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An insight into current concepts and techniques in resinbonding to high strength ceramics

R Luthra,* P Kaur†

*Professor, Department of Prosthodontics, Swami Devi Dyal Hospital and Dental College, Barwala, Panchkula, Haryana, India.†Reader, Department of Prosthodontics, Swami Devi Dyal Hospital and Dental College, Barwala, Panchkula, Haryana, India.

ABSTRACT

Background: Reliable bonding between high strength ceramics and resin composite cement is difficult to achieve becauseof their chemical inertness and lack of silica content. The aim of this review was to assess the current literature describ-ing methods for resin bonding to ceramics with high flexural strength such as glass-infiltrated alumina and zirconia,densely sintered alumina and yttria-partially stabilized tetragonal zirconia polycrystalline ceramic (Y-TZP) with respectto bond strength and bond durability.Methods: Suitable peer reviewed publications in the English language were identified through searches performed inPubMed, Google Search and handsearches. The keywords or phrases used were ‘resin-ceramic bond’, ‘silane couplingagents’, ‘air particle abrasion’, ‘zirconia ceramic’ and ‘resin composite cements’. Studies from January 1989 to June 2015were included.Results: The literature demonstrated that there are multiple techniques available for surface treatments but bond strengthtesting under different investigations have produced conflicting results.Conclusions: Within the scope of this review, there is no evidence to support a universal technique of ceramic surfacetreatment for adhesive cementation. A combination of chemical and mechanical treatments might be the recommendedsolution. The hydrolytic stability of the resin ceramic bond should be enhanced.

Keywords: Air particle abrasion, resin-ceramic bond, resin composite cements, silane coupling agents, zirconia ceramic.

Abbreviations and acronyms: AIN = aluminium nitride; APA = airborne particle abrasion; APF = acidulated phosphate fluoride; HIM= heat induced maturation; MTBS = microtensile bond strength testing; MVD = molecular vapor deposition; SIE = selective infiltrationetching; TSC = tribochemical silicoating.

(Accepted for publication 6 August 2015.)

INTRODUCTION

In recent years, an increasing demand for high perfor-mance aesthetic restorations has led to the develop-ment of several new ceramics with high flexuralstrength such as glass-infiltrated alumina and zirconia,densely sintered alumina and yttria–partially stabilizedtetragonal zirconia polycrystalline ceramic (Y-TZP).1–5

Clinical fracture of zirconia is rarely seen.6,7 Due totheir high fracture resistance, these restorations canbe cemented using conventional cements such aszinc phosphate and resin modified glass ionomer.8

However, resin cements offer the advantage of shade-matching, marginal adaptation, high flexural strengthand fracture resistance, especially in short clinicalcrowns and heavy occlusal forces.9–16 Resin bondingalso helps to improve retention in CAD/CAM-milledceramic restorations and to seal minor internal surface

flaws created by acid-etching or airborne particleabrasion.9,17,18

A strong resin-ceramic bond relies on micromechan-ical interlocking and chemical bonding. Insufficientsurface modification could affect the retention of cera-mic.19,20 Conventional adhesive bonding techniquessuch as surface etching and silanization are wellrecognized for silica based or feldspathic ceramics,but establishing a strong and stable bond with highstrength ceramics like alumina and zirconia hasproved to be difficult as the materials are hard, acid-resistant and silica free.21,22 The silica content of alu-mina ceramics is below 5 wt% and that of zirconiaceramics is below 1 wt%. The silica content oflithium-disilicate (IPS Empress 2) and feldspathicceramics is approximately 50–60 wt%.22

Various researchers have investigated differentsurface pretreatments to optimize the surface of

© 2016 Australian Dental Association 163

Australian Dental Journal 2016; 61: 163–173

doi: 10.1111/adj.12365

Australian Dental JournalThe official journal of the Australian Dental Association

high strength ceramic materials but results havevaried.13,23,24 The aim of this review was to assess thecurrent literature for laboratory studies on resin bond-ing to high strength dental ceramics with respect tobond strength and bond durability.

