Some slide should follow references for your knowledge

1. The adhesion techniques for
metal to resin material
Resin
Noble
alloy
Base
metal
Mr Jarungvit Lorwicheanrung
Faculty of Dental Medicine rangsit university

2. The era of mechanical retention systems
Early 1970;metal-ceramic restoration
Macromechanical retention
was used before the development of systems
that could bond metal and polymer material.
One
problem
The bulkier
framework
need
History and current state of metal
adhesion systems used in prosthesis
fabrication and placement
;journal oral Science,Vol55(1),1-7,2013

3. The era of mechanical retention systems
Countersunk holes
1973; Rochette first reported the use of metal structures that were bonded by
resin to acid-etched enamel of abutment teeth,using retainers with countersunk
holes for retention and a chemical polymerizing composite resin for filling
Problem
1 Risk of fracture due to
insufficient retainer strenght
2 Considerable Skill was required
during placement because of
short polymerization time of
composite resin

4. Micromechanical retention
Early 1980s, micromechanical retention by electrolytic or acid-gel etching
“ micro-mechanical interlock”
Between metal frameworke and resin material
Produced Small pit or groove thickness of 0.3 mm for retainer.
Scanning electron microscope view of the surface of a
Ni-Cr alloy after etching with gel etchant

5. Maryland bridge
The bridge made using the electro-etching method
Was call
Other term in current
when effective of metal-
resin bone achieving
“ Maryland bridge” “Resin bonded bridge”

6. Chemical modification of the alloy surface
1 Apply coating to the surface that will created a
micromechanical bond (Tin plate)
2 Change the surface chemistry by silica coating or
tribochemical coating
3 Apply specially formulated metal primer

7. Tin plating produce oxidized layer on
noble alloy
Before the development of adhesive primers for noble alloy,tin coating produce
surface are for mechanical attachment and oxidized layer for chemical bond on the
surface of noble metal alloys
before
By heating
Tin plating
after
MDP/4META primer

8. Pyrochemical silica-coating

9. Silicoater
(Kulzer Co GmbH,Friedrichsdorf,Germany)
• In systems, a tetraethoxysilane solution is injected into a flame and burned with
butane in oxygen. The silane decomposes and forms reactive SiOx-C fragments,
which are deposited on the substrate surface.
After cooling to room
temperature,a layer of silane
coupling agent is applied onto
the fresh silica layer surface and
it is allowed to react for
5min.Then,an opaquer is
applied onto the surface and
light-cured.Then,the veneering
resin is built on.

10. Tribochemical silica-coating

11. Tribochemical silica-coating
-The alloy surface is grit-blasted at high pressure (no heat)with a powder that
“Fine alumina and colloidal silica particle”
-High-energy colloidal silica particles impacting the alloy surface cause physical fusion
of a silica layer to metal.
Laboratory base system
: Rocatec
A Chair-side technique
: Cojet

12. Rocatec system
-Under a operating air pressure of 280 kPa for 13 s/cm2
Step1 microblasting sand Rocatec Pre (cleaning and activating the surface)
with 110 μm aluminium oxide sand
Microretentive roughness is achieved

13. Rocatec system
Step2 Coating sand Rocatec Plus (110 μm silica coated alumina)or Rocatec Soft (30 μm
silica coated alumina)
Triboplasma surface
a depth of 15 μm of SiO2
partially coated with SiO2

14. Cojet system
The COJET sand-blasting system consists of ;
1.the actual coating medium (COJETSand) fine particle size (30 μm)
2.the silane solution ESPE SIL
3.SINFONY Opaquer
4.the light-cured bonding material VISIO-BOND

15. COJETSand
fine silica coated particle size (30 μm)

16. Tribochemical coating with CoJet Sand

17. The qualitative compositions of
the components used in the COJET system
SINFONY Opaquer
1. 3.2.
4. 1:1 ratio and mixing time 45 seconds
layer of 0.1 mm. Handling time is 5 minutesLight-cure for 10 seconds
allow to dry for 30
seconds
Light-cure for 20 seconds

