Available
online
at
journalhomepage:www.intl.elsevierhealth.com/journals/dema
A
novel
dentin
bonding
system
containing
poly(methacrylicacid)grafted
nanoclay:
Synthesis,
characterization
andproperties
LalehSolhi,MohammadAtai
,AzizollahNodehi,MohammadImani
IranPolymerandPetrochemicalInstitute(IPPI),P.O.Box14965/115,Tehran,Iran
a
r
t
i
c
l
e
i
n
f
o
Articlehistory:
Received7April2012Receivedinrevisedform4June2012Accepted18June2012
Keywords:
DentinbondingsystemNanoclayGraftpolymerizationPoly(methacrylicacid)
a
b
s
t
r
a
c
t
Objectives.
Developinganoveldentinbondingsystemcontainingpoly(methacrylicacid)-grafted-nanoclay(PMAA-g-nanoclay)asreinforcingfiller,withhighstabilityofnanoparticledispersionandimprovedbondstrengthandmechanicalpropertieswerethemainobjectivesof
thisstudy.
Materialsandmethods.
Poly(methacrylicacid)(PMAA)wasgraftedontothepristinesodiummontmorrillonite(Na-MMT)nanoclaysurfaceandcharacterizedusingFTIR,TGA,andX-ray
diffraction(XRD).ThePMAA-g-nanoclaywasincorporatedintoanexperimentaldentinbondingsystemasfillerindifferentconcentrationsandstabilityofnanoclaydispersionin
thediluteadhesive,morphologyofnanoclaylayersinthephotocuredadhesivematrix,shearbondstrengthtocaries-freeextractedhumanpremolarteeth,andmodeoffailurewerestudied.Themechanicalpropertiesincludingdiametraltensilestrength(DTS),flexuralstrength(FS),andflexuralmodulus(FM)werealsoinvestigated.ThemeasuredFMwasalsocomparedtotheoreticalpredictionmodels.
Results.
ThegraftingofPMAAontothenanoclaysurfacewasconfirmedandtheresultsrevealedapartiallyexfoliatedstructureforPMAA-g-nanoclay.Thedispersionstabilityof the
modifiednanoparticlesinthediluteadhesiveincreasedmore
than45timesincom-parisonwiththepristinenanoclay.Theincorporationof0.5wt.%PMAA-g-nanoclaytotheadhesiveresultedinasignificantincreaseinmicroshearbondstrength,DTS,andFS.HigherPMAA-g-nanoclaycontentsresultedinincreasedflexuralmodulus.Theexperimentalflex-ural
moduluswasingoodagreementwiththeHalpin–Tsaitheoreticalmodel.
Significance.
IncorporationofPMAA-g-nanoclayparticlesasnovelfunctionalfillersintoden-tal
adhesivecouldresultinthedevelopmentofbondingsystemswithimprovedphysical,mechanical,andadhesionproperties.©2012AcademyofDentalMaterials.PublishedbyElsevierLtd.Allrightsreserved.
1.
Introduction
Theadhesion
∗
Correspondingauthor
.Tel.:+982148662446;fax:+982144580023.E-mailaddresses:m.atai@ippi.ac.ir,m.atai@yahoo.com(M.Atai).
Dentinisahydratedbiologicalcompositewhichconsistsofwater,organicmatrixandmineralmaterialswithdentinaltubuleslocatedintheradiusofdentininwhichafluidflows
frominsideto
0109-5641/$–seefrontmatter©2012AcademyofDentalMaterials.PublishedbyElsevierLtd.Allrightsreserved.http://dx.doi.org/10.1016/j.dental.2012.06.004
1042
complicatedthanenamel[6].Penetrationofbondingmonomersintothedentinstructures,whichsubsequentlyresultsinahybridlayerofpolymer-izedresinandcollagenfibrilsandstrengtheningofadhesiontodentin,isincreasedbyusingwaterchasingsolventslikeethanol[7].
Formationofthehybridlayeralongwiththeresintagsprovideamicromechanicalretentionbetweenresinanddentin[8,9].Theelasticmodulusoftheadhesivelayer
formedattheresin–dentininterfaceisthelowestcomparing todentinandrestorativematerials[2,10].Thelowelasticmod-
uluscausesthefailureoftherestorationwhentheocclusalloadingismore
thanthestrengthofthelayer[7,11].Ithasbeen
shownthattheincorporationofsmallamountsofnanofillersintopolymericmatricesimprovesmechanicalandfracturepropertiesofthecomposites[12,13].
