2002

79% retention at 2 yrs

van Dijken, Am J Dent 2004

Special Considerations
Incompatibilities
self-cure composites with simplified adhesives
two-step etch & rinse one-step self-etch

Acidic monomers react with basic catalyst of overlying composite Adhesive permeability leads to superficial water blisters via water trees
Click here for details

Adverse Acid-Base Reaction

Simplified Adhesives

Composite
Neutral

O2 Inhibited Layer

Composite
BPO+Amine Acidic Monomers

Adhesive Primer Dentin

Dentin Two-step Etch & Rinse One-step Self-Etch

Suh, 2002

Three-step Etch & Rinse Two-step Self-Etch

Water Trees
Simplified adhesives
Act as semi-permeable membrane Conduct fluid Osmotic blistering
along the composite-adhesive interface slows self-curing of composite

Click here for details

Lindemuth 2004

Composite

Water Tree Formation

Hybrid Layer Trapped Moisture

Dentin

Lindemuth 2004

Hydrolytic Degradation of Resin Dentin Bond

Failure over time

Dual Cure
Dual- and self-cure composites
cores cements

Separate activator Examples

Optibond Solo Plus Prime and Bond NT

Features
Fluoride release Unit-dose

Fluoride Release
Anti-caries effect?
no proof of efficacy
in resin-based adhesives

Examples
FL-Bond One-up Bond F PQ1 Tenure Quick Optibond Solo Plus

Unit Dose
Improved infection control Convenience Minimizes loss of volatile components over time Higher cost Examples
Optibond Solo Plus Excite Prime and Bond NT Prompt L-Pop

Adhesive Categories
Etch & Rinse
Three-Step
conditioner, primer, adhesive

Two-Step
conditioner, (primer & adhesive)

Self-Etch
Two-Step
(conditioner & primer), adhesive

One-Step
(conditioner & primer & adhesive)

Glass Ionomer
Two-Step
conditioner, resin-modified glass-ionomer mixture

Resin-modified Glass-Ionomer
Weak conditioner pretreatment
polyacrylic acid
removes smear layer exposes collagen

Mechanical bonding
hybrid layer

Chemical bonding
carboxyl groups with calcium in tooth

Resin-modified Glass-Ionomer
Two-step
weak conditioner mix and apply glass ionomer adhesive

Fluoride release Example

Fujibond LC

Pros/Cons of Resin-Modified Glass-Ionomer

Chemical and mechanical bonding Fluoride release Limited clinical data
Class V study
Fuji Bond LC
96% retention at five years Class 5 Tyas, Oper Dent 2002

% 20
15

Average Annual Failure Rate

Class V Restorations

Standard Deviation

10 5 0
1.9 %
Glass Ionom er

4.8 %
3-Step Etch&Rinse

4.7 %
2-Step Self-Etch

6.2 %
2-Step Etch&Rinse

8.1 %

1-Step Self-Etch

Peumans, Dent Mater 2005 Click here for details

Adhesive Preferences with Light-Cured Composites*

Civilian Practitioners Total-etch Self-etch Other 70% 62% 3%

*Multiple responses

DPR 2005

Conclusions
Etch & rinse
favorable long-term data

Self-etch promising??
do not require rinsing
demineralize and infiltrate to same depth

reduced technique sensitivity reduced application time potential decreased post-operative sensitivity??
Van Meerbeek, Oper Dent 2003 Click here for abstract

Conclusions
Trend toward simplified application
reduced number of steps not necessarily better

Van Meerbeek, Oper Dent 2003

Purchasing Considerations
(Federal Dental Services)

4th generation
etch & rinse three-step
several available

5th generation
etch & rinse two-step
multiple available

6th generation
self-etch two-step
Clearfil SE Bond

self-etch one-step ????

Click here for synopsis of self-etching adhesives

Acknowledgements
Dr. David Charlton Lt Col Steve Klyn