18. Repair of Defects in Ceramic
COJET Sand ESPE SIL VISIO-BOND Composite
Repair of Defects in Composite
COJET Sand ESPE SIL VISIO-BOND Composite
Pretreatment of Metal, Ceramic or Composite
Restorations before Cementing
COJET Sand ESPE SIL Luting cement
Repair with CoJet systems

19. Repair of Defects in Composite with Exposed Metal
Broken porcelain expose metal CoJet Sand
ESPE SilSinfony Opaquer and applied Visio-bond
Repair with composite Finished restoration

20. Repair of Defects in Composite with Exposed Metal
Metal surface
Composite

21. Metal primer

22. First-generation metal adhesion system
In 1978 Takeyama et al increased the bond strength of acrylic
resin to 175 kg/cm2(17.17 MPa) with bovine enamel by adding a
newly discovered material, 4-methacryloyloxyethyl trimellitate
anhydride (4-META)
4-META use in dentistry: A literature review
The Journal of Prosthetic Dentistry Volume 87 issue 2 2002

23. After addition of water to 4-META powder, an easy and
swift hydrolysis reaction will take place to form 4-MET
Inactive form Active form
Systematic review of the chemical composition of contemporary
dental adhesives(Biomaterials 28 (2007) 3757–3785)

24. -Esterification of 4-MET when mixed with ethanol as solvent.
One of the carboxylic groups may react in an esterification
reaction with subsequent inactivation of the carboxylic group for
demineralization and adhesion promotion..
Systematic review of the chemical composition of contemporary
dental adhesives(Biomaterials 28 (2007) 3757–3785)

25. 4-META products

26. varied 5-15% of 4-META
4-META use in dentistry: A literature review
The Journal of Prosthetic Dentistry Volume 87 issue 2 2002

27. Orthomite Super-Bond was first developed as orthodontic cement in Japan.
Meta-Dent was developed as a heat-polymerized acrylic resin denture base. The
material contains the conventional polymethyl methacrylate (PMMA)/MMA acrylic
resin but has 5% of 4-META in the monomer.

28. Meta-Fast was introduced to the United States in 1985. This autopolymerizing denture
base resin is similar in composition to Acrylic Solder.(93% methyl methacrylate and 7%
4-META)
Cover-Up was tooth-colored autopolymerizing resin was intended for use as a cover-up material
for unesthetic RPD clasps

29. Cover-Up II, as described on the product label, was a “veneering system for chemically
bonding composite to amalgam, precious or non-precious alloys and stainless steel.
Amalgambond and Amalgambond Plus are autopolymerizing bonding agents for
dentin .Both consist of an activator and an adhesive (catalyst and base)

30. Quadrant Uni-1-Bond adhesive
(Cavex)
Contain: 4-methacryloxy-ethyltrimellitate
anhydride 10wt% (10%4-META) on ethanol/water
• Light-cure adhesive
• primer and sealer combined in one bottle for
direct restorations

31. • 10-MDP is a monomer that was originally synthesized by Kuraray (Osaka, Japan)
• It is mainly used as an etching monomer, due to the “dihydrogenphosphate group”
The long carbonyl chain renders this monomer quite
hydrophobic.
Also, it is clear that 10-MDP will be relatively hydrolysis
stable.
10-MDP
Phosphoric acidic monomer
Systematic review of the chemical composition of contemporary
dental adhesives(Biomaterials 28 (2007) 3757–3785)

32. 1.Methacryloyl group
Is indispensable to copolymerize the MDP
monomer and the matrix monomer in the resin
cement
2.Decyl group
Prevent penetration of water into the
adhesive interface, reducing or retarding
hydrolysis
3.Dihydrogen
phosphate group

34. Panavia cement

35. Epricord Opaque Primer(MDP)

36. Clearfil SE bond primer
• Hydrophilic dimethacrylate,MDP,HEMA,
dl-Camphorquinone

37. Clearfil liner bond 2v
(Kuraray Medical Inc, Okayama,Japan)
Bond A;
Light cure
Bond B;
Chemical cure
Primer A&B ;
10-MDP
self-etching primer