Na-MMTisananoclaywhichoccursinthenatureasplateletswhichare1nmthickandupto1
mindiameter.Becauseofthehighaspectratio,nanoclayisefficientlyusedtoimprovemechanicalpropertiesofpolymericsystems[14].Incorporationofclaynanoparti-
clesintothedilutesystemssuchasdentinbondings,however,resultsinthefastsedimentationoftheparticlesduetotheirhigherdensities.Surfacemodificationofnanoclayplateletswithapolymer,hasbeenshown,tosolvetheproblemduetothedecreaseinthedensityoftheparticlesandprovidinginter-actionsbetweenthenewlyattachedfunctionalgroupsonthesurfaceofparticleswiththesolvent.Graftingisanefficientmethodtointroducefunctionalgroupsontothesurfaceof nanoparticles[12,15,16].
via
graftpolymerizationof methylmethacrylateandacrylicacidtobeusedasreinforcing fillersfordentaladhesives[15,17].Inthisstudy,theNa-MMT
pristinenanoclaysurfacewasmodifiedwithmethacrylicacidmonomers,whichconsistofcarboxylicgroups.ThecarboxylicacidfunctionalgroupscouldinteractwithCa
2+
ionsofhydroxyapatite[18]promot-
ingtheadhesionbetweentherestorativematerialsanddentin[12,15,18].HavinggraftedPMAAchainsontothesurfaceof nanoclay,thegraftednanoclayplateletswerecharacterizedandtheirdispersionstabilityinanexperimentaldentaladhe-sivewasinvestigated.MechanicalpropertiesandmicroshearbondstrengthofthedentinbondingsystemcontainingPMAA-g-nanoclaywereinvestigated.Theelasticpropertiesoftheadhesiveswerealsomodeledusingtheoreticalpredictionmodels.
2.
Experimental
2.1.
Materials
2-Hydroxyethylmethacrylate(HEMA),2,3-butanedione(BD),2-ethyl-2-hydroxymethyl-1,3-propandioltrimethacrylate(TMPTMA),methacrylicacid(MAA),acetone,ethanolandmethanolwaspurchasedfromMerck(Germany).
tert
-Dodecylmercaptan(TDM)wereobtainedfromFluka(Germany).2,2-Bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane(Bis-GMA)waskindlydonatedbyEvonik(Germany).Na-MMT(Cloisite
®
Na
+
)wasobtainedfromSouthernClaysProduct,Inc.(USA).2-Acrylamido-2-methyl-1-propane-sulfonicacid(AMPS),ammoniumpersulfate,andlithiumchloride(LiCl)werepurchasedfromSigma–Aldrich(Germany).Adper
TM
Sin-gleBond2,acommerciallyavailablenanoparticlecontaining dentinbonding,wasobtainedfrom3MESPE(USA).The37.5%phosphoricacidgel(KerrGelEtchant)wasobtainedfromSDSKerr(USA).Deionizedwaterwasusedthroughoutalltheexperiments.
2.2.
Methods
2.2.1.
Graft
polymerization
of
methacrylic
acid
onto
thesurfaceof
nanoclay
platelets
Thegraftpolymerizationofmethacrylicacidontothesur-faceofnanoclaywascarriedoutaccordingtothepreviousworks[15,17].
Briefly,MAAwasgraftedontotheclayplateletsinanaqueoussolutioninthepresenceofAMPSasreactivesurfactantandTDMasachaintransferagenttocontrolthemolecularweightofthegraftedpolymer.
2.2.2.
