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

Bond Strength (MPa)

One-Step (Bisco)
16
14
12
10
8
6
4
2
0
moist

dry 1 sec

dry 5 secs

dry 5 secs + rewet

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

MPa

25

Two-Step

20

Three-Step

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

24 hr
4 yr

Single Bond Scotchbond Optibond

MP
Solo

Optibond FL

40 uTBS
30
20
10
0

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)

Crosslinking
monomers

BisGMA
UDMA
TEGDMA
GDMA
HEMA

Solvent

usually water based

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

pt
L

Seconds

O
PQ
pt
ib
on 1
Sc
d
ot
So
ch
lo
bo
nd
M
P

-P
o
Xe p
n
O
ne o I
II
-u
p
B
on
C
le
d
ar
fil
SE
Ad
he
SE
iB
on
d
Ex
Si
ci
te
n
Pr
gl
e
im
e& B o
n
B
on d
d
N
T
Ty
ria
n

Pr
om

Application Time
Etch&Rinse
Self-Etch

120

100

80

60

40

20

Source: USAF DECS N=3

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
Self-Etch

50
40
MPa

30
20
10
0
C le a r fil
SE

PBNT

PQ 1

E x c ite

1 -U p

Ad h e S E X e n o III

T yr ia n

iB o n d

P ro mp t

B ond

Source: USAF DECS Horizontal lines connect nonsig diff at 0.05 level N=10

L -P o p

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

O2 Inhibited
Layer

Neutral

Adhesive
Primer
Dentin

Three-step Etch & Rinse

Two-step Self-Etch

Composite
BPO+Amine
Acidic
Monomers

Dentin
Two-step Etch & Rinse
One-step Self-Etch
Suh, 2002

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

Dentin

Trapped Moisture

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

Average Annual Failure Rate

Class V Restorations

15
Standard Deviation

10
5
0

1.9 %
Glass
Ionomer

4.8 %

4.7 %

3-Step
Etch&Rinse

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

*Multiple responses

70%
62%
3%

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