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