38. Others Phosphoric acidic monomer

39. Adhesion of resin to Noble metal alloy
“ Sulfur-containing component”

40. Second generation metal adhesion system
Late 1980s;the first adhesive monomer for noble alloy was introduced by Kojima
who synthesized 6-(4-vinyl benzyl-n-propyl)amino-1, 3, 5-triazine-2, 4-dithiol. (The
tautomer of dithiol and dithione.) (J Jpn Dent Mater 1987(6)702-7)
Thiol group

41. The first marketed was V-Primer
(Sun Medical Co.,Ltd) in 1994
Adhesive monomer: VBATDT
Indication use: Noble metal alloy
Thiol group

42. Alloy primer
(Sun Medical Co.,Ltd)
Adhesive monomer: VBATDT,MDP
Indication use: Noble and non noble metal alloy

43. There are reports that the VBATDT monomer
harms the polymerization reaction of resin-
based materials that contain the benzoyl
peroxide- amine initiator system,such as
panavia F,Bistite II DC
Water durability of resin bond to pure gold treated with various adhesion promoting
thiirane monomers Dent Mater J 2007;26:29-37)

44. Other products of Sulfur-containing
component adhesive monomer

45. Metaltite
(Tokuyama Dental Corp.,Tokyo,Japan)
Adhesive monomer: 1.5wt%MTU-6(6-methacryloyloxyhexyl 2-thiouracil-5-
carboxylate)
Indication use: Noble metal alloy
Thiouracil group

46. M.L.Primer
(Shofu Inc.,Kyoto,Japan)
Adhesive monomer: 10-MDDT(10-methacryloyloxydecyl-6,6-dithiooctanoate)
, 6-MHPA ( 6-methacryloyloxyhexyl phosphonoacetate)
Indication use: Noble and non noble metal alloy
Disulfide group

47. Metal Primer II
(GC Corp.,Tokyo,Japan)
Adhesive monomer: 1wt%MEPs(thiophosphate methacryloyloxyalkyl
derivatives),MMA
Indication use: Noble and non noble metal alloy

49. Metal primer that contained VBATDT
monomer should not use with panavia ?
Effect of a new metal primer on the bond strenght between a resin cement and two
high-noble alloys;Maria Antoniadou,ChristianAlbrechts University,Kiel,Germany
Journal of Prosthetic Dentistry Volume 84, Issue 5, Pages 554–560, November 2000

50. High gold alloy Surface treatment
Au(71%)-Ag-
Cu(12.2%)-Pt alloy
Grit blasting
Alloy primer
(VBATDT+MDP)
Panavia 21 Ex
cement
Au(77.8%)-Pd-Ag-
Pt-In alloy
Grit blasting
Alloy primer
(VBATDT+MDP)
Effect of a new metal primer on the bond strenght between a resin cement and two
high-noble alloys;Maria Antoniadou,ChristianAlbrechts University,Kiel,Germany
Journal of Prosthetic Dentistry Volume 84, Issue 5, Pages 554–560, November 2000

51. Mean tensile strenghts of the bonding groups
Group Au-Ag-Cu-Pt alloy Au-Pt-Pd-Ag-In alloy
150days/37,500TCs
Mean
Grit blasting 38.8 20.6
Alloy primer 40.8 31.9
Significant

52. A Study of self-sdhesive resin cements for bonding to Ag-Pd-Cu-Au
alloy- Effect of including primer components in cement base
(Koichi Muraguchi,Hiroyuki Minami,Shiro Suzuki ,Yoshito Menesaki and Takuo Tanaka)
Dent Mater J. 2011;30(2):199-205.pub 2011 Mar 12.
Ag-Pd-
12%Cu-
71%Au
alloy
PanaviaF2.0
cement
Alloy primer
+ PanaviaF
cement
No statistically
Significant in shear bond
strenght before and after
50,000 thermocycling

53. Sulfur-containing monomer can bond
to base metal?

54. Effects of metal primers on the bonding of an adhesive resin cement
to noble metal ceramic alloys for porcelain fusing
Dent Mater J 29:177-187
(VBATDT)
(10-MDDT)(MTU-6)

