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ContentslistsavailableatScienceDirectCeramicsInternationaljournalhomepage:www.
elsevier.
com/locate/ceramintAnewlow-temperaturerable0.
95Pb(ZrxTi1-x)O3-0.
05Bi(Mn1/2Ti1/2)O3ceramicforhigh-powerapplicationsBoZhang,HeQi,RuzhongZuoInstituteofElectroCeramics&Devices,SchoolofMaterialsScienceandEngineering,HefeiUniversityofTechnology,Hefei230009,PRChinaARTICLEINFOKeywords:PiezoelectricceramicsHigh-powerapplicationLow-temperaturesinteringMorphotropicphaseboundaryDefectdipoleABSTRACTAnewternarysolid-solutionpiezoelectricceramicof0.
95Pb(ZrxTi1x)O30.
05Bi(Mn1/2Ti1/2)O3(x=0.
49–0.
55)wassuccessfullypreparedviaaconventionalsolid-statereaction.
ThecrystalstructurewasfoundtograduallytransformfromtetragonaltorhombohedralphaseswithincreasingtheZr/Tiratio.
Amorphotropicphaseboundarywasrealizedintheproximityofx=0.
51,whichexhibitedoptimumelectromechanicalpropertiesofd33=275pC/N,ε33T/ε0=1226,kp=0.
53,Qm=1164,tanδ=0.
66%andTc=341°Cassinteredatarelativelylowtemperatureof1120°C.
ComparedwithtypicalPb-basedcomplexperovskitessuchasPb(Mn1/3Nb2/3)O3andPb(Mn1/3Sb2/3)O3,thesubstitutionofBi(Mn1/2Ti1/2)O3providesobviousadvantagesinbothsinteringtemperatureandrawmaterialcost.
Theachievementofpiezoelectricandelectromechanicalpropertieswasinterpretedbymeansofatypicalmodelconcerningtheinteractionbetweendefectdipolesanddomainsthroughcomparativeexperiments.
Thedesirablepropertiesofthestudiedmaterialsystemsuggestagreatpotentialforhigh-powerdeviceapplications.
1.
IntroductionPb(Zr,Ti)O3(PZT)-basedternaryorquaternarypiezoelectriccera-micshavebecomeindispensablefunctionalmaterialsasactuators,ul-trasonicmotorsandtransducers[1–3].
Inordertomeettherequire-mentoftheminiaturizationandhighpowerinpractice,thepiezoelectricceramicsarenecessarytoexhibithighelectromechanicalcouplingfactor(kp),mechanicalqualityfactor(Qm),piezoelectricconstant(d33),Curietemperature(Tc)andlowlossvalues.
Untilnow,alotofattemptshavebeenmadetoimproveelectro-mechanicalpropertiesofPZTbasedmaterials[4–7].
However,highQm,kpandd33arenoteasilyobtainedsimultaneously.
Themostwidelyusedmethodtosatisfytheabove-mentionedrequirementistointroduceacceptordopantsinsoftbasematerials[4–6],suchasthesubstitutionofFe3+ionsforZr4+/Ti4+sitesinPZTbyformingacceptor-oxygenva-cancydefectdipoles(′FeVZrTiO,).
AnothermainmethodisviaaddingperovskiteswithB-sitemultivalenceions[8,9],forexample,Pb(Mn1/3Nb2/3)O3(PMN)orPb(Mn1/3Sb2/3)O3(PMS),toformthepinningofthedomainwallsbymeansofoxygenvacanciesasaresultofcoexistingMn2+/Mn3+ionsduringhigh-temperaturesintering[10,11].
Un-fortunately,theabovecompositionsystemsusuallyneedhighersin-teringtemperaturethan1250°C.
Itisratherdiculttoobtainceramicsbasedonthemwithexcellentpiezoelectricandelectromechanicalpropertiesandlowersinteringtemperaturessuitablefortheapplicationofmultilayerpiezoelectricdevices[10,11].
Inaddition,theproductioncostwouldbealsoobviouslyincreasedowingtotheusageofNb2O5andSb2O3.
Bi-basedperovskitescompoundspossessgoodferroelectricproper-tiesandhighTc[12–14].
Inaddition,theintroductionofBi-basedperovskitesintoPZTwouldhaveapositiveeectonthedecreaseofthesinteringtemperature[15].
Bi(Mn1/2Ti1/2)O3(BMT)wouldbeexpectedtoplaythesameroleasPMNandPMSasmentioned.
TheeectoftheBMTadditiononthedensicationandelectricalpropertiesofPZTceramicshasneverbeenreportedintheliteratures.
Inthiswork,anewternarysolidsolutionceramicofBMT-PZTwaspreparedbyatradi-tionalmixed-oxideroutewithaspecialfocusonthevariationofdi-electric,ferroelectricandelectromechanicalpropertiesoftheternarysystem.
2.
ExperimentalprocedureThe0.
95PZxT1x0.
05BMT(x=0.
49–0.
55)ceramicswerepre-paredbyaconventionalsolid-statereactionmethodusinganalytic-gradeBi2O3,PbO,ZrO2,TiO2andMnO2asrawmaterials.
Stoichiometricamountsofrawpowderswereweighedandball-milledinalcoholwithZrO2ballsfor6h.
Theresultantmixturewasdriedaftercalcinationat850°Cfor2hinair.
Thecalcinedpowersweremilledagainwith5wt%PVAasabinderfor10handsubsequentlypressedhttps://doi.
org/10.
1016/j.
ceramint.
2017.
12.
178Received14December2017;Receivedinrevisedform23December2017;Accepted25December2017Correspondingauthor.
E-mailaddress:rzzuo@hotmail.
com(R.
Zuo).
CeramicsInternational44(2018)5453–5458Availableonline26December20170272-8842/2017ElsevierLtdandTechnaGroupS.
r.
l.
Allrightsreserved.
Tintodisksampleswithadiameterof10mm.
Thespecimenswerehe-atedat550°Cfor4htoburnoutthebinder,andthensinteredat1100–1150°Cfor2hinair.
InordertopreventthevaporizationofBiandPb,samplediskswereburiedinthesacricialpowderofthesamecomposition.
Silverpastewaspaintedonbothsidesofthedisksandredat550°C.
Thesamplesnaturallycooledtoroomtemperatureinthefurnaceaftersinteringweremarkedas"furnace-cooledsamples",whilethesamplesachievedbyawater-quenchingprocessweremarkedas"quenchedsamples".
Thespecimenswerepoledinasiliconeoilbathatdierenttemperaturesunderadceldof5kV/mmfor15min.
ThebulkdensitiesofthesinteredceramicsweremeasuredbytheArchimedesmethod.
ThecrystalstructureoftheredceramicswasidentiedviaanX-raydiractometer(XRD,D/Max2500V,Rigaku,Japan)usingCuKαradiation.
Thedielectricpropertiesweremeasuredat1kHzusinganLCRmeter(AgilentE4980A,SantaClara,CA)inatemperaturerangeof25–500°C.
Thequasi-staticd33wasmeasuredbyaBelincourt-meter(YE2730A,Sinocera,Yangzhou,China).
ThekpandQmvaluesweredeterminedbyaresonance-antiresonancemethodwithanimpedanceanalyzer(PV70A,BeijingBandERACo.
Ltd.
Beijing,China).
Themicrostructureofthesinteredsampleswasobservedusingaeld-emissionscanningelectronmicroscope(FE-SEM,SU8020,JEOL,Tokyo,Japan).
BeforetheSEMobservation,sampleswerecarefullypolishedandthenthermallyetchedat950°Cfor30min.
Thepolar-izationversuselectriceld(P-E)weremeasuredusingaferroelectrictestsystem(Precisionmultiferroelectric;RadiantTechnologiesInc,Albuquerque,NewMexico).
3.
ResultsanddiscussionFig.
1(a)showsthedensicationbehaviorofafewrepresentative0.
95PZxT1x0.
05BMTcompositionsasafunctionofsinteringtem-perature.
Withanincreaseofsinteringtemperature,therelativedensityofallthreesamplesrstlyincreasesuptotheirrespectivemaximumvalues(>96%)at1120°C,andthendecreaseswithfurtherincreasingsinteringtemperature.
Fig.
1(b)-(d)showthemicrostructureof0.
95PZxT1x0.
05BMTceramicssinteredat1120°C.
Itcanbeseenthatallsamplesarewellcompactedwithoutanyobviouspores.
WithincreasingtheZr/Tiratio,thegrainsizeremainsalmostunchanged(~2minaverage).
ComparedwithtraditionalPZT-basedceramics,theoptimumsinteringtemperatureofthestudiedmaterialsystemislow-eredbyalmost150°CpossiblyasaresultoftheexistenceoftheBielement[15].
Itwillexhibitlargerpotentialsinfurtherreducingthesinteringtemperatureinfutureforapplicationswhereamuchlowersinteringtemperaturethan1000°Cisneeded.
Fig.
2(a)indicatestheXRDpatternsof0.
95PZxT1x0.
05BMTsamplesasafunctionofx.
Alldiractionpeakscouldbewellindexedtoasingleperovskitestructurewithoutanysecondaryphases,indicatingthatBi3+and(Mn1/2Ti1/2)3+havefullydiusedintothelatticeandformedsolidsolutionswithPZT.
Inaddition,thecrystalstructureisfoundtoevolvefromatypicaltetragonal(T)phasetoarhombohedral(R)phasewithincreasingx,asevidencedbythevariationofthe(200)diractionlines.
Withincreasingx,thesplit(200)diractionpeaksgraduallymergeintoasingleone,asshowninFig.
2(b).
Inordertoquantitativelyanalyzetheevolutionofthephasestructure,the(200)diractionpeakproleswerettedbyusingapseudo-Voigtpeakshapefunction,asshowninFig.
2(c).
TherelativecontentofT(FT)andR(FR)phaseswasroughlycalculated,asshowninFig.
2(d).
Itisevidentthatamorphotropicphaseboundary(MPB)betweenRandTphasesexistsinthecompositionrangeof0.
50Tc),asshowninFig.
6(b).
Moreover,alargerPrthanthatofthefurnace-cooled(Fig.
6(a))andpoled(Fig.
4(a))sampleswasobtainedforquenchedsamples.
AppropriatepiezoelectricpropertiescouldbedetectedjustafterthemeasurementoftheP-EloopfortheFig.
2.
(a)Room-temperatureXRDpatternsof0.
95PZxT1x0.
05BMTceramics,(b)locallyenlargeddiractionpeaksinthe2θrangeof43°46°,(c)peakttingplotsforthere-presentativecompositionswithx=0.
51,0.
52and0.
54,and(d)thevariationofFRandFTwithx.
Fig.
3.
Dielectricpermittivityandlosstangentvaluesat1kHzasafunctionoftem-peratureforafew0.
95PZxT1x0.
05BMTceramics.
B.
Zhangetal.
CeramicsInternational44(2018)5453–54585455quenchedsamples,asshowninFig.
6(c).
Thisphenomenonisquitedierentfromthatobservedinfurnace-cooledsamples,whichneedtobepoledathightemperatures,asshowninFig.
4.
Thed33valuesachievedinquenchedsamples(Fig.
6(c))areapproximatelyequaltothatofthefurnace-cooledsamplesafterbeingpoledat150°C(seeFig.
5(b)),however,muchsmallerQmvaluesareachievedforthequenchedsamplesafterelectriccycling.
However,afteragingat150°Cfor3days,theQmvalueforthequenchedsampleincreasesandap-proximatestothevalueofthecorrