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2/15/2016 NOVELSUPERABSORBENTHYDROGELCOMPOSITEBASEDONPOLY(ACRYLAMIDECOACRYLATE)/NONTRONITE:CHARACTERIZATIO

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Qum.Novavol.38no.3SoPauloMar.2015

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http://dx.doi.org/10.5935/01004042.20150008

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NOVELSUPERABSORBENTHYDROGEL
COMPOSITEBASEDONPOLY(ACRYLAMIDECO
ACRYLATE)/NONTRONITE:CHARACTERIZATION
ANDSWELLINGPERFORMANCE

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RenanC.F.Leitoa,CceroP.deMourab,LindomarR.D.
daSilvac,NgilaM.P.S.Ricardoc,JudithP.A.Feitosac,Edvani
C.Munizd,AndrR.Fajardode*,FranciscoH.A.Rodriguesad

Automatictranslation

CoordenaodeQumica,UniversidadeEstadualValedoAcara,Campus
daBetnia,62040370SobralCE,Brasil
b

DepartamentodeQumica,InstitutoFederaldeEducao,Cinciae
TecnologiadoCear,63900000QuixadCE,Brasil
c

DepartamentodeQumicaOrgnicaeInorgnica,UniversidadeFederaldo
Cear,60455760FortalezaCE,Brasil
d

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DepartamentodeQumica,UniversidadeEstadualdeMaring,87020900
MaringPR,Brasil
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CentrodeCinciasQumicas,FarmacuticasedeAlimentos,Universidade
FederaldePelotas,96010900PelotasRS,Brasil

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ABSTRACT
Anovelsuperabsorbenthydrogel(SH)compositebasedonapoly(acrylamidecoacrylate)matrixfilledwith
nontronite(NONT),aFe(III)richmemberofthesmectitegroupofclayminerals,isdescribedinthismanuscript.A
varietyoftechniques,includingFTIR,XRD,TGA,andSEM/EDX,wereutilizedtocharacterizethisoriginalcomposite.
ExperimentaldataconfirmedtheSHcompositeformationandsuggestedNONTwascompletelydispersedinthe
polymericmatrix.Additionally,NONTimprovedthewateruptakecapacityofthefinalmaterial,whichexhibitedfast
absorption,lowsensitivitytothepresenceofsalt,highwaterretentionandapHsensitiveproperties.These
preliminarydatashowedthattheoriginalSHcompositepreparedherepossesseshighlyattractivepropertiesfor
applicationsinareassuchastheagriculturefield,particularlyasasoilconditioner.
Keywords:compositesuperabsorbenthydrogelcompositesnontroniteswellingperformance

INTRODUCTION
Superabsorbentshydrogels(SH)arethreedimensional(3D)crosslinkednetworksbuiltbyhydrophilicpolymers
thatcanabsorb,swell,andretainlargecontentsofwateroraqueousfluids.Ingeneral,SHsshowexcellent
propertieswhencomparedtothetraditionalwaterabsorbingmaterials.Asconsequence,theinterestaboutthey
haveincreasedconsiderableandtheresultistheSHsutilizationinthemostvariedfields,suchashygienic
industries,agriculture,pharmaceutical,biomedical,biotechnology,andothers.1SomeSHmatricesareableto
swellupto1,500timesrelativetoitsdryweight2andmaintainingtheirstructure,whichisformedbyaporous
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structure.Suchmorphologyaswelltheaveragedporoussize,andporoussizedistribution,aredependenton
severalfactorssomeofthemassociatedtothemethodusedforhydrogelpreparation(thepolymertype,
concentrationofpolymerand/ormonomersolution,crosslinkingagent,etc.)andothers.3Beyondthefactors
associatedtothepreparingconditions,theexternalstimuli(temperature,solvent,ionicstrength,etc.)can
affecttheSHproperties.3Inspecificconditions,stimuliresponsiveSHintheswollenstatecancollapsein
responsetoenvironmentalstimulichangesreleasingtheabsorbedwaterorfluid.Duringthedeswellingprocess,
theporoussizeofa3Dnetworkchangeandanyencapsulatedsolutecaneventuallydiffuseoutwardsof3D
matrix.4Theswellingdeswellingswellingcycleisoftenreversible.2Thisisakeyfactorforapplicationof
stimuliresponsivehydrogelsinseveralfields.5,6
SincetheSHsappearing,theresearcheshavebeenfocusedontheirupgrading.Differentmaterialshavebeen
testedtoformulateandtotailorthiskindofmaterialforthoseapplications.Inrecentyears,clayshave
acquiredimportantroleintheformulationofaplentyorganic/inorganicbasedsuperabsorbentcomposites,
especiallytoimprovetheirswellingproperties.Thisstatementcanbeprovedbyabriefsearchintheliterature,
whereispossibletofindoutseveralworksdiscussingthepreparationofsuperabsorbenthydrogelcomposites
withdifferentclays,suchaskaolin,montmorillonite,attapulgite,mica,sericite,sepiolite,andvermiculite.39On
theotherhand,nontronite(NONT),otherclaywithpotentialtoactasfillerinsuperabsorbentmatrices,has
beenpoorlyexplored.NontroniteisaFe(III)richsmectitewithadioctahedralstructureandlowdegreeof
aluminumhydroxide,withlamellarchargeoriginatedintetrahedrallayer,duetosubstitutionsofcationsof
silicon(Si4+)forthecationsofaluminum(Al3+),andwithaconcentrationofFe(III)higherthan3.0mol%.7
AlmostalloctahedralaluminumionspresentinsmectitesarereplacedfortheFe(III)ionsinNONT.The
chemicalrepresentationofNONTis((M+)x nH2O(Fe+3))4(Si4x Alx )O20(OH)4,whereM+representsthecationsof
ioniccompensationexchangeable.8ThenegativechargeexcesscanbeattributetothesubstitutionofSi4+by
Al3+cationsintothetetrahedralsitesinthesilicalayer.Additionaly,intheoctahedralsitesofNONT,practically
alltheoctahedralaluminumisreplacedbyFe(III)ions.9
ThedevelopmentofanovelSHfilledwithNONTisdescribedinthismanuscriptinordertoevaluatethe
potentialofthisclaytoactasfillerandtostudyitseffectonswellingproperties.Additionaly,thecomplete
characterizationconcerningthestructureofthisoriginalmaterialisprovidedinthismanuscript.Thedataand
discussionpresentedhereincreasetherangeofapplicabilityofthispoorlyexploredclayandcontributeto
formulationortailoringofsuperabsorbenthydrogelcompositestobeappliedwithbetterefficiencyandbenefits
indifferentfields.

