The adhesion techniques for metal to resin material
Resin
Noble alloy
Base metal
Mr Jarungvit LorwicheanrungFaculty of Dental Medicine rangsit university
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
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
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
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”
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
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
Pyrochemical silica-coating
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 silanecoupling 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.
Tribochemical silica-coating
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
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
Rocatec system
Step2 Coating sand Rocatec Plus (110 μm silica coated alumina)or Rocatec Soft (30 μmsilica coated alumina)
Triboplasma surfacea depth of 15 μm of SiO2
partially coated with SiO2
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
COJETSandfine silica coated particle size (30 μm)
Tribochemical coating with CoJet Sand
The qualitative compositions ofthe 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
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
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
Repair of Defects in Composite with Exposed Metal
Metal surface
Composite
Metal primer
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 trimellitateanhydride (4-META)
4-META use in dentistry: A literature review The Journal of Prosthetic Dentistry Volume 87 issue 2 2002
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 contemporarydental adhesives(Biomaterials 28 (2007) 3757–3785)
-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 contemporarydental adhesives(Biomaterials 28 (2007) 3757–3785)
4-META products
varied 5-15% of 4-META
4-META use in dentistry: A literature review The Journal of Prosthetic Dentistry Volume 87 issue 2 2002
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.
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
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)
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
• 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 contemporarydental adhesives(Biomaterials 28 (2007) 3757–3785)
1.Methacryloyl groupIs 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
Panavia cement
Epricord Opaque Primer(MDP)
Clearfil SE bond primer• Hydrophilic dimethacrylate,MDP,HEMA,
dl-Camphorquinone
Clearfil liner bond 2v (Kuraray Medical Inc, Okayama,Japan)
Bond A;Light cure
Bond B;Chemical cure
Primer A&B ;10-MDPself-etching primer
Others Phosphoric acidic monomer
Adhesion of resin to Noble metal alloy“ Sulfur-containing component”
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
The first marketed was V-Primer(Sun Medical Co.,Ltd) in 1994
Adhesive monomer: VBATDTIndication use: Noble metal alloy
Thiol group
Alloy primer(Sun Medical Co.,Ltd)
Adhesive monomer: VBATDT,MDPIndication use: Noble and non noble metal alloy
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)
Other products of Sulfur-containing component adhesive monomer
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
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
Metal Primer II(GC Corp.,Tokyo,Japan)
Adhesive monomer: 1wt%MEPs(thiophosphate methacryloyloxyalkylderivatives),MMAIndication use: Noble and non noble metal alloy
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,GermanyJournal of Prosthetic Dentistry Volume 84, Issue 5, Pages 554–560, November 2000
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,GermanyJournal of Prosthetic Dentistry Volume 84, Issue 5, Pages 554–560, November 2000
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
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%Aualloy
PanaviaF2.0 cement
Alloy primer
+ PanaviaFcement
No statistically Significant in shear bond strenght before and after 50,000 thermocycling
Sulfur-containing monomer can bond to base metal?
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)
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
Highest
(VBATDT)
(MTU-6) (10-MDDT)
Primers Thermal Cycles
W85 IFK88 N40 MC12
ML primer 050,000
CM
CM
CM
CM
Metaltite 050,000
CM
CM
CA
CM
V-primer 050,000
CA
CA
CA
CM
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
Vinyl group
Benzene ring
Methacryloylgroup
Methacryloylgroup
Hexyl group
Decyl group
Thiol group
Thiouracil group
Disulfide group
Three component different of V-primer/Metaltite/ML primer
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)
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 1Thiouracil
Group2
10-MDP
Group3Dual-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)
Low group
High group
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
PrimerMetaltite
Metal
Primer IIV-primer
Shear bond strenght High to Low
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 bond2.Wettability
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)
3-trimethoxysilylpropyl methacrylate [3-MPS]
Silanol group
Siloxane oligomer group1. 2.
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))
One bottle
(Pre hydrolyzed silane)
• Acid activate to form “Silanol group” already
• Short shelf life
: Recommends re-frigeratedstorage 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 bondingComp Cont Educ Dent 2008;29:324-35.
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
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%
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
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
Commercial Dental Silane
Which optimum concentration of 4-META and 3-MPS?
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)
Advantage
Zirconia(Yttria stabilized tetragonal zirconium dioxide)
• Ideal properties
-High flexural strenght
-toughness
-Biologically inert
-Esthetic appearance
-Good radiopacity
“Transformation toughening”Tetragonal crystalineMonoclinic phase;Limits crack initiation
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)
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)
Zirconia surface
treatment
Hydrofluoric acid
Selective acid infiltration(SLE)
Airborne-particle abrasion with
alumina particles
(50micron)
Tribochemicaltreatment
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 degradationZr-O-Si bond are not Long -term durable
Adhesive primer for Zirconia?
• The primers containing a phosphate ester monomer, including (phosphonicacid) 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)
Phosphate ester monomer
Sulfur-containing monomer ?