Characterization
of
the
PMAA
grafted
nanoclay
ThepristineNa-MMTandPMAA-graftednanoclaywereana-lyzedbyFTIRspectroscopy(EQUINOX55,Bruker,Germany)ataresolutionof4cm
−
1
and32scansintherangeof 4000–400cm
−
1
usingKBrdisctechnique.Thermogravimet-ricanalysesofthepristineNa-MMT,PMAA-g-nanoclayandpurePMAAwereperformed(TGA-1500,PolymerLaborato-ries,UK)fromroomtemperatureto600
◦
Cataheatingrateof10
◦
Cmin
−
1
andunderN
2
atmosphere.X-raydiffractionpatternsofpristineNa-MMTandPMAA-g-nanoclaywerecol-lectedintherangeof2
=2–10
◦
andstepsizeof0.02
◦
,using aPhilipsX-raydiffractometer(Philips,X’pert,Netherlands)withcoppertarget,
=1.54056 ˚Aoperatingatavoltageof 40kVandacurrentof40mA
attherateof2
◦
min
−
1
.The
d
001
spacingswerecalculatedaccordingtotheBragg’sequa-tion:
n
=2
d
sin
.ThePMAA-g-nanoclaywasthenstirredat50
◦
Cfor5daysina10gL
−
1
LiClsolutiontodebondthePMAAchainsfromtheclaysurface[19].Thedebondednanoclaywas
filteredanddried,andthepolymerinthesolutionwaspre-cipitatedinacetone,washedanddried.Thermogravimetricanalysesofthedebondedpolymerandnanoclaywereper-formed.ThemolecularweightofthedebondedpolymerandthemolecularweightoftheunbondedhomopolymerwhichwasextractedduringSoxhelet-extractionweredeterminedbyGPC(GPC,Agilent1100series,USA)usingAquagelcolumnof 7.5mm
×
300mm(ID
×
L)withtheflowrateof1mL
min
−
1
at23
◦
C.
2.2.3.
Preparation
of
adhesives
TheadhesivewaspreparedaccordingtotheformulationshowninTable1.PristineNA-MMTandPMAA-g-nanoclay
wereaddedtotheadhesivein0.2,0.5,1,2and5wt.%.Thefillerswerewelldispersedintheadhesivesolutionbyultrasonicationusingaprobesonicationapparatus(Sono-plusUW2200,Bandelin,Germany)for3min
inanicebath.Thestabilityofthedispersionswasinvestigatedbyasepa-rationanalyzer(LUMiReader
®
416.1,LUM,Germany)working withvisiblelightandintensitiesof25%andtiltof0,for20h(PMAA-g-nanoclay)and30min
(pristinenanoclay),including 256intervals.
1043
Table1–Adhesivecomposition.
Materials%Weight
Bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane(Bis-GMA)142-Hydroxyethylmethacrylate(HEMA)262-Ethyl-2-hydroxymethyl-1,3-propandioltrimethacrylate(TMPTMA)8Urethanedimethacrylate(UDMA) 12Ethanol392,3-Butanedione(BD)1
aa
Thephotoinitiatorwasaddedaftersonicationtopreventun-wantedpolymerizationbeforeapplyingtheadhesive.
2.2.4.
Measurement
of
degree
of
conversion
Adropletoftheadhesivescontaining1%BDasphotoini-tiatorwasplacedonapolyethylenefilm.Thesolventof theadhesivewasgentlyevaporatedfor10sapplyingalow-pressureairstreamandasecondfilmwasthenplacedonittoformaverythinlayer.ThesandwichwasplacedintotheFTIRspectrometer’ssampleholderandtheabsorbancepeaksobtainedbytransmissionmodeofFTIRbeforeandafter40sphotocuringusingadentallightsourcewithanirradi-anceofca.600mWcm
−
2
(Optilux501,SDSKerr,Germany).Thedegreeofconversion(DC%)wasdeterminedfromtheratioofabsorbanceintensitiesofaliphaticCC(peakat1638cm
−
1
)againstinternalreferenceofaromaticCC(peakat1608cm
−
1
2.2.5.
Transmission
and
scanning
electron
microscopies(TEM
and
SEM)
Adhesivespecimencontaining1wt.%PMAA-g-nanoclaywassolventevaporatedandlightcuredinamold.Anultra-microtome(DMU3,Reichert,Austria)wasusedtoprepareapproximately70nmthickTEMspecimen.APhilipsTEM(CM200,FEG,Netherlands)wasusedforTEMobservations.Thecomposite–dentininterfacewasobservedusingSEM(TESCAN,VEGAII,XMU,
CzechRepublic)tostudythemodeoffailureinthemicroshearbondstrengthtest.EDXelementalcomposi-tionanalyzerwasusedtomap
thedistributionofnanoclayinthephotocureddentinbondingsystem.Aprobecurrentof 2.0
×
10
−
9
A,anacceleratingvoltageof30kV,andspotsizeof 500nmwithacollectiontimeof100s,wereusedduringthemapping.TheelementalcompositionsoftheproductswerequantitativelyidentifiedbyenergydispersiveX-rayanalysis(EDXA,Model:QX2,RONTECCo.)whichwascoupledwiththeSEM.