55. The effects of primers on alloys of
varying gold content(12-88%)
Effects of metal primers on the bonding of an adhesive resin cement
to noble metal ceramic alloys after thermalcycling
J Prosthet Dent. 2011 Dec;106(6):378-85

56. Highest
(VBATDT)
(MTU-6) (10-MDDT)

57. Primers Thermal
Cycles
W85 IFK88 N40 MC12
ML primer 0
50,000
C
M
C
M
C
M
C
M
Metaltite 0
50,000
C
M
C
M
C
A
C
M
V-primer 0
50,000
C
A
C
A
C
A
C
M
Table; Failure mode of each group
Resin cement interface;
M;Mixed failure of cohesive(Ramnants of resin cement on metal surface)
C; Cohesion failure of adhesive resin cement and adhesive
A; Adhesion failure at adherend-adhesive resin cement interface

58. Vinyl group
Benzene ring
Methacryloyl
group
Methacryloyl
group
Hexyl group
Decyl group
Thiol group
Thiouracil group
Disulfide group
Three component different of V-primer/Metaltite/ML primer

59. Thiouracil
Mixing
10-MDP
10-MDP
Thiouracil
group
Which one are The best for noble alloy?
1. 2.
3.
Effects of primers containing Thiouracil and Phosphate monomers on bonding of resin
to Ag-Pd-Au alloy
(Dent Materials journal ;27,1:69-74,2008)

60. Which groups have the most shear bond strenght ?
Metaltite(MTU-6), Vprimer(VBATDT)
,MetalprimerII(MEPs)
Epricord(10-MDP) ,PM, PE, PP
Alloy primer, Metaltite + Epricord /PM /PE / PP
Group 1
Thiouracil
Group2
10-MDP
Group3
Dual-function
monomer
Ag-Pd-Au
12%alloy
SuperbondC&B
Effects of primers containing Thiouracil and Phosphate monomers on bonding of resin
to Ag-Pd-Au alloy
(Dent Materials journal ;27,1:69-74,2008)

61. Low group
High
group

62. Effective of metal primer commercial products
High
gold
contain
Low
gold
contain
Au
78%,88%
Au
12%
M.L.Primer Metaltite V-Primer
Shear bond strenght High to Low
Alloy
Primer
Metaltite
Metal
Primer II
V-primer
Shear bond strenght High to Low

63. Silane Coupling Agents
(They can be bifunctional or dual reactivity)
Organic groupInorganic group
Inorganic
material;
Glass,
Metal,silica
stone
• methoxy (–O-
CH3)
• ethoxy
(–O–CH2CH3)
and others
Alkoxy groups
(Siloxane group)
Organic
material;
Resin
material
Methacrylate group
• Vinyl groups
• Epoxy groups
• Amino groups
• Methacryloxy groups
• Mercapto groups and
other
1.Chemical bond
2.Wettability

64. g-MPS or 3-MPS
(gamma- methacryloxypropyl-trimethoxy silane)
or(3- methacryloxypropyl-trimethoxy silane)
• The most commonly appled in dental laboratories and
chairside
• Usually dilute,often less than 2wt% in water-ethanol solution
with it PH of 4 to5(adjusted with acetic acid)
• The bond strenghts and water resistance are excellent when
mixture of silane and 3- methacryloxypropyl-
trimethoxy(monofunctional)
as be “ 3- methacryloxypropyl-trimethoxy silane(bifunctional)”
An Introduction to silanes and Their Clinical Applications in dentistry
(Quintessence Vol17(2),2004)

65. 3-trimethoxysilylpropyl methacrylate [3-MPS]

66. Silanol group
Siloxane oligomer group
1. 2.

68. Luting resin cementSilica base material
1.
2.
3.
Roulet JF,Sodeerholm KJ reported: For good bond strenght ;we should remove outer
and hydrolyzable layer with hot air dry 40-50 C for 2 minutes
Effect of post-silanization drying on the bond strength of composite to ceramic.
(J prosthet Dent 2004;91(5))

69. One bottle
(Pre hydrolyzed silane)
• Acid activate to form
“Silanol group” already
• Short shelf life
: Recommends re-frigerated
storage and replacement after
one year
(The solution may appear
cloudy or turn milky after
opening)
Two bottles
• Separation solution of
1.aqueous acetic acid
2.unhydrolyzed silane in
ethanol
• Longer shelf life
• Spend of time for mixing
Silane Coupling Agents
Preparing porcelain surfaces for optimal bonding
Comp Cont Educ Dent 2008;29:324-35.

70. Monobond S (Ivoclar Vivadent)
 MPS 1.0wt% pH 4 in Ethanol-water
Clearfil Porcelain bond activator (Kuraray Osaka,japan)
 MPS 40-60wt% pH 2.3 in hydrophobic aromatic -
dimethacrylate

71. RelyX Ceramic Primer(3M,ESPE,USA)
 MPS<1wt% pH 4.6 in Ethanol-water
ESPE Sil(3M,ESPE)
MPS<3wt% pH 4.5 in Ethanol>90%

72. Bis Silane(Bisco,Schaumburg,USA)
 MPS 1-10wt% pH 4 in Ethanol
Bisco Porcelain Primer (Bisco,Schaumburg,USA)
 MPS >1% pH 5.9 in Ethanol/acetone

73. Ultradent silane(Ultradent,South Jordan,USA)
MPS 5-15wt% pH 5.3 in Isopropanol 92%
Vitasil (Vita Zahnfabrik,Germany)
 MPS <2.5wt% pH N/A in Ethanol

74. Commercial Dental Silane

75. Which optimum concentration of 4-META
and 3-MPS?

76. Group Primer Shear bond strenghts
Group1 Without primer 5.05+0.19
Group2 5wt% of 4-META 10.84+0.14
Group3 10wt% of 4-META 11.71+0.18
Group4 15wt% of 4-META 10.64+0.21
Group5 1wt% of 3-MPS 8.66+0.18
Group6 2wt% of 3-MPS 10.19+0.24
Group7 3wt% of 3-MPS 9.54+0.20
Group8 ML primer(MDDT,6-MHPA) 12.01+0.14
Group9 Alloy primer(MDP,VBATDT) 15.08+0.13
Group10 Metal/Zirconia primer 10.04+0.15
Group11 Monobond S(1wt%3-MPS) 8.77+0.17
Group12 Monobond Plus(MPS,MDP,) 13.87+0.24
Shear bond strength between autopolymerizing acrylic resin
and Co-Cr alloy using different primers
(sasiwimol Sanohkan,Somchai Urapepon,Choltacha Harnirattisai,Chakrit Sirisinha and
Panya Sunintaboon)Dent Mater J 2012;31(5)

77. Advantage
Zirconia
(Yttria stabilized tetragonal zirconium dioxide)
• Ideal properties
-High flexural strenght
-toughness
-Biologically inert
-Esthetic appearance
-Good radiopacity
“Transformation toughening”
Tetragonal crystaline
Monoclinic phase
;Limits crack initiation

78. Disadvantage
• Cannot chemical bond to
veneering porcelain (can
use only CTE)
• Cannot be ecthed with
Hydrofluoric acid
(not increase micromechanical
, wettability)
• Cannot chemical bond to
some resin cement
Zirconia
(Yttria stabilized tetragonal zirconium dioxide)
The nonreactive surface
of zirconia present a
poor adhesion strenght .
Lohbauer et al reported
that native surface had
approximately 5.4% -OH
coverage
Hydroxylationn of dental surfaces: characterization and bonding potential.
Lohbauer U,Zipperle M,Rischka K ; J Biomed Mater Res B Appl Biomater. 2008 Nov;87(2)

79. Selective infiltration etching (SIE)
The zirconia surface is coated with a thin layer of glass-containing
conditioning agent which is then heated to above the glass transition
temperature.The molten glass at gain boundary enable sliding and splitting
of surface grains
Aspects of silane coupling agents and surface conditioning in dentistry:An overview
(Dental Materials 28(2012)467-477)