EXPERIMENTAL
Materials
Acrylamide(AAm),acrylicacid(AAc),N,N,N',N'tetramethylethylenediamine(TEMED),ascatalyst,and
potassiumpersulfate(K2S2O8),asinitiator,werepurchasedfromSigmaAldrich(USA).N,N
methylenebisacrylamide(MBA),ascrosslinker,waspurchasedfromPharmaciaBiotech(USA).Allthese
chemicalshaveanalyticalgradeandwereusedasreceived.Potassiumacrylatesalt(KAc)waspreparedby
neutralizationofacrylicacidwithpotassiumhydroxide.NONT,kindlydonatedbyCompanyBentoniteNortheast
(Paraba,Brazil),waspreviouslygroundandsievedthrougha325mesh(44m).Theclayhascationic
exchangecapacityof145miliequivalent(meq)per100gramsandchemicalcompositionevaluatedbyXray
fluorescence:silicon(5.32meq/g),iron(0.82meq/g),aluminium(0.60meq/g),sodium(0.48meq/g),
magnesium,(0.12meq/g)andcalcium(0.08meq/g).Thecommercialhydrogels(labeledasPAMACOM)
producedforagricultureuseswerepurchasedinalocalagriculturalproductsandsuppliesstore(Cear,Brazil).
Accordingtomanufacturer'sinformation,PAMACOMisbasedonacrylatemonomerssalts(sodiumand
potassium).ThePAMACOMsamplesweresievedinordertoobtainparticlesintherangeof9to35mesh(2.00
0.71mm).

Poly(acrylamidecoacrylate)SHformation
Thepoly(acrylamidecoacrylate)SHs(labeledasPAMACRYL)werepreparedaccordingtothefollowprocedures.
Inaroundflask,distilledwater(30mL)wasmagneticallystirredandN2(g)degasedfor15min.Subsequently,
AAM(2.1g)andKAc(3.5g)wereaddedtothereactionsystem.Afterawhile,K2S2O8(16.2mg)wasadded,in
ordertopromotetheradicalformation.MBA(0.05,0.1,and0.2mol/wt%relativetothemonomerstotalmass)
andTEMEDsolution(0.57gL1100L)werealsoadded.Thereactionsystemwasclosedandkeptunder
magneticstirringandN2(g)atmosphereuptothegelformation(~30min).Tocompletethegellingprocessthe
systemwaslefttorestby15h.Atlast,theasobtainedPAMACRYLhydrogelwascollectedandcutintosmall
pieces,whichwereextensivelywashedwithdistilledwatertoremovesomeunreactedchemicals.Then,the
PAMACRYLhydrogelwasovendriedat70Cuptoconstantweightandthensmashed.Thesampleswere
samplesweresievedinordertoobtainparticlesintherangeof9to35mesh(2.000.71mm).

Poly(acrylamidecoacrylate)/nontroniteSHcompositeformation

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Thepoly(acrylamidecoacrylate)/nontroniteSHcompositewaslabeledasPAMACRYL/NONT.Theproceduresto
preparetheSHscompositeweresimilartothoseusedtopreparethePAMACRYLgels.However,differentNONT
contentswereaddedtoreactionsystem.ThreesamplesofPAMACRYL/NONTwerepreparedhereintheNONT
contentswerefixedat5,10,and20wt/wt%relativetothemonomerstotalmass.Thesesampleswerelabeled
as:PAMACRYL/NONT5,PAMACRYL/NONT10,andPAMACRYL/NONT20,respectively.Foreachcompositesample,
theacrylamideandacrylatemonomers(AAmandKAc)weresolubilizedinanaqueousdispersionofnontronite.
Theresultingsolutionwasstirredfor30minandthenK2S2O8,MBAandTEMEDsolutionwereaddedtothe
reactionsystem.Itisworthytosaythatearlierthemonomersaddition,theaqueousdispersionofnontronite(~
30mL)waskeptundermagneticstirringfor24h.

Fouriertransforminfraredspectroscopy(FTIR)
FTIRspectraofNONT,SHandSHscompositeswererecordedusingaShimadzuspectrometer(modelFTIR
8300,Japan)operatingintheregionfrom4000to500cm1withresolutionof4cm1and64scanacquisitions.
DrysamplesweremixedwithKBrpowderandpressedintopelletsforspectrumacquisition.

