A Novel Dentin Bonding System Containing Poly Methacrylic Acid Grafted Nanoclay Synthesis, Characterization and Properties

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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
Themainfunctionofdentaladhesivesistobonddentalrestorativematerialstothetoothstructure[1].
Theadhesion
Correspondingauthor
.Tel.:+982148662446;fax:+982144580023.E-mailaddresses:m.atai@ippi.ac.ir,m.atai@yahoo.com(M.Atai).
isnecessarytoavoidsecondarycarries,sensitivityafterrestoration,colorchange,andmicroleakage[2].
Dentinisahydratedbiologicalcompositewhichconsistsofwater,organicmatrixandmineralmaterialswithdentinaltubuleslocatedintheradiusofdentininwhichafluidows
 
frominsideto
0109-5641/$seefrontmatter©2012AcademyofDentalMaterials.PublishedbyElsevierLtd.Allrightsreserved.http://dx.doi.org/10.1016/j.dental.2012.06.004
 
1042
 
outsidedirection[3–5].Duetothewetanddynamicstruc- ture,adhesiontodentinismore
 
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].
Inourpreviousworks,Na-MMTpris-tinenanoclaysurface,wasmodified
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,acommerciallyavailablenanoparticlecontainindentinbonding,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
and32scansintherangeo4000–400cm
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
,usinaPhilipsX-raydiffractometer(Philips,X’pert,Netherlands)withcoppertarget,
=1.54056 ˚Aoperatingatavoltageo40kVandacurrentof40mA
 
attherateof2
min
1
.The
d
001
 spacingswerecalculatedaccordingtotheBraggsequa-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)withtheowrateof1mL
 
min
1
at23
C.
2.2.3.
 
Preparation
 
of 
 
adhesives
TheadhesivewaspreparedaccordingtotheformulationshowninTable1.PristineNA-MMTandPMAA-g-nanoclay wereaddedtotheadhesivein0.2,0.5,1,2and5wt.%.Thellerswerewelldispersedintheadhesivesolutionbyultrasonicationusingaprobesonicationapparatus(Sono-plusUW2200,Bandelin,Germany)for3min
 
inanicebath.Thestabilityofthedispersionswasinvestigatedbyasepa-rationanalyzer(LUMiReader
®
416.1,LUM,Germany)working withvisiblelightandintensitiesof25%andtiltof0,for20h(PMAA-g-nanoclay)and30min
 
(pristinenanoclay),including 256intervals.
5
 
1043
Table1Adhesivecomposition.
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-tiatorwasplacedonapolyethylenelm.Thesolventotheadhesivewasgentlyevaporatedfor10sapplyingalow-pressureairstreamandasecondlmwasthenplacedonittoformaverythinlayer.ThesandwichwasplacedintotheFTIRspectrometerssampleholderandtheabsorbancepeaksobtainedbytransmissionmodeofFTIRbeforeandafter40sphotocuringusingadentallightsourcewithanirradi-anceofca.600mWcm
2
(Optilux501,SDSKerr,Germany).Thedegreeofconversion(DC%)wasdeterminedfromtheratioofabsorbanceintensitiesofaliphaticCC(peakat1638cm
1
)againstinternalreferenceofaromaticCC(peakat1608cm
1
)beforeandaftercuringofthespecimen[17].
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-pointbendinmethodsuggestedinISO4049[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.1FTIRspectrumsofpristineNa-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.
 
Themicroshearbondtestwasperformedaccordingtopreviousworks[12,15].
Acommer-ciallyavailabledentinbonding(Adper
TM
SingleBond
®
2,3MESPE,USA),ascontrolgroup,wasalsoappliedfollowinthemanufacturer’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-nanoclayandcuredadhesivecontainin1wt.%PMAA-g-nanoclay.ComparisonoftheXRDpatterns
5
 
1044
 
0204060801006005004003002001000
Temperature (°C)
   W  e   i  g   h   t   l  o  s  s   (   %   )
nanoclaynanoclay after ion exchangePMAA-g-nanoclayPMAA
Fig.2TGAthermogramsofPMAA,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.3XRDpatternsofpristineNa-MMT,PMAA-g-nanoclayandadhesivecontaining1wt.%PMAA-g-nanoclay.
showsthatthepeakpositionfrom2
=9.41
,correspond-ingtoaninterlayerspacingo
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
 
forthepristinenanoclaycontaininadhesivewhereasthesametransmissionwasreachedafterca.315min
 
fortheadhesivecontainingPMAA-g-nanoclay,whichshowsabout45timesincreaseinthestabilityofthemodifiedparticlesintheadhesivesolution.Toinvestigatethedispersionofmodifiedparticlesintheadhesives,thecrosssectionofcuredadhesiveswasexaminedbyEDXA.TheSimap
 
ofthecuredadhesivecontaining0.5wt.%PMAA-g-nanoclaywascollected(Fig.6).Figs.7and8showDTSand
Fig.4TEMmicrographoftheadhesivecontaining1wt.%PMAA-g-nanoclayshowingpartiallydelaminatedclayplatelets.
FSoftheadhesivesamplescontainingdifferentconcentra-tionsofPMAA-g-nanoclay.DTSandFSshowamaximumcorrespondingtotheadhesivecontaining0.5wt.%PMAA-g-nanoclaysignificantlyhigherthanthoseoftheunfilledresin(
 p
=0.000).Fig.9presentstheFMoftheadhesivescontaining  PMAA-g-nanoclay.AnincreasingtrendisobservedintheFMoftheadhesivecompositesupontheincreaseinfillercon-tent.ThemodelpredictionsfortheFMofadhesivescontainindifferentamountsofPMAA-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
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