80. Zirconia
surface
treatment
Hydrofluoric acid
Selective acid
infiltration(SLE)
Airborne-particle
abrasion with
alumina particles
(50micron)
Tribochemical
treatment
Find-grit
diamond
rotary
cutting
May use
cleaning surface
with 37%
phosphoric acid
Contaminate :
Saliva , Bleeding
, Silicon(fitchecker)
Casucci A ;Improve
initial bond but not
the longevity of
bond strenght
(Dent Mater
2011;27:1024-30)
Some reported that airborne
particle abrasion induce
surface damage that
weakens the ceramic by
about 25% after cyclic
loading for sintered Y-TZP
plates (0.5 mm thickness)
(Zhang Y,Thompson VP)
(J Dent Res2010;89:592-6)
But;Siloxane bond sensitive
to hydrolytic degradation
Zr-O-Si bond are not Long -
term durable

81. Adhesive primer for Zirconia?

82. • The primers containing a phosphate ester monomer, including (phosphonic
acid) ex;6-MHPA and (phosphoric acid) ex;MDP, were the most effective ones
in improving the bonding of resin cements to zirconia ceramic.
Bonding of resin-based luting cements to zirconia with and without the use of
ceramic priming agents. Koizumi H et al. (J Adhes Dent 2012;14:385-92)

83. Phosphate ester monomer
Sulfur-containing monomer?

84. Effect of metal primers on microtensile bond strenght
between Zirconia and resin cement
(Grace M.,Dias de Souza,DDS,MS,PhD,Van P. Thompson,DDS,PhD and Roberto R.
Braga,DDS,MS,PhD ;University of Toronto, Canada; New York University, New York city)
(J Prosthet Dent. 2011 May;105(5):296-303)
Metaltite
(MTU)
Totalbond
(VBATDT)
Metal
primerII
(MEPs)
Alloy
primer
(MDP,
VBATDT)
Zirconia
Panavia
F2.0
RelyX
Unicem
The metal primer can
increase initial and long-
term bond strenght of
zirconia?

85. Means and standrard deviations for bond strenght(MPa)
Primer RelyX Unicem Panavia
Alloy primer 22.1 19.1
Toltalbond 13 14.7
No primer 10.4 13.9
Metal Primer II 9.4 14.9
Metaltite 9.1 12.2
So; The MDP-base monomer had superior bond strenght
than others molecules

86. Phosphonic acid monomer
Phosphoric acid monomer
Phosphonic acid acrylate
, 6- MHPA ,others
10-MDP
Zirconia Primer

87. Zirconia surface
Tribochemical
(Silica coated)
Airborne-
particle
abrasion
No treatment
A fine-grind
diamond
Mechanical
treatment
Clean surface
After try in
1.air-pressure
for 15 s.
3. Apply 37%
phosphoric
acid
2.Ultrasonically
cleaned for 3-5
mins. In 99%
alcohol or
distilled water
Chemical
treatment
Phosphonic
acid monomer
silane
4-META
10-MDP
10-MDP
Mixing silane

88. Which were the best mechanical
surface treatment for zirconia ?

89. The effect of zirconia surface treatment on flexural strenght and
shear bond strenght to a resin cement
(J Prosthet Dent. 2010 Apr;103(4):210-20)
Mechanical
treatment
1.control(no
treatment)
(n=48)
2.airborne-
particle abrasion
(n=48)
3. Silicoating
(n=48)
4. Wet hand
grinding
(n=48)
Chemical
treatment
1.control(no
treatment)
2. Acid etching
followed by
Monobond S
3. Monobond S
only
4. Apply
Metal/zirconia
primer(Ivoclar)
All 16 group
Multilinkresincemment
Adulthumanmolars
TC; 6,000 over 90 days

90. Metal/Zirconia Primer
(Ivoclar Vivadent,Schaan,Liechtenstein)
• To use, a single layer of Metal/Zirconia Primer should be applied to
the metal or ceramic surface and left to react for 180 seconds.
Contain ; phosphonic acid
acrylate 2.5-10wt%
, dibenzoyl peroxide, tert-
Butylalkohol