MATERIALS AND METHODS

Suitable peer reviewed publications in the English lan-guage were identified through searches performed inPubMed, Google Search and handsearches. The key-words or phrases used were ‘resin-ceramic bond’, ‘si-lane coupling agents’, ‘air particle abrasion’, ‘zirconiaceramic’ and ‘resin composite cements’. Studies fromJanuary 1989 to June 2015 were included. Titles andabstracts were evaluated for appropriateness to fulfillthe inclusion and exclusion criteria. Articles that didnot focus exclusively on resin–ceramic bonding andproperties of zirconia ceramics were excluded fromfurther evaluation. Non-peer reviewed dental litera-ture, abstracts and clinical reports were excluded fromreview. Of the retrieved articles, a total of 37 articleswere selected on the resin bond to silica-based ceram-ics, and 78 articles on bonding to high strength dentalceramics, which included aluminium-oxide ceramics(16 articles) and zirconium-oxide ceramics (62 arti-cles). An additional 27 references were included toprovide supplementary information about the charac-teristics of resin bonding to ceramics.Common surface treatment options were airborne particle

abrasion with aluminium oxide,22,23,25–44 diamond blastingwith synthetic diamond particles,25 grinding,29,30 abrasionwith diamond rotary instruments,35,41 application of fused glassmicropearls,45 plasma spraying,45 tribochemical silicoating(TBS),21,22,26,32,34,37,46–58 Pyrosil-Pen technology,59 silica seedtreatment,60 laser treatment,61 selective infiltrationetching,39,62,63 alumina coating,64 acid-etching,19,21,28,32,65–86

silane coupling agents,13,19,20,58,66–68,74,84,87–100 zirconiaprimers,41,101–107 and luting agents containing adhesive phos-phate monomer.20,34,39,47,52,55,56,58,75,81,108–126 Table 1shows a chronological overview of some studies onresin bonding to high strength ceramics including thetype of ceramic tested, surface treatment and cement,method of artificial ageing, method of testing andmean bond strength in each experiment. The effect ofartificial ageing127–129 and testing methods130–139 hasalso been studied widely. This article presents a com-prehensive review on various mechanical and chemicaltreatments currently being used for bonding to highstrength ceramics.

Mechanical methods

Airborne particle abrasion (APA) may substantiallyincrease the roughness and surface area of ceramicsurfaces, enhance the potential for micromechanical

retention and increase the bond strength.27,32,33,42

APA is performed using 50 lm to 110 lm grain sizedaluminium trioxide powder under 0.2 MPa pressurefrom a distance of 10–25 mm for 13–20 seconds untila white opaque colour appears. Hummel et al. stated‘neither stable micromechanical retention nor stablechemical bonds could be achieved without sandblast-ing’.34 APA also cleans the surface of any contami-nants or saliva which might prevent chemicalbonding.28,40

On the other hand, few studies stated that APA didnot change the surface microstructure of silica freeceramics and recommended alternate protocols toensure adequate bonding.20,22,26,31 Borges found thatAPA of high purity alumina ceramic with 50 lm alu-minium oxide caused flattening of the alumina crystalsrather than creation of microretentive features.31 Fewstudies have expressed concerns about the potentiallong-term adverse effect of surface abrasion such asstructural damage, creation of sharp crack tips, grainpullout and material loss, especially at the margins ofthe restorations.23,26,30,38,39 Zhang et al.23 found thatstrengths of sandblasted alumina and zirconia speci-mens showed significant reduction in both dynamicand cyclic tests, indicative of larger crack initiatingflaws. These defects could further weaken the bondstrength and compromise the fatigue strength of alu-mina and zirconia ceramics.38

In contrast, several studies found that APAincreases the flexural strength of Y-TZP zirconia.29,35–37,41,44 Low stresses developed during this processmay cause a transformation of surface crystals from atetragonal (t) to a monoclinic (m) phase, with conse-quent volume expansion and a compressive stress fieldaround the crack tip, thus preventing its further prop-agation.35–37,41,44 Mild sandblasting (110 lm particlesize and 0.2 MPa pressure) could be beneficial,whereas severe sandblasting (250 lm and 0.4 MPa)induces much larger damage.43

Tribochemical silicoating

The ceramic surface is blasted with silica coated alu-mina particles using compressed air.21,26 The impactresults in a partial coating of silica on the surface thatis further primed by silanization, after which therestoration may be cemented using resin compositecement.49

The tribochemical effect has two aspects: microme-chanical bonding to resin due to surface topographyand promotion of a chemical bond between silica andresin via silane coupling agent.Several investigations have demonstrated higher

bond strength after silicoating and silanation than thatachieved by APA alone.22,26,32,34,37,46–50,53–57,90,95,135

Most of the studies which have used TBS along with

164 © 2016 Australian Dental Association

R Luthra and P Kaur

Table1.