Effect of metal primers on microtensile bond strenghtbetween 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
PanaviaF2.0
RelyXUnicem
The metal primer can increase initial and long-term bond strenght of zirconia?
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 strenghtthan others molecules
Phosphonic acid monomer
Phosphoric acid monomer
Phosphonic acid acrylate, 6- MHPA ,others
10-MDP
Zirconia Primer
Zirconia surface
Tribochemical
(Silica coated)
Airborne-particle abrasion
No treatment
A fine-grind diamond
Mechanicaltreatment
Clean surfaceAfter 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
Phosphonicacid monomer
silane
4-META
10-MDP
10-MDP Mixing silane
Which were the best mechanical surface treatment for zirconia ?
The effect of zirconia surface treatment on flexural strenght andshear 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
Mu
ltilink resin
cemm
ent
Ad
ult h
um
an m
olars
TC; 6,000 over 90 days
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
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/monobondS 12.8 17.1 14.5 22.2
MonobondS 17.3 22.9 30.9 17.2
Metal/Zirconia 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
SignumZirconia bond
AZ Primer
Others Phosphonic acidic monomer
Metal/Zirconia Primer
AZ primer (Shofu Inc.,Kyoto,Japan)
• containing a phosphonic acid monomer
6-MHPA (6-methacryloxyhexylphosphonoacetate)
Signum zirconia bond(Heraeus Kulzer in Hanau, Germany)
(Phosphonic ester monomer)
• 2,4,6-trimethylbenzoyl- Diphenyl-phosphinoxide
TokusoCeramic Primer
Clearfil ceramic primer(Kuraray ,Osaka,japan)
• 3-MPS, 10-MDP, Ethanol
Tokuso Ceramic Primer(Tokuyama Dental, Tokyo,Japan)
• 3-MPS,10-MDP,alcohol
Silane
Carboxylic monomer
Porcelain liner M
Porcelain liner M(Sun Medical,Moriyama,Japan)
Contain; MMA,4-META,Stabilizer Contain; MMA, Silane couplingagent,Stabilizer
Phosphoric acidic
monomer
Silane
Sulfur acidic
monomer
MonobondPuls
Monobond Plus(Ivoclar Vivadent,Schaan,Liechtenstein)
1.
2.
3.
3-MPS
10-MDP
10-MDDT
3-MPS
10-MDP
10-MDDT
Zirconia surface
Tribochemical
(Silica coated)
Airborne-particle abrasion
Mechanicaltreatment Clean surface
1.air-pressure for 15 s.
2.Ultrasonically cleaned for 3 mins. In 99% alcohol
Chemical treatment
ESPE Sil
MonobondPlus
Long-term resin bonding to zirconia ceramic with a New universal primer
J Prosthet Dent. 2011 Nov;106(5)
TC;37,500/150days
Tested groups 3 Days Storage with(TC)
150 Days Storage with
(TC)
P3 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 cleaningStatistically significant difference between group(P<.05)
ESPESil
Monobond Plus
Siloxane bond to Zirconia were not long-termdurable bond strenght
Phosphoric acidic
monomer
Carboxylic monomer
Z Primer Plus
Z primer Plus(Bisco, Schaumburg,IL)
• The co-monomer between ;
10-MDP(phosphoric acid group) and 4-META(carboxylic acid monomer)
New zirconia primer improves bond strenght of resin-based cements
Pascal Magne,Maria P.G.Paranhos,Luiz H.BurnettDental material 26(2010)345-352
No primer
Zirconia primer(Bisco)
Clearfil Ceramicprimer(Kuraray)
(4-META + MDP)
(MDP,silane)
Silane increase effectivness of MDP base primer for bonding to Zirconia?
True or Flase?
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,NobutakaAKAZAWA 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)
Zirconia disks (n=154)
Group 1-7
Wet grinding(1500 grit)
Luting (MMA-TBB)Storage in 37 C water for 24 hr.
10,000Thermocycling
Shear testing
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
Zirconia surface
Tribochemical
(Silica coated)
Airborne-particle abrasion
Mechanicaltreatment
Clean surfaceAfter try in
air-pressure for 15 s.
Ultrasonically cleaned
Chemical treatment
10-MDP Mixing silane
EX:monobondplus,Clearfil
Ceramic primer
Ultrasonically cleaned
10-MDPEX: Alloy primer
10-MDP Mixing silane
10-MDP Mixing4-META
EX: Z Primer Plus
1.
2.
Conclusion for Zirconia treatment
TrendZirconia surface treatment
No apply any primer
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.)
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
Development of a novel surface modification for improved bonding to zirconia(Dental Materials 2011,27;99-105)
Plasma Fluorination(No primer)
Apply three commercially YSZ primers
without surface
roughening
Surface fluorination of zirconia: Adhesive bond strengthcomparison to commercial primers:Jeffrey R. Piascik Edward J. Swift(Dental Materials 2012,28)
Bond to
RelyX Unicem 3M(methacrylated
phosphoric ester)
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