2.2.6.
Mechanical
tests2.2.6.1.
Diametral
tensile
strength.
Diametraltensilestrength(DTS)testwasperformedadoptingtheprocedureofANSI/ADAspecificationno.27forlightcuredresins[20]usingauniversal
testingmachine(STM-20,Santam,Iran)atacross-headspeedof10mmmin
−
1
witha5KNloadcell.
2.2.6.2.
Flexural
strength.
Flexuralstrengthofthesolvent-freeadhesiveswasconductedaccordingtothe3-pointbending methodsuggestedinISO4049[21]usingthesameuniversal
5001000150020002500300035004000
Wavenumber (cm
-1
)
T r a n s m i t t a n c e
pristine nanoclayPMAA-g-nanoclayCarbonyl group of PMAA
Fig.1–FTIRspectrumsofpristineNa-MMTnanoclayandPMAA-g-nanoclay.
testingmachineatacross-headspeedof1mmmin
−
1
witha200Nloadcell.Anumberoftheoriesandmodelshavebeendevelopedtodescribetheelasticpropertiesofpolymericcompositesbasedonthevolumefraction,shape,size,aspectratio,anddistri-butionofthereinforcingparticles,thestiffnessofthematrixandfillerphase,andfiller–matrixinteractions.AmongthemHalpin–Tsaiequationhassuccessfullybeenusedtopredicttheelasticpropertiesofnano-particlecontainingpolymericcomposites[22,23].
Theexperimentaldatawerefittedtothemodelequationsandcompared.
2.2.6.3.
Microshear
bond
test.
Acommer-ciallyavailabledentinbonding(Adper
TM
SingleBond
®
2,3MESPE,USA),ascontrolgroup,wasalsoappliedfollowing themanufacturer’sinstructionandresincomposite(Premise,Kerr,USA)wasusedasthefillingmaterial[24].
2.2.7.
Statistical
analyses
Theresultswereanalyzedandcomparedusingone-wayANOVAandTukeytestatthesignificancelevelof0.05.Thereportedvaluesaretheaverageof10measurementsformicroshearbondstrength,5repeatsforDTS,FS,andFMand3measurementsfordegreeofconversion.
3.
Results
FTIRspectraofthepristineNa-MMTandPMAA-g-nanoclayareshowninFig.1.DeterminedbyGPC,theSoxhelet-
extractedPMAAhomopolymershowsaweightaveragemolecularweight(
M
w
)of7500(PDI=1.8),whilethechro-matogramofthereverseionexchangedebondedPMAA,revealsa
M
w
ofabout2300(PDI=1.4).TheTGAcurvesofthepristineNa-MMT,PMAA-g-nanoclay,nanoclayafterionexchangeprocessandneatPMAAarerepresentedinFig.2.ThePMAAwassynthesizedinthesameconditionsasthegraftpolymerization.ConsideringtheashcontentofneatPMAAinthethermogravimetricanalysis(
≈
5wt.%at550
◦
C),thegraftingPMAApercentagewascalculatedabout43wt.%.Fig.3illustratestheXRDpatternsofpristineNa-MMT,PMAA-g-nanoclayandcuredadhesivecontaining 1wt.%PMAA-g-nanoclay.ComparisonoftheXRDpatterns
1044
0204060801006005004003002001000
Temperature (°C)
W e i g h t l o s s ( % )
nanoclaynanoclay after ion exchangePMAA-g-nanoclayPMAA
Fig.2–TGAthermogramsofPMAA,PMAA-g-nanoclay,pristineNa-MMT
nanoclayandnanoclayafterdebondingthegraftedPMAA.