Stud

ieson

resinbo

ndingto

high

streng

thceramics

Studyandyear

Ceramic

Recommended

surface

treatm

ent

andcement

Methodofartificialageing

Methodof

testing

Meanbondstrength

(MPa)

KernandThompson471995

glass

infiltered

aluminium

oxide(InCeram,Vita)

Tribochem

icalsilica

coating+BIS-G

MA

basedresincement

150days

inwater37500

cycles

thermocycling

tensile

49.85

Jandaet

al.592003

Zirconium

oxide(D

egussit)

PyroSilPen

(Flametreatm

ent)+silane+

BIS-G

MA

basedresincement

24hrdry

storageand5000

cycles

thermocycling

shear

16

Blatz

etal.1092003

Aluminium

oxide(Procera

AllCeram,Nobel

Biocare)

APA

with50-lm

Al 2O

3+silane+Panavia

180days

inwaterand

12000cycles

thermocycling

shear

16.09

Blatz

etal.1112004

Procera

AllZirkon

(Nobel

Biocare)

Airparticle

abrasionwith50-lm

Al 2O

3+

ClearfilSEBond/Porcelain

BondActivator

(Kuraray)+PanaviaF

180days

inwater,and

12000cycles

thermocycling

shear

16.85

Kim

etal.222005

InCeram

Alumina,(V

ita)

Silicacoating+silanebondingagent/primer

andbondingresin+Z100Composite

(3M

ESPE)

72hours

insalinesolution

at37°C

tensile

18.6

Bottinoet

al.532005

InCeram

Zirconia

(CEREC

In-Lab

,VITA)

Tribochem

icalsilica

coating+silane+PanaviaF

7daysin

distilled

waterat

37°C

.microtensile

26.8

Valandro

etal.542005

Procera

AllCeram

Tribochem

icalsilica

coating+Silane+PanaviaF

7daysin

distilled

waterat

37°C

microtensile

18.5

Derandet

al.452005

Y-TZPProcera

Zircon

Micropearlsoflow

fusingporcelain

+silane+

VariolinkII(IvoclarVivadent)

Airstoragefor1hr

shear

18.4

Atsuet

al.552006

zirconium-oxide(C

ercon,

DegussaDental)

Airparticle

abrasionwith125-lm

(Al2O3)+

Tribochem

icalsilica

coating+M

DP–containing

bonding/silanecouplingagentmixture

+PanaviaF

24hrs

indistilled

waterat

37°C

shear

22.9

Kumbuloglu

etal.1142006

zirconium-oxide(D

CS)

Airparticle

abrasionwith50-lm

(Al2O3)+

Tribochem

icalsilica

coating+

PanaviaF/RelyX

unicem

24hrs

inwater

and2000

cycles

thermocycling

shear

20.9

Luthyet

al.562006

ZrO

2-TZP(C

erconSmart)

Tribochem

icalsilica

coating+RelyX

unicem

/Panavia21

48hrs

inwater

at37°C

and

10000cycles

thermocycling

shear

36.7-73.8

Amaralet

al.572006

InCeram

Zirconia

(VITA)

Tribochem

icalsilica


7daysin

waterat37°C

microtensile

26.7

Valandro

etal.1292007

InCeram

Zirconia

(VITA)

Tribochem

icalsilica


300days

inwaterand

12000cycles

thermocycling

microtensile

4.3

Wolfart

etal.1182007

Zirconia

(Cercon,Degudent)

Airparticle

abrasionwith50-lm

(Al2O3)+PanaviaF

150days

inwaterand

37500cycles

thermocycling

tensile

39.2

Aboushelib

etal.392007

Y-TZP(C

ercon,DeguDent)