91. Initial Shear bond strenght means in MPa by mechanical and chemical treatment
no
mechanical
treatment Airborne Silicoated grinding
no chemical
treatment 10.2 15.7 15.3 11.6
Acid
etched/mono
bondS 12.8 17.1 14.5 22.2
MonobondS 17.3 22.9 30.9 17.2
Metal/Zirconi
a primer 22 20.8 21.2 25.5
But; After TC 6,000/90 days The Airborne/Zirconia primer group is the
most durable bond strenght

92. Signum
Zirconia bond
AZ Primer
Others Phosphonic acidic monomer
Metal/Zirconia
Primer

93. AZ primer
(Shofu Inc.,Kyoto,Japan)
• containing a phosphonic acid monomer
6-MHPA (6-methacryloxyhexylphosphonoacetate)

94. Signum zirconia bond
(Heraeus Kulzer in Hanau, Germany)
(Phosphonic ester monomer)
• 2,4,6-trimethylbenzoyl- Diphenyl-phosphinoxide

95. Tokuso
Ceramic Primer

96. Clearfil ceramic primer
(Kuraray ,Osaka,japan)
• 3-MPS, 10-MDP, Ethanol

97. Tokuso Ceramic Primer
(Tokuyama Dental, Tokyo,Japan)
• 3-MPS,10-MDP,alcohol

98. Silane
Carboxylic
monomer
Porcelain
liner M

99. Porcelain liner M
(Sun Medical,Moriyama,Japan)
Contain; MMA,4-META,Stabilizer Contain; MMA, Silane coupling
agent,Stabilizer

100. Phosphoric
acidic
monomer
Silane
Sulfur
acidic
monomer
Monobond
Puls

101. Monobond Plus
(Ivoclar Vivadent,Schaan,Liechtenstein)
1.
2.
3.
3-MPS
10-MDP
10-MDDT

102. 3-MPS
10-MDP
10-MDDT

103. Zirconia surface
Tribochemical
(Silica coated)
Airborne-particle
abrasion
Mechanical
treatment Clean surface
1.air-pressure
for 15 s.
2.Ultrasonically
cleaned for 3
mins. In 99%
alcohol
Chemical
treatment
ESPE Sil
Monobond
Plus
Long-term resin bonding to zirconia ceramic
with a New universal primer
J Prosthet Dent. 2011 Nov;106(5)
TC;37,500/150days

104. Tested groups 3 Days
Storage
with(TC)
150 Days
Storage with
(TC)
P
3 Days vs 150
Days
Mean-+SD Mean-+SD
SC-A-S 38.3+-9.7 11.3+-5.1 <.001
SC-U-S 31.5+-8.5 4.8+-6.9 <.001
SC-A-P 44+-6.4 36+-7.3 0.6
SC-U-P 45.2+-4.7 38.1+-6.2 0.8
AB-A-P 42.5+-7 21.7+-6 <.001
AB-U-P 44.1+-8.9 33+-9 0.2
SC=Silica coating,AB=Airborne-particle abrasion,A=cleaning with air,U =Ultrasonic cleaning
Statistically significant difference between group(P<.05)
ESPE
Sil
Mono
bond
Plus
Siloxane bond to Zirconia were not long-term
durable bond strenght

105. Phosphoric
acidic
monomer
Carboxylic
monomer
Z Primer
Plus

106. Z primer Plus
(Bisco, Schaumburg,IL)
• The co-monomer between ;
10-MDP(phosphoric acid group) and 4-META(carboxylic acid
monomer)

107. New zirconia primer improves bond strenght of
resin-based cements
Pascal Magne,Maria P.G.Paranhos,Luiz H.Burnett
Dental material 26(2010)345-352
No primer
Zirconia primer(Bisco)
Clearfil Ceramic
primer(Kuraray)
(4-META + MDP)
(MDP,silane)