9.58.57.56.55.54.53.52.51.5
2Theta (°)
I n t e n s i t y ( a r b i t r a r y u n i t s )
nanoclayPMAA-g-nanoclayPMAA-g-nanolay containing adhesive
Fig.3–XRDpatternsofpristineNa-MMT,PMAA-g-nanoclayandadhesivecontaining1wt.%PMAA-g-nanoclay.
showsthatthepeakpositionfrom2
=9.41
◦
,correspond-ingtoaninterlayerspacingof
d
001
=9.39 ˚AforpristineNa-MMT,
isshiftedto2
=6.15
◦
,representinganinterlayerspacingof
d
001
=14.36 ˚AforPMAA-g-nanoclay;thispeakisdisappearedfortheadhesivecontaining1wt.%PMAA-g-nanoclay.TEMimage
oflightcuredadhesivecontaining1wt.%PMAA-g-nanoclayisshowninFig.4,whichindicatesintercala-
tion/exfoliationofPMAA-g-nanoclayparticlesintheadhesivesystem.Fig.5istheseparationanalysisresultswhichshows
thesedimentationbehaviorofthenanoparticlesintheadhe-sivesforthespecimenscontaining1wt.%ofpristineNa-MMTandtreatednanoclay.Thetransmissionoftheadhesivecon-tainingPMAA-g-nanoclaydidnotreach100%during20h.Thetransmissionof80%(atthemiddlepointoftestingtube)wasobtainedafterca.7min
forthepristinenanoclaycontaining adhesivewhereasthesametransmissionwasreachedafterca.315min
fortheadhesivecontainingPMAA-g-nanoclay,whichshowsabout45timesincreaseinthestabilityofthemodifiedparticlesintheadhesivesolution.Toinvestigatethedispersionofmodifiedparticlesintheadhesives,thecrosssectionofcuredadhesiveswasexaminedbyEDXA.TheSimap
ofthecuredadhesivecontaining0.5wt.%PMAA-g-nanoclaywascollected(Fig.6).Figs.7and8showDTSand
Fig.4–TEMmicrographoftheadhesivecontaining1wt.%PMAA-g-nanoclayshowingpartiallydelaminatedclayplatelets.
FSoftheadhesivesamplescontainingdifferentconcentra-tionsofPMAA-g-nanoclay.DTSandFSshowamaximumcorrespondingtotheadhesivecontaining0.5wt.%PMAA-g-nanoclaysignificantlyhigherthanthoseoftheunfilledresin(
p
=0.000).Fig.9presentstheFMoftheadhesivescontaining
PMAA-g-nanoclay.AnincreasingtrendisobservedintheFMoftheadhesivecompositesupontheincreaseinfillercon-tent.ThemodelpredictionsfortheFMofadhesivescontaining differentamountsofPMAA-g-clayarealsocalculatedandpre-sentedinFig.9.DC%valuesoftheadhesiveswereintherange
of78–85%andtherewerenosignificantdifferencebetweentheDC%oftheadhesiveswithdifferentfillercontentsandSingleBond
®
(
p
>0.05).Fig.10showsthemicroshearbondstrengthoftheadhe-sivescontainingdifferentpercentagesofPMAA-g-nanoclay.Itrevealsasignificantincrease(
p
=0.025)inthemicroshearbondstrengthoftheadhesivecontaining0.5wt.%PMAA-g-nanoclay.InFig.11thepenetrationoftheadhesiveintothedentinaltubulesisclearlyobservedinlowfillerconcentra-tions(0.5wt.%)whilemostofthetubulesareleftunfilledinhighconcentrations(5wt.%).Agglomerationoftheparticlesinhigherconcentrationsofthefillersresultsinthedecreaseoftheadhesivepenetrationintothedentintubules.Thefailuremodeintheshearbondtestwasmostlyadhesivefromtheadhesive–dentininterfacewhichisrepresentativelyillustratedinFig.12.
4. Discussion
Inthegraftpolymerization,thepristineNa-MMT
isdispersedinwaterinthepresenceofareactivesurfactant,AMPS,whichcontainsamidoandsulfonicacidgroupsinitsstructure.IthasbeensuggestedthattheinteractionofAMPSwithclayoccursbyprotontransferfromsulfonicacidtonitrogen,toformaprotonatedamidogroupandionexchangewithsodiumionsonthesilicatelayers[25].AMPScanalsobeadsorbed
ontothesurfaceoftheclaygalleriesbyformationofhydro-genbondsbetweenitsamidogroupsandwatermolecules