Airparticle

abrasionwith110-lm

(Al2O3)+

selectiveinfiltration-etching+PanaviaF2.0

1month

inwaterat37°C

microtensile

52.2

Aboushelib

etal.622008

Zirconia

Procera

Selective-infiltration-etching+silanebased

zirconia

primers+PanaviaF2.0

24hours

atroom

temp

microtensile

28-40.6

Aboushelib

etal.1022009

Zirconia

Procera

selective-infiltrationetching+silanebased

zirconia

primers+PanaviaF2.0

90days

waterstorageat

37°C

microtensile

15-18

Oyagu

eet

al.1212009

Zirconia

(Cercon)

Tribochem

icalsilica

coating+Clearfil

Esthethic

cement(K

uraray)

6monthswater

storageat

37°C

microtensile

15.36

Piascik

etal.602009

Zirconia

ZirCAD

(Ivo

clarVivad

ent)

Airparticle

abrasionwith50-lm

(Al2O3)+

Si xO

4seed

layer

+silane+resinadhesive+

resinlutingcement(C

&BBisco)

Room

tempfor24hrs

microtensile

23.2

Cavalcantiet

al.612009

Zirconia

(Y-TZP,Cercon)

Airparticle

abrasionwith50-lm

(Al2O3)+

metalprimer

+BISGM

Abasedresin

cement(C

alibra,Dentsply)

24hrs

inwater

at37°C

microshear

27.99

(continued)


Current concepts and techniques in resin bonding

Table

1continued

Studyandyear

Ceramic

Recommended

surface

treatm

ent

andcement

Methodofartificialageing

Methodof

testing

Meanbondstrength

(MPa)

Qeblawiet

al.412010

Y-TZP(Z

irCAD,

IvoclarVivad

ent)

Tribochem

icalsilica

coating+silane+

resinlutingcement(M

ultilink

Automix,IvoclarVivadent)

90days

inanincubatorat

100%

humidityat37°C

and6000thermal

cycles

shear

30.9

Magneet

al.1032010

Zirconium

oxide

(LAVA,3M

ESPE)

Airparticle

abrasionwith50-lm

(Al2O3)+

zirconia

primer

(amixture

oforganophosphate

andcarboxylicacidmonomers)

+resin

lutingcement(D

uolink,Bisco)

24hrs

indistilled

water

shear

26.68

Jevnikaret

al.642010

TZ-3YB-E

Zirconia

(Tosoh,Tokyo,Japan)

Airparticle

abrasionwith110-lm

(Al2O3)+

nanostructuralaluminacoating+phosphate

estercontainingresinlutingcement(R

elyX

Unicem

,3M

ESPE)

12000cycles

thermocycling

shear

27.32

Kitayamaet

al.982010

Zirconia

(CerconBase)

Airparticle

abrasionwith110-lm

(Al2O3)+

phosphonic

acidcontainingceramic

primers

(AZ

primer,Shofu)+resinlutingcement

(Resicem

,Shofu)

24hrs

water

storage

tensile

22.3

Attia

etal.582011

Zirconia

(e.m

axZirCAD,

IvoclarVivad

ent)

Tribochem

icalsilica

coating+universal

primer

containingasilaneandaphosphate

monomer

(MonobondPlus,IvoclarVivadent)+resinluting

cement(M

ultilinkAutomix,IvoclarVivad

ent)

30daysin

waterat37°C

and7500cycles

thermocycling

tensile

39.7

deSouza

etal.1222011

Zirconia

(Lava

Frame,

3M

ESPE)

Primer

containingMDP,VBATDT

(AlloyPrimer,Kuraray)+RelyX

Unicem

150daysin

waterat37°C

microtensile

6.1

Matinlinnaand

Lassila1

042011

Procera

AllZircon

Tribochem

icalsilica

coating+silanization

withsilanemonomer

primers

(glycidoxypropyltrimethoxysilane)

+RelyX

Unicem

6000cycles

of

thermocycling

shear

17.6

deC

astro

etal.1232012

Zirconia

(YZ-In

Ceram

YZ,VITA)

Tribochem

icalsilica

coating+RelyX

Ceramic

Primer

+resinlutingagent

(RelyX

ARC,3M

ESPE)

60daysin

waterand10000

cycles

thermocycling

microtensile

12.9

Piascik

etal.1062012

Zirconia

(LAVA,

3M

ESPE)

Plasm

aFluorinationgasphase

treatm

entfor

5mins.+FiltekUltra

Supreme(3M

ESPE)