108. Silane increase effectivness of MDP
base primer for bonding to Zirconia?
True or Flase?

109. Effect of silane and phosphate primers on the adhesive
performance of a tri-n-butylborane initiated luting agent
bonded to Zirconia
(Yusuke OBA,Hiroyasu Koizumi,Daisuke NAKAYAMA,Takaya ISHII,Nobutaka
AKAZAWA and Hideo Matsumura ; Dental Material 2014;33(2);226-232)
Groups Primer(Monomers)
Group 1 Monobond Plus (MDP,3-MPS)
Group 2 Clearfil Ceramic Primer (MDP,3-MPS)
Group 3 Alloy Primer (MDP,VBATDT)
Group 4 Alloy Primer + Porcelain Liner M Liquid B
(MDP,VBATDT,3-MPS)
Group 5 Porcelain Liner M Liquid A + Liquid B
(4-META,3-MPS)
Group 6 Porcelain Liner M Liquid A (4-META)
Group 7 Porcelain Liner M Liquid B (3-MPS)

110. Zirconia disks
(n=154)
Group 1-7
Wet grinding(1500
grit)
Luting (MMA-TBB)
Storage in 37 C water for 24 hr.
10,000
Thermocycling
Shear testing

111. Group Primer 0 thermocycle 10,000 thermocycle
Mean Median Mean Median Post/Pre-
bs ratio%
P-Value
Group 1 MP 28.6(0.9) 28.8 7.7(2.9) 7.4 25.7 P<0.01
Group 2 CP 29.6(0.9) 29.7 7.6(1.7) 7.4 24.9 P<0.01
Group 3 AP 26.8(2.1) 27.9 5.5(2.3) 6.6 23.7 P<0.01
Group 4 AP+PLM-B 28.4(1.1) 28.5 3.9(1.6) 4.1 14.4 P<0.01
Group 5 PLM-A+PLM-B 22.8(2.4) 22.5 0.3(0.2) 0.3 1.3 P<0.01
Group 6 PLM-A 20.7(2.0) 20.5 0.1(0.1) 0.2 0.5 P<0.01
Group 7 PLM-B 15.5(3.8) 17.1 0.2(0.1) 0 1.2 P<0.01
High bond strenght
Low bond strenght

112. Zirconia
surface
Tribochemical
(Silica coated)
Airborne-
particle
abrasion
Mechanical
treatment
Clean surface
After try in
air-pressure
for 15 s.
Ultrasonically
cleaned
Chemical
treatment
10-MDP Mixing
silane
EX:monobond
plus,Clearfil
Ceramic primer
Ultrasonically
cleaned
10-MDP
EX: Alloy
primer
10-MDP
Mixing silane
10-MDP Mixing
4-META
EX: Z Primer
Plus
1.
2.
Conclusion for Zirconia treatment

113. Trend
Zirconia surface treatment
No apply any primer

114. Plasma Fluorination pre-treatment
Development of a novel surface modification for improved bonding to
zirconia
(Dental Materials 2011,27;99-105)
• Zirconia were fluorinated ,inductively coupled 13.56 MHz plasma
reactor at 800 W with a DC bias of 300 V. to created a “reactive
surface”(Zirconium Oxyfluoride 1-3 nm.)

115. Surface fluorination of zirconia: Adhesive bond strength comparison to
commercial primers; Jeffrey R. Piascik Edward J. Swift
(Dental Materials 2012,28;604-608)
The phosphor group bond directly
to the oxygen in the oxyfluoride

116. Development of a novel surface modification for improved bonding to
zirconia
(Dental Materials 2011,27;99-105)

117. Plasma
Fluorination
(No primer)
Apply three
commercially
YSZ primers
without
surface
roughening
Surface fluorination of zirconia: Adhesive bond strength
comparison to commercial primers
:Jeffrey R. Piascik Edward J. Swift(Dental Materials 2012,28)
Bond to
RelyX Unicem 3M
(methacrylated
phosphoric ester)

118. Wetibility (contact angle)and shear bone strenght
• For this study ; two types of failure were adhesive and cohesive (composite left on
surface)
• The three group had 100% adhesive failure
• Z-primer had 70% and The fluorinated had 40% adhesive ; remaining were cohesive
failure