Xraydiffraction(DRX)
Xraydiffraction(XRD)measurementswereperformedusingaShimadzudiffractometer(modelXRD600,Japan)
equippedwithaCuKradiationsource(30kV20mA)inascatteringangle(2)from5to70,witha
resolutionof0.02,atascanningspeedof2/min.

Thermogravimetry(TGA)
Thermogravimetricanalyses(TGA)werecarriedoutinaSimultaneousThermalAnalysesSystem,Netzsch
(modelSTA409PG/4/GLuxx,Germany)withascanningrateof10C/minundergasN2flowingat20mL/min
inarangeoftemperatureof22to800C.

Scanningelectronmicroscopy/energydispersiveXrayanalyzer(SEM/EDX)
Scanningelectronmicroscopy(SEM)imageswererecordedusingaShimadzu(ModelSS550Superscan,Japan)
microscopecoupledwithanenergydispersiveXray(EDX)analyzer.Priortotheanalyses,theSHandSHs
compositeswereimmersedindistilledwateratroomtemperatureuptotheequilibriumswelling(~24h).
Then,thesampleswerefrozenusingliquidnitrogen.Thereafter,thefrozensampleswerelyophilizedona
freezedryer(Christ,Alpha12LDPlus,Germany)at55Cfor24h.Thedriedsampleswerecarefully
fracturedandthengoldcoatedbysputteringbeforeSEM/EDXvisualization.

Wateruptakecapacity
TheabilityofPAMACRYLandPAMACRYL/NONT(520)hydrogelstoabsorbwaterwasevaluatedbyagravimetric
method.Forthis,drygelssamples(15mg)wereplacedincruciblesfilters(porosityn0)premoistenedand
withadriedouterwall.Thissetwasinsertedindistilledwater(atroomtemperature)insuchawaythegel
samplewascompletelysubmerged.Afterpredeterminedtimeintervals,theset(filterwiththesample)was
removedthefilterouterwallwasdriedandthenthesetwasweighed.Thisprocedurewascarriedoutthree
timestoeachgelsample(n=3).ThewateruptakecapacityofeachsamplewasdeterminedusingEquation
(1),wheretheparameterWestimatesthemassofwaterabsorbedpergramofgel,misthemassofthe
swollenmaterialandm0isthemassofthedrymaterial.10Thismethodisconventionalandversatilebecauseit
allowsfollowingtheswellingkineticsofeachgelsample.

Effectofsaltsolutiononwateruptakecapacity
TheeffectofdifferentsaltsolutionsonthewateruptakecapacityofPAMACRYLandPAMACRYL/NONT(520)
hydrogelswasevaluatedhere.Forthis,hydrogelssampleswereimmersedindifferentsaltaqueoussolutions
withconcentrationsrangingfrom0.001to0.10molL1atroomtemperature.NaClandNaHCO3solutionswere
usedforstudyingtheanioneffectwhileNaClandCaCl2solutionswereusedforevaluatingthecationeffecton
theswellingproperties.Thewateruptakecapacityofeachhydrogelsamplewasdeterminedaccordingtothe
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gravimetricmethoddescribedinthesection2.4.1.10Again,foreachsampletheprocedureswerecarriedoutin
triplicates(n=3).

EffectofpHonwateruptakecapacity
TheeffectofpHonwateruptakecapacityofSHandSHscompositewasevaluatedbyimmersionofthesamples
indifferentbufferssolutions(pH2.4,9.4,and7.4)withconstantionicstrength(0.1molL1)atroom
temperature.Thewateruptakecapacityofeachhydrogelsamplewasdeterminedaccordingtothegravimetric
methoddescribedinthesection2.4.1.10Foreachsampletheprocedureswerecarriedoutintriplicates(n=3).
Atleast,theeffectoftheswelling/deswellingcyclesontheSHandSHscompositeswateruptakecapacitywas
alsoevaluated.Foreachrun,thehydrogelsamplewasimmersedindistilledwater(atroomtemperature)for
24handthentheWparameterwasdeterminedasdescribedabove.Afterwards,theswollensamplewasputin
ovenat70Cfor24h.Thedrysamplewasresubmittedtotheswellingprocessagain.Thiscyclewasrepeated
5timesforeachhydrogelsample.

RESULTSANDDISCUSSION
Characterization
TheFTIRspectrumofNONT(Figure1a)showedbands(28403000cm1)assignedtoCHbondsstretching
characteristicofalkanes,whichevidencesthepresenceoforganicmattercommonlyaggregatetosuch
material.Aspreviouslyreported,thesebandsarefoundinthe29292858cm1wavenumberregion.11The
broadbandbetween30003750cm1isassignedtotheOHstretchingofhydroxylgroupsbelongingtothe
octahedrallayersandtothewatermoleculescoordinatedtocationsforioniccompensation.12Thebands
assignedtoSiObondsstretchingareshowedin960to1150cm1region.Thebandsareinfluencedbythe
compositionofatomsonoctahedrallayer.Isworthytosaythebandat1039cm1,alsoassignedtoSiObond
stretching,isduetothepresenceofoctahedralcoordinatedironatoms.12Thebandsfoundinthewavenumber
regionbetween550960cm1areassignedtooctahedraldeformationsofROHgroups,inwhichRcanbeiron
ormagnesiumions.Finally,thestrongbandcloseto550cm1isassignedtothestretchvibrationsofionsin
octahedralplaneandtoitsadjacentoxygenatoms.12TheFTIRspectrumofPAMACRYL(Figure1b)showbands
at1670and1564cm1,whichareassignedtotheC=OandNHstretching,confirmingthecopolymerformation.
TheFTIRspectrumofPAMACRYL/NONT10(Figure1c)showedallthecharacteristicsbandsobservedfor
PAMACRYL.Additionaly,thebandsat1035and470cm1,whichareassignedtotheSiObondsproceedingfrom
theNONTincorporation,areobservedinFigure1c.

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Figure1FTIRspectraof(a)NONT,(b)PAMACRYL,and(c)PAMACRYL/NONT10

TheXRDpatternofNONT,showedinFigure2a,providesimportantinformationaboutitsmainmineral
constituentsandstructuralparameters.TheXRDbasalpeaksat7.14(001)and19.78(061)arecharacteristic
ofclayslikeNONT,adioctahedralsmectite.13Similarly,thepeaksat21.7(101)and26.6(011)characterize
thepresenceofsilicaminerals,anyoftheformsofsilicondioxide(SiO2),includingquartz,tridymite,
cristobalite,coesite,stishovite,lechatelierite,andchalcedony,whichareconsideredasclaysimpurities.These
mineralsshowparticlesizesimilartothosefoundforclayparticlesandasconsequencetheyhardlyevercanbe
separateoftheclay.MihaboubandVreysenobtainedsimilarXRDpatternsofNONTintheirworks.13,14TheXRD
patternsofPAMACRYL/NONT5,PAMACRYL/NONT10andPAMACRYL/NONT20(Figure2ac)didnotshowthe
characteristicbasalpeaksofNONT,regardlesstheconcentrationofclayinsuchgels.Thissuggeststhe
copolymerizationofAAmandKAcmonomerstopoly(acrylamidecoacrylate)andsubsequentcrosslinking
processhaspromotedagooddispersionofNONTplateletsintheSHscomposites.Suchdispersionoccursdueto
formationofHbondsbetweentheamideandacidgroupspresentontheSHmatrixandwatermolecules
surroundingtheexchangeablecationsonNONT.Further,iondipoleinteractionsamongtheacrylategroupsand
theinterlayerexchangeablecationscanbeformed.Bothinteractionsmightleadtoaslightincreasinginthe
basalspacingofNONT.

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Figure2XRDdiffractogramsof(a)PAMACRYL/NONT5,(b)PAMACRYL/NONT10,(c)PAMACRYL/NONT20,and(d)NONT

TheXRDpatternscorroboratewiththeFTIRdataandbothconfirmtheformationofthesuperabsorbenthydrogel
compositeandevidencethepresenceofNONTinthepoly(acrylamidecoacrylate)SHmatrix.Theeffectofthe
NONTincorporationonthethermalpropertieswasevaluatedbythermogravimetricanalyses(TGA)(Figure3).

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Figure3TGAandDTGcurvesofPAMACRYLandPAMACRYL/NONT10

ThePAMACRYLandPAMACRYL/NONT10TGAcurvesshowclearlythreestagesfortheweightlosses.Thefirst
stage(50200C)canbeattributedtothemoistureandvolatilecompoundslossesbythesamples.Following,
inthetemperaturerangeof300450Ctheweightlossesareattributedtothethermaldecompositionofthe
acrylateandamidesidegroupsofthecopolymersandalsoMBAmoietiesspreadintheSHmatrix,leadingto
theevolutionofammoniaandothergasesforinstance.Duringthisperiod,theonsetsinthePAMACRYLand
PAMACRYL/NONT10TGAcurvesaresimilarhoweverispossibletoobserveaslightincreaseinthermalstability
oftheSHcompositeduetoNONTpresence.ForPAMACRYL,thermaldecompositiontemperatureis391C
(33.5%),whileforPAMACRYL/NONT10is399C(33.3%).Thelaststagewasattributedtothebreakageof
copolymerchains,inwhichwasobservedadisplacementforhighertemperatureswhenareNONTis
incorporatedintheSHmatrix.Additionally,thetotalresidueat900Cwasc.a.1.55%forPAMACRYLandc.a.
25.46%forPAMACRYL/NONT10.Figure3showstheNONTincorporationonthePAMACRYLmatrixhaspositive
effectonitsthermalstability.
ThefracturemorphologyoftheSHandSHcompositewasexaminedbySEMasshowninFigure4.Asitisclear
fromFigure4a,PAMACRYLshowsmicroporoussurface,withlargeandirregularporesheterogeneously
distributed.SuchmorphologyallowsSHabsorbinghighamountsofliquid.Ontheotherhand,itcanbeseenin
Figure4bthesurfacemorphologyofsuperabsorbentchangesduetotheNONTincorporationinitsformulation.
ThemorphologyofthePAMACRYL/NONT10superabsorbentexhibitrugged,coarsened,andcorrespondinglyloose
surfaces.Undulantandcoarsenedsurfacesincreasethesurfacecontactarea,whichmakeseasythediffusionof
liquidinwardtheSHmatrix.Thisensureshighwateruptakecapacityforthefinalsuperabsorbentcomposite.
Additionaly,suchmorphologydemonstratesthefiller(NONTinthiscase)iscompletelyincorporatedwithinthe
copolymerchainsandwelldispersedintheSHmatrix(seeFigure4b).Suchsceneryisverydesirablesincethe
highdispersionofNONTparticlesintheSHnetworkpreventsflocculationofclayparticlesandenhancesthe
wateruptakecapacityoftheSHcomposite.

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Figure4SEMimagesof(a)PAMACRYLand(b)PAMACRYL/NONT10(fractureimagesmagnificationx3000scalebar5m)

InadditionfromtheSEMimages,EDXspectraofthePAMACRYLandPAMACRYL/NONT10werecollectedto
evaluatetheirelementalcomposition.AscanbeseeninFigure5,bothPAMACRYLandPAMACRYL/NONT10
spectrashowedthreewellresolvedpeaksaccountingtotheelementsC,O,andK.Ontheotherhand,theEDX
spectrumofPAMACRYL/NONT10(Figure5)alsoshowsthecharacteristicpeaksassignedtotheelementsSiand
Al.Theappearingofsuchpeakscorroborateswiththedataobtainedbyothertechniquesutilizedhere.Allof
themconfirmthesuccessfullyformationoftheSHcomposite.Further,toconfirmtheNONTdispersionintothe
SHmatrix,theSielementaldistributionmap(EM)wasrecordedfromPAMACRYL/NONT10sample(Figure5).As
itisclearintheEMfigurethecharacteristicSielementpresentintheNONTstructurecanbeeasilyobserved
throughtheentiremappedregion.TheEMconfirmseithertheNONTpresenceasitshighdispersion.

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Figure5EDXspectraof(a)PAMACRYLand(b)PAMACRYL/NONT10

Swellingperformance
Typically,hydrogelsandsuperabsorbenthydrogelsconsistofphysicallyorchemicallycrosslinkedhydrophilic
polymerchainsformingathreedimensionalnetwork.Theprocessofswellingofahydrogelisdrivenby
chemicalandphysicalforcesandbytheconsequentelasticresponseoftheconstituentchainsofthematrix.
Swellingisprimarilyduetothepenetrationofaqueousliquidinwardthehydrophilicpolymermatrixbycapillary
anddiffusionforces.Thus,liquidisabsorbedbyhydrophilicgroupssuchashydroxyl,carboxyl,andaminodue
toformationofHbonds.15Thewateruptakecapacityandtherateofswellingofhydrogelhasadirectrelation
tointernalfactors,suchasthevariationofosmoticpressurebetweentheinteriorofthegelandtheexternal
mediathecrosslinkingdensitytheaffinitybetweenthehydrogelandtheliquidandbyexternalfactors(i.e.
presenceofsalts,pH,andtemperature,etc.)Forhydrogelcompositesotherfactorhastobeconsideredthe
fillercontent.BeforetocomparetheswellingperformanceoftheSHcompositeinrelationtotheconventional
SHsomeoptimizationconditionsweretested.Besides,twovariablesfortheSHformulationsweretested:(i)
theeffectofNONTcontentand(ii)theeffectofMBAcontent(crosslinkeragent)onthewateruptakecapacity.
AsdemonstratedinFigure6a,theincorporationof10wt%ofNONTontheSHformulationleadstoamaximum
inthewateruptakepropertywhencomparedtotheotherformulations.AccordingtoWangandXie,16cations
presentintheclayincreasethehydrophilicityofthecompositeandthedifferenceinosmoticpressurebetween
thepolymerandtheoutsidesolution.Ontheotherhand,theincorporationof20wt%ofNONTresultedina
significantreductionintheWprofile.ThisbehaviorcanbeattributedtoextracrosslinkingpointsintheSH
networkduetotheNONTincorporation.Highcrosslinkingdensityreducesthematrixelasticityandthewater
uptakecapacityisnegativelyaffected.10,17Furthermore,theentrapmentofNONTintheinterconectedporous
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structure,causedbytheexcessivecontentofclayparticles,decreasestheemptyspaceinsidetheSHmatrix,
whichconsequentlydecreasesthecontentofabsorbedwater.TheSHwith5wt%ofNONTshoweda
intermediarewateruptakebehaviorbetweenthoseothertwoformulations.Accordingtothesedata,theSH
compositeformulatedwith10wt%ofNONT(thesamplePAMACRYL/NONT10)wasutilized,asreferenceofSH
composite,forallthesubsequentswellingassays.

Figure6(a)EffectofNONTand(b)MBAcontentsonthewateruptakecapacityoftheSHcomposite(*PAMACRYL/NONT10
wasutilizedtoperformtheassayshowedinb)

PAMACRYL/NONT10werepreparedusingdifferentcontentsofMBA,acrosslinkingagentthatplaysanimportant
roleintheswellingprocess.18AccordingtotheFlory'stheory,19thecrosslinkingdensityisakeyfactorthat
influencesthewateruptake.Inorder,thewateruptakeisinverselyproportionaltothecrosslinkdensity.
Herein,thecontentofMBAutilizedinthePAMACRYL/NONT10formulationwasvariedfrom0.05to0.20mol/wt
%.AsitcanbeobservedinFigure6bthewateruptakecapacityofPAMACRYL/NONT10decreasessignificantly
asthecontentofMBAisincreasedfrom0.10to0.20mol/wt%.Ontheotherhand,suchvariationwasnot
observedwhentheMBAcontentis0.05or0.10mol/wt%.ThePAMACRYL/NONT10swellingprofileisthesame
forbothformulations.WhenhighMBAcontents(>0.10mol/wt%inthiscase)areusedintheSHcomposite
formulationagreatnumberofcrosslinkingpointsamongthecopolymerchainsareformed.Consequently,the
crosslinkingdensityincreasesandtheSHmatrixgetrigidity.Thisreflectsinasmallernetworkexpansionand
hindersthewaterdiffusionavoidingitsswelling.20Accordingtothesedata,theMBAcontentusedtoprepare
bothPAMACRYLandPAMACRYL/NONT10samplesappliedinthesubsequentswellingassayswasfixedin0.05
mol/wt%.
Figure7showstheswellingkineticscurvesofPAMACRYL,PAMACRYL/NONT10,andPAMACOMindistilledwater
mediaatroomtemperature.HerethelabelPAMACOMwasusedtodenoteacommercialSHbasedon
poly(acrylamide).

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Figure7SwellingkineticscurvesforPAMACRYL,PAMACRYL/NONT10,andPAMACOM

TheswellingdatadisplayedinFigure7highlightallthesampleshavehighequilibriumswellingratio,acommon
characteristicfoundinsuperabsorbenthydrogels(SH).ThemainpropertyofSHsistheircapacityofabsorbs
hundredtimesitsownweightofwater.PAMACRYLandPAMACOMsamplesshowedverysimilarswellingkinetics
curves,wheretheequilibriumswellingisachievedfastinbothcasesandsuchequilibriumremainsuptothe
assaysend.TheWvaluescalculatedforPAMACRYLandPAMACOMattheequilibriumwere645and634
gH2O/ggel.FromFigure7ispossibletoobservePAMACRYL/NONT10samplepresentedthehighestwateruptake
capacity.TheWvaluecalculatedtothePAMACRYL/NONT10sampleattheequilibriumwas1,104gH2O/ggel,
almosttwotimeshigherthanthosecalculatedforPAMACRYLandPAMACOM.Theswellingkineticcurveof
PAMACRYL/NONT10showedaquickincreasingduringthefirst15minofimmersion,reachingabout90%ofthe
equilibriumvalueuptothisimmersiontime,followedbyaslowerprocessuntiltheequilibriumbeingreachedat
about30min.Themechanismthatdrivestheswellingprocessofeachsampleasevaluatedusingasecond
orderswellingkineticsmodel,21whichcanbeexpressedasfollows:

where:
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and

TheAparametercorrespondstoaninitialswellingrate[(dW/dt)0]ofthehydrogelsample,ksistheconstant
rateforswellingandWtisatheoreticalswellingvalueatequilibrium.Wtandkswerecalculatedbyfitting
experimentaldatashowninFigure5toequations(2),(3),(4)andtheresultsaregiveninTable1.

Table1Kineticsparametersevaluatedforthehydrogelssamplesswollenindistilledwateratroomtemperature

Hydrogel
PAMACRYL/N0NT10
PAMACRYL
PAMCOM

bW

1,10428
64521
63423

1,125
649
633

ct

eq(min)

262
243
311

dk

1
s(min )
1.56x10 4

er2

0,99976
0,99958
0,99948

6.54x10 4
9.78x10 4

Equilibriumswelling(gH2O/ggel)bTheoreticalequilibriumswelling(gH2O/ggel)cNecessarytime(min)toreach
theequilibriumswellingdRateofswelling(gH2O/ggel)/mine rsquaredcorrelationvalue.

SwellingdatapresentedinTable1corroborateswiththedatadisplayedinFigure7andbothconfirmstheSH
compositepresentsthehighestwateruptakecapacity.Thiscanbeexplainedbytwofactors:thefirstoneisthe
formationofintenseinteractionsamongOHgroupsonthesurfaceoftheclayandthewatermolecules.The
dispositionofthoseOHgroupsinsidetheSHmatrixincreasesitshydrophilicitycauseahigherwateruptake.
ThesecondfactorcanbeexplainedanalyzingtheXRDpatternofNONT(seeFigure2).Whenclaysaredispersed
intheSHmatrixonananometricscale,asobservedinthiscase,ahigherinteractionamongtheclaylayersand
thecopolymerchainsoccursandpromotestheimprovementofthewateruptakecapacity.Similarresultswere
reportedbySantiagoetal.22
ThehighwateruptakecapacitypresentedbytheSHaftertheincorporationofNONTisadesirablefeature.Such
outstandingcapacitypotentizestheapplicationofouroriginalSHcompositeinseveralfields,especiallyinthose
werehighabsorptionrateandcapacityarenecessary(i.e.waterreservinginsoilandsoilconditioning).The
wateruptakedatapresentedhereareveryexpressivewhencomparedtoothersSHmatricesfilledwith
differentclays.Takingintoaccount,Table2showssomewateruptakedataforSHscompositesfilledwith
differentclays.

Table2Comparativechart:WateruptakecapacitiespresentedbySHscompositesfilledwithdifferentclays

SHmatrix
Poly(acrylamidecoacrylamide) c
Poly(acrylamidecoacrylamide)
Poly(acrylicacidcoacrylamide)
Poly(acrylicacidcoacrylamide)
Poly(acrylicacidcoacrylamide)
Poly(acrylicacid)
Poly(acrylicacid)
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Clay

wt%

bW

Ref.

Nontronite
Montmorrilonite
Organoattapulgite
Kaolinite
Organomontmorillonite
Sodiumhumate
Attapulgite

10
2
10
10
12
5.3
50

1,104
750
1,282
433
510
684
675

23
24
25
26
27
28
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Poly(acrylicacid)
Poly(sodiumacrylamide)

Bentonite
Sepiolite

20
5

1,562
1,419

29
30

InrelationtothepolymericmatrixtotalmassbEquilibriumswelling(gH2O/ggel)cSHcompositepreparedin
thiswork.
Inthiswork,theeffectofsomecationsandanionsonthewateruptakecapacityofPAMACRYL/NONT10was
evaluatedindifferentconcentration(0.0010.1molL1)ofNaCl,NaHCO3,andCaCl2saltsolutions.TheW
valuescalculatedfromtheswellingassaysareshowninFigure8.Asitcanbeseen,theWvalueswere
appreciablyreducedascomparedtothosecalculatedindeionizedwater.Additionaly,forallthesaltsolutionsW
graduallydecreasedasthesaltconcentrationisincreased.Thiswellknownphenomenoniscommonlyobserved
whenhydrogelsswellinionicenvironments,duetoadecreaseddifferenceintheosmoticpressure(ionic
pressure)betweenthepolymernetworkandtheexternalsolution.31Withtheincreasingofsaltconcentrations
inthesolutionwherethegelisimmersed,thedifferenceinosmoticpressurebetweenthegelnetworkandthe
externalsolutiondecreasedand,asaresult,thewaterabsorbencyofPAMACRYL/NONT10issignificantly
decreased.Despitethisbehavior,theWvalueswereverysimilarofbothClandHCO3ions,whichsuggestSH
compositedoesnotshowsensibilitytotheseanionsneithertotheirsizes.Ananalogousobservationwas
recentlyreportedforapoly(acrylamidecoacrylate)matrixfilledwithcellulosenanowhiskers.20

Figure8WateruptakevariationofPAMACRYL/NONT10insaltsolutionswithdifferentconcentrations

Toachieveacomparativemeasureofsaltsensitivityofthehydrogels,adimensionlesssaltsensitivityfactor,f,
definedasfollow:32

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whereWsaline andWwaterare,respectively,theswellingcapacityinsalinesolutionandindeionizedwater.Thef
valuescalculatedforPAMACRYL/NONT10andPAMACRYLaredisplayedinTable3.

Table3W(ingH2O /ggel)andfvaluescalculatedfor(a)PAMACRYLand(b)PAMACRYL/NQNT10hydrogelsswollenindifferent
saltsolutions

Saltsolution
NaCl
NaHCO 3
CaCl2

(a)
(b)
(a)
(b)
(a)
(b)

0.001
W
3614
6458
3536
6287
1733
3636

f
0.44
0.41
0.45
0.43
0.73
0.67

Concentrationofsaltsolution(molL1)
0.01
0.05
W
f
W
f
1952
0.70
851
0.87
3475
0.69
1523
0.86
1823
0.72
762
0.88
3185
0.71
1393
0.87
902
0.86
351
0.95
1813
0.84
642
0.94

0.10
W
631
1212
591
1132
171
311

f
0.91
0.89
0.91
0.90
0.97
0.97

Theincreaseintheionicstrengthreducesthedifferenceintheconcentrationofmovableionsbetweenthebulk
ofpolymermatrixandtheexternalsolution.Twomainfactorsrelatedtothecationpresencecanaffectthe
wateruptakecapacity:(i)Shieldingeffectofthemonovalentcationsonthenegativelychargedgroupspresent
inthehydrogelmatrix.Thisfactorcontributestothecompressionorcontractionofthethreedimensional
structuredrivenbyreductionontherepulsiveforcesproceedingfromthenegativelychargedgroups.Therefore,
theosmoticpressuredifferencebetweenthehydrogelmatrixandtheexternalsolutiondecreases,whichresults
inaloweruptake.32(ii)Physicalcrosslinkingpromotedbythepresenceofmultivalentcations(e.g.Ca2+and
Al3+),whichincreasesthematrixrigidityandavoidsthatconsiderableamountsofwaterhadbeenabsorbed.
Mahdaviniaetal.(2004)reportsadecreasinginthewateruptakeofchitosangraftPANhydrogelsasfunctionof
thecationcharge.32Thiseffectwasattributedtothecomplexationabilityofthosemultivalentcationswith
negativelychargedgroupsofthecopolymerbasedonchitosan,acrylicacidandacrylamide.Here,salts
containeddivalentandtrivalentcationsreducetheswellofPAMACRYLandPAMACRYL/NONTmuchmorethan
saltcontainedonlymonovalentions.Thisisduetothecomplexingabilityofthecarboxymideoracrylategroups
andtheformationofinterandintramolecularcomplexes.33Differentlyofthetypeofcation,theswellof
PAMACRYLandPAMACRYL/NONT10wasnotinfluencedbyexternaltypeofanions,ascanbeseeninTable3.The
effectofpHontheswellingprocessofSHandSHcompositeshashugeimportancefortargetingapplicationof
thesekindsofmaterials.Normally,thevariationofpHintheenvironmentswherethehydrogelisplacedcauses
fluctuationsinthefreevolumeaccessibleforpenetratingwatermolecules,which,thenaffectsthe
characteristicsofswellingofthehydrogel.34Inlightofthis,aseriesofswellingassayswerecarriedout,in
ordertodeterminatethewateruptakecapacityforthePAMACRYL,PAMACRYL/NONT10,andPAMACOMin
differentpHsolutionsrangedfrom2.4to9.4.AccordingtothedatadisplayedinFigure9,ispossibletoverify
allthesamplestestedarepHsensitive.PAMACRYL,PAMACRYL/NONT10,andPAMACOM,showedanincreasein
thewateruptakewiththepHincreasingfrom2.4to9.4.AtlowpH,theacrylateanionsareprotonatedandthe
anionanionrepulsiveforcesnolongerexist.ThisleadstoaminimuminthewateruptakeoftheSHsandSH
composite.Ontheotherhand,athighpHsthoseacrylategroupsgetchargeandsuchchargespromote
electrostaticrepulsionamongCOOgroups.Therepulsiveforcesweakenthepolymericmatrixstabilityand
allowitsexpansion.Asresult,ahighwateramountdiffusesinwardtheSHascanbeseeninFigure9a.34AtpH
9.4alltheSHsamplesswelledabout10foldsormorethanatbufferofpH2.4duetotherepulsionofthe
ionizedgroups.PAMACRYL/NONT10showedthehighestWvaluesforallthepHrangeascanbeseen.AtpHlow
pHconditionsthecarboxylategroupspresentinhydrogelmatrixareintheirprotonatedform,whichreducesthe
repulsiveforcesamongthenegativechargesandthewateruptake.However,athighpHconditions,those
carboxylategroupsareintheirionizedform.Therefore,thenegativechargedensitywithinthehydrogelmatrix
increasesaswelltherepulsiveforcesthatdestabilizesandexpandtheSHandSHcompositesmatricesthat
absorbconsiderablewateramounts.