Waterstorageat37°C

for

24hrs

shear

37.3

Lunget

al.1052012

Zirconia

(LAVA,

3M

ESPE)

Tribochem

icalsilica

coating+silanecouplingagent+

RelyX

Unicem

30daysin

water

and6000

cycles

ofthermocycling

shear

14.5

Chen

etal.1072013

Zirconia

(Cercon;

Dentsply)

Airparticle

abrasionwith50-lm(A

l2O3)+

zirconia

primer

containingM

DPandBisGMA

(ZPrimePlus,Bisco)+resincomposite

cement(D

uolink,Bisco)

Waterstorageat37°C

for

24hrs

shear

29.0

Saryazdiet

al.1242014

Zirconia

(TZPBIO

HIP;

MetoxitAG)

Airparticle

abrasionwith50-lm

(Al2O3)

+RelyX

Unicem

224hrs

inwater

at37°C

+5000cycles

thermocycling+

dynamic

axialloading

tensile

3.7

APA

=airparticle

abrasion.


R Luthra and P Kaur

zirconia primers or phosphate monomer containingcements have shown bond strength value after artifi-cial ageing (late bond strength) greater than 20 MPa(Table 1). Systems such as the Rocatec� system (3MESPE) consist of an APA pretreatment with RocatecPre powder (110 lm aluminium oxide) under0.2 MPa pressure to clean the alumina/zirconiumceramic surface, then a silica coating with RocatecPlus powder (110 lm aluminium oxide, coated withsilicon dioxide) and finally, the application of silane.The CoJet System (3M ESPE) uses 30 lm aluminiumoxide particles modified with salicylic acid. CoJet isused for clinical procedures, such as the intraoralrepair of fractured metal-ceramic and all-ceramicrestorations with resin composites. An oil-free airstream or ultrasonic cleaning in alcohol may be usedto remove visible dust resulting from APA as loosesurface particles might negatively influence adhe-sion.58 However, the cleaning method should notremove the silica coating layer from the ceramic sur-face. It is crucial to perform silica coating perpendicu-lar to the surface to obtain the greatest benefit, as it ismore difficult to achieve on the intaglio surface of acrown than on a flat ceramic specimen.52

Silicoating can also be achieved chairside by usingPyroSil Pen� technology using flame treatment.59 Pias-cik et al. advocated an approach to surface functional-ize zirconia with a SixOy ‘seed’ layer of thickness2.6 nm by a molecular vapor deposition (MVD) ofvapor phase mixture of water and tetrachlorosilane for15 minutes in a vacuum chamber. The improved chem-ical reactivity of the silica seed treated surfaces wasfound to be superior to that of the tribochemicaltechnique.60

While the TSC system significantly increased thebond strength for InCeram (Vita) and ProceraAllCeram (Nobel Biocare) ceramics,48,51 it requiredthe use of a resin composite containing an adhesivephosphate monomer for improved bond strength forzirconia ceramic.20,123

Cavalcanti et al. investigated the role of erbium-doped yttrium aluminum garnet laser (Er:YAG) toenhance the bond strength of resin composites toceramics.61 They used laser equipment emitting a2.94 lm wavelength with a 1000 lm diameterstraight-type contact probe perpendicular to the sur-face. The energy intensity was set low at 200 mJ.Er:YAG laser has the ability to remove particles bymicro explosions and by vaporization, a process calledablation. The ceramic surface was irradiated for fiveseconds using a fine water spray. Results indicatedthat laser irradiation was not as effective in improvingbond strength as air abrasion. SEM images showedthat Er:YAG laser resulted in a smooth surface ofY-TZP plates, with some perceivable cracks. Themechanical properties of Y-TZP ceramics can be

negatively affected by changes in temperature duringlaser treatment.Aboushelib et al. proposed selective infiltration

etching (SIE), that uses principles of heat induced mat-uration (HIM) and grain boundary diffusion of mol-ten glass, to selected areas of zirconia, providingnanomechanical retention.62 The bond strength of theHIM/SIE group was higher than APA treated speci-mens and not affected by artificial ageing.39 A similartechnique was tested by atomic force microscopy andconsidered a promising treatment for conditioning zir-conia.63