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Figure9(a)WateruptakevariationatdifferentpHconditionand(b)swelling/deswellingcyclesforPAMACRYL,
PAMACRYL/NONT10,andPAMACOM

ThedatapresentedinFigure9a,assaidabove,showPAMACRYL/NONT10isapHsensitiveSHcomposite.Such
featureallowsapplyingthisoriginalSHcompositewithgreatefficacyinagriculture,forinstance.Besidesthe
abilityoftoabsorbandtoretainconsiderablewateramount,whichcontributestoconservethesoilmoisture,
PAMACRYL/NONT10canbeactasasoiladdictive.Severalactivesubstancesutilizedinagricultureassoil
conditioners(i.e.fertilizers,minerals,pesticides,etc.)canbeincorporatedintheSHcompositeformulationand
thenbereleasedinacontrolledway.ThepHsensibilityshowedbytheSHcompositepresentedinthiswork
encouragesitsapplicationasasoilconditioner.ThevariationinthesoilpHcanstimulatethereleaseorthe
retentionofthoseactivesubstances.Takingintoaccountthispossibleapplication,ifaSHisundergoingan
applicationassoilconditioner,itwillbesubjectedtowaterswelling/deswellingcyclesanditmustmaintainas
longaspossibleitswaterabsorptioncharacteristics.Therepetitionoftheswelling/deswellingcyclesignificantly
affectsthewaterabsorptioncapacity.Forthisreason,inthisworkthewateruptakebehaviorofPAMACRYL,
PAMACRYL/NONT10,andPAMACOMwasstudiedafterseveralswelling/deswellingcycles(Figure9b).According
totheexperimentaldata,thetrendfordecreasingthewateruptakeupto4thor5thcycleisobservedforallthe
hydrogelsandtheswellingseemtobestabilizedafterthe6thcycle.IncomparisontotheothertwoSHs,
PAMACRYL/NONT10showedthesmallestreductioninthewateruptakecapacitywhentheswelling/deswelling
processisdone6times.Suchreductionwasabout38%inthevaluecalculatedforW.Thisdemonstratesclearly
theincorporationofNONTcontributestoincreasethenumberoftimesthatPAMACRYL/NONT10canbeutilized.
Fromtheeconomicpointofviewthisisaveryattractiveaspect.Ontheotherhand,PAMACRYLhydrogelshowed
moderatereductioninthewateruptakecapacity(ca.46%),whilePAMACOMshowedthegreatesttrendin
reduction(ca.49%).

CONCLUSIONS
AnoriginalSHcompositebasedonpoly(acrylamidecoacrylate)matrixfilledwithnontronite(NONT)based
weresuccessfullypreparedandcharacterizedhere.TheSHcompositesshowedtobemoreefficientinwater
uptakethantheconventionalSHwithoutNONT.TheincorporationofNONTinthepoly(acrylamidecoacrylate)
matriximprovedthewateruptakecapacityoffinalmaterial,providinganincreaseof71%intheWwhen
comparedtoconventionalSH.ThewateruptakecapacitypresentedbytheSHcompositesdependsontheclay
andMBAcontents,andthemaximumvaluesofWwererecordedforthesamplepreparedwith10wt%of
NONTand0.05wt/mol%,ofMBA.ThesamplePAMACRYL/NONT10showedfasterandmoreefficientwater
absorption,lowersensibilitytopresenceofsaltandhigherwaterretentionthanthePAMACOM,acommercial
SH.Furthermore,thisnovelSHcompositehasapHsensitiveproperty,whichcanimproveitsapplicability,
especiallyassoilconditioner.ThesepreliminarydatasuggestPAMACRYL/NONT10possessesveryattractive
propertiesandencouragefuturestudiesaboutitsapplicationinagriculturefield,aspotentialsoilconditioner.

ACKNOWLEDGEMENTS
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TheauthorswouldliketothankFUNCAP(BPI006700084.01.00/12)andCNPqfortheirfinancialsupport.The
authorsarealsogratefultoCOMCAP/UEMforXRDandSEM/EDXanalysis.

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Received:August21,2014Accepted:November19,2014
*email:drefajardo@hotmail.com

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