Chemical methods

Chemical etching

In feldspathic ceramics, hydrofluoric acid (HF acid5–9.5%) applied for 60 seconds66,68,69,80,83 selectivelydissolves the glassy components, producing a porous,irregular honeycomb-like surface,65,67,76 that providesmore surface area and surface energy prior to combin-ing with the silane solution.21,66,74,77,78,81,82 Variousother chemicals have been used for etching of silicacontaining ceramics including orthophosphoricacid,28,72,73 sulphuric acid, nitric acid, ammoniumhydrogen bifluoride71 and acidulated phosphate fluo-ride (APF);70 HF acid, being more aggressive, gave thehighest bond strength.79,84–86

However, as the silica phase in ceramic is the onlyphase able to be etched by HF acid, it is inefficient inproviding adequate retention in high strength silicafree ceramics which cannot be etched.32,47,67,75

A silane coupling agent, 3-methacryloxypropyl-trimethoxysilane (3-MPS), is often used prior to theapplication of an adhesive resin on the roughenedceramic surface as a standard practice of porcelainrepair. Silane increases the substrate surface energyand improves surface wettability.13,49,58,68,87,93,95,96,99

Due to its bi-functional characteristics, it is capable offorming a siloxane network with the silica phase inceramics on one side and copolymerizing with theorganic matrix of the resin composite on the other,producing strong chemical bonds between compositesand ceramics.19,74,84,88–94,98 Della Bona et al.93 foundthat the chemical adhesion produced by silane pro-moted higher mean bond strength values than themicromechanical retention produced by any etchantfor the resin-ceramic systems.The traditional silane chemistry is not applicable to

zirconia unless it is silicoated.45 Another clinical prob-lem is the bond degradation over time in the oralenvironment.20,39,47,51,55,111,113,116,129 Kern and Weg-ner reported good initial bond strength of resincement to APA treated zirconia. However, adding asilane did not improve the durability of the bond in



water. Excessive thickness of silane (40 nm) can com-promise its beneficial effect due to structural stratifica-tion in three layers. The innermost layer provides astrong siloxane bond, whereas the outermost andintermediate layers are only physically adsorbed. Heattreatment at 100 °C consolidates these three layersinto a monolayer (30 nm) and eliminates silane by-products like water or alcohol. Rinsing in hot waterat 80 °C showed thinner silane films (14 nm).100 Heattreatment of the silane film improves its chemicalreactivity and the resistance to hydrolysis.Derand et al. investigated plasma spray technique to

deposit a siloxane coating (hexamethyldisiloxane) onzirconia.45 Bond strength with resin was improved butthe exact mechanism of bond formation was unclear.

Zirconia primers

In recent years, manufacturers have developed severalcommercial zirconia primers (phosphate monomers)or silane primers.41,107 Aboushelib et al. used novelengineered zirconia primers in combination with selec-tive infiltration etching as a surface pretreatment.These primers were 3-Acryloyloxypropyltrimethoxysi-lane, 3-Isocyanatopropyltriethoxysilane, 3-Styrylethyl-trimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane.102 Presence of specific organofunc-tional groups in these primers may improve spatialcompatibility and increase the reactivity of silanemonomers. These primers initially showed high bondstrength values but significant reduction in bondstrength was seen after 90 days of water storage.Long-term bond stability requires developing morehydrophobic compounds. The bonding should rely onchemical interaction as well as a mechanically reten-tive surface of zirconia.102 Matinlinna et al. in a simi-lar study found a significant increase in bond strengthwhen these primers were applied to silica coatedzirconia.104

Phosphate monomer

10-methacryloyloxydecyl dihydrogen phosphate(MDP), has a long carbonyl chain and plays a benefi-cial role in establishing a relatively hydrolyticallystable chemical bond to zirconia.20,34,39,56,116 Theapplication of an MDP containing bonding/silane cou-pling agent mixture (Clearfil SE Bond Primer andClearfil Porcelain Bond Activator, Kuraray) to intagliosurfaces of Procera All Ceram alumina109 and ProceraAll Zirkon restorations abraded with airborne Al2O3

particles has shown high bond strength.58,111,119 MDPincorporated into the resin composite also showedhigh and durable bond strengths for air-abradedalumina and zirconia specimens,108,109,118 e.g. Panavia21 (Kuraray-Noritake, Tokyo, Japan). Applying a

TSC and a silane coupling agent in combination withPanavia 21 could be a recommended option,47,121

whereas de Oyague stated that with a phosphatemonomer containing luting system, other surfacetreatments like air abrasion or silica coating are notnecessary.120

Various investigations have found cements likeglass-ionomer cement110 or a 4-META containingadhesive resin (Superbond C&B, Sun Medical)52,75,112

produce a superior bonding to Y-TZP than Panavia21. No inorganic filler is contained in Super-BondC&B, as the primary ingredient is referred to as4-META/PMMA-TBB (4 methacryloxyethyl-trimellitat-anhydrid/polymethylmethacrylate-tri-n-butylborane)resin. This cement has a low modulus of elasticity.The ductile resin cement thus functions as a shockabsorber so that it can distribute forces duringfracture testing on the tooth-cement-ceramic complex.In addition, Super-Bond C&B contains long flexiblechains of high molecular weight, which tend to result inhigher fracture toughness values when compared withhighly cross-linked brittle materials contained in othercomposite cements. Plastic deformation delays theonset of brittle fracture, resulting in higher fracturetoughness values. However, Hummel stated that waterabsorption of PMMA over long-term storage dimin-ishes the bond strength of Superbond C&B.34

Another cement, RelyX Unicem (3M ESPE, Seefeld,Germany), a self-adhesive dual polymerizing phos-phate ester containing resin composite, has showngreater bond strength than Panavia.56,81,112–115,122

The phosphate ester methacrylate monomer in RelyXUnicem’s composition was found to be more efficientfor bonding to zirconia than the MDP monomer.Panavia has a high viscosity that results in a greaterfilm thickness which compromises its adaptation tothe zirconia surface. Saryazdi et al. stated thatPanavia F and Rely X Unicem cements providedsignificantly higher retention than the Bis-GMA basedresin cement. According to them, zirconia crownretention is dependent on the adhesive cement usedand not on the internal surface treatment.124 How-ever, Aboushelib et al. stressed that mechanical reten-tion is important to gain any benefit from the MDPresin composite and cement alone will not be able toprovide long-term bond strength.102

Cassuci et al.63 evaluated the effect of an experi-mental hot etching solution on the bonding potentialof zirconia. The solution consisted of methanol, 37%HCl and ferric chloride, and was earlier used to etchthe wings of Maryland bridges. They assumed thatthe solution may be somewhat beneficial for etchingzirconium due to the metallic nature of pure zirco-nium. The results of their work showed that the solu-tion improved surface roughness of zirconium througha corrosion-controlled process.


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Metal primers, such as VBATDT (6-(N-(4-vinylbenzyl)propylamino)-1,3,5-triazine-2,4-dithione;Kuraray-Noritake, Tokyo, Japan), Metaltite (MTU-6:6-methacryloxyhexyl 2-thiouracil-5-carboxylate;Tokuyama Dental Corporation, Tokyo, Japan) andMetal Primer II (MEPS: thiophosphoric methacrylate;GC Corporation, Tokyo, Japan), capable of bondingto noble and base metals also have been tested toimprove bond strength between Y-TZP and lutingresin systems.34,61,101 The presence of phosphatemonomer in these primers is the reason for the stabil-ity of the bond. Metal primers and air abrasion canhave a synergistic effect on bonding to zirconia.A new light-polymerizable zirconia priming agent

(Z-Prime Plus Bisco, Schaumburg, IL, USA) that is amixture of organophosphate and carboxylic acidmonomers has also showed a positive influence on theinitial bond strength regardless of the luting agentused but the durability of the bond was not investi-gated.103,106 Kitayama et al. found that a new primer(AZ Primer, Shofu, Kyoto, Japan) containing a phos-phonic acid monomer 6-MHPA (6-methacryloxyhex-ylphosphonoacetate), was effective in improvingbonding performance.98

Lung et al. evaluated the application of three novelcoupling agents: 2-hydroxyethylmethacrylate, itaconicacid and oleic acid to silicoated zirconia samples.These three coupling agents are cheap, have longershelf life and do not require hydrolysis compared tosilane coupling agents. However, the bond showeddegradation after artificial ageing.105

Jevnikar proposed a non-invasive method where ananostructured alumina coating was achieved byhydrolysis of aluminium nitride (AlN) powder to formcAlOOH (boehmite). Boehmite, when subjected toheat treatment, thermally decomposes to form the alu-mina coating.64 The coating had a high surface area,good wetting ability and achieved a micromechanicalinterlocking as it created nanosized interlamellarspaces, providing a highly retentive surface of Y-TZPceramics for resin penetration.64 The coating thicknesswas found to be only 240 nm, so it did not alter theclinical fit of zirconia restorations. This can be classi-fied as a chemical pretreatment method that increasesthe surface area.Plasma fluorinated zirconia has shown improved

chemical bonding compared to zirconia primers byimproving surface wetting.106 However, these methodsrequire handling of very toxic and hazardous precur-sors like sulphur hexafluoride and tetrachlorosilane.

Artificial ageing

Besides establishing a strong resin-ceramic bond, main-taining this bond under functional conditions of fati-gue, saliva and temperature changes for an acceptable

period of time is a crucial aspect. Artificial ageing givesa measure of bond durability and is done either bywater storage or thermocycling, with thermocyclinghaving a greater impact than water storage at a con-stant temperature.128 A decrease in the resin-ceramicbond strength value after artificial ageing was observedfor many commercial systems in severalstudies.20,39,47,51,55,95,111,113,116,129 However, severalother studies did not subject their specimens to artificialageing, or the ageing period was too short to simu-late clinical conditions.22,39,45,53–55,57,60–62,98,103,106,107

Kumbuloglu et al.114 found that water storage for oneweek or 2000 cycles of thermocycling after water stor-age for 24 hours did not significantly affect the bond-ing properties of both Panavia F and Rely X Unicemcements to air abraded zirconia. In the literature, thereis no consensus on a regimen for artificial ageing andthe cycles are set arbitrarily, ranging from 100 to50 000, which make it difficult to compare results.Gale and Darvel concluded that 10 000 cycles corre-spond to approximately one year of clinical func-tion.127 Moreover, a meaningful test of ceramicbonding should involve cyclic loading, high numbersof low load chewing cycles and water storage for atleast six months.42,112 All these investigations wereperformed under controlled laboratory conditions andno clinical trials were done to validate the results.

Testing methods

Many basic concepts of shear testing used in severalinvestigations have been shown to be incorrect.42,138

Recently many authors have advocated microtensilebond strength testing (MTBS) where the load isapplied perpendicular to the bonded interface and thespecimen size is small.78,84,102,123,131,132,139 However,the MTBS test is a tedious and meticulous methodwhich requires time and effort, especially duringpreparing and sectioning of the specimens, to avoiddamaging the microbars.39,61,133

Furthermore, bond strength test findings should becombined with chemical analysis,117 fractographicanalysis134–137 and cyclic loading.23,42,133 Future stud-ies should also include a combined tooth/composite/porcelain interface in the test complex.42,61,123,130,133

Kern emphasized the need for clinical evidence ofsuccessful bonding of ceramic restorations as a vastmajority of the articles present laboratory research,while clinical trials are rare.125 He reviewed the clini-cal trials with resin bonded alumina and zirconia cera-mic restorations that had limited mechanical retentionand relied solely on adhesion. He concluded that airabrasion at a moderate pressure and using phosphatemonomer containing luting resins provides long-termdurable bonding to alumina and zirconia ceramicunder humid and stressful oral conditions.



CONCLUSIONS

Adhesion between high strength ceramics and resincements remains controversial compared with the highpredictability of silica based ceramics and resincements. To date, many different studies conductedon bond strength have not been able to provide astrong and durable bond, especially after thermalcycling or artificial ageing. The aim of ongoingresearch in this field is to achieve improved bondstrength which can stand the test of time.Air abrasion of acid-resistant ceramics is important

to improve bonding to resin. The use of tribochemicalsilica coating along with zirconia primers or phos-phate monomer containing cements has shown ahigher late bond strength values. The studies whichused a combination of mechanical and chemical meth-ods showed greater bond strength values than studieswhich used these methods alone.There are still some possibilities for improving bond

strength and durability that need to be tested, includ-ing modern cements and adhesive primer materials.Further laboratory studies, as well as controlled clini-cal trials, are needed before clinical recommendationscan be given.

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Address for correspondence:Dr Reena Luthra

House No. 2127, Sector 38-CChandigarh

IndiaEmail: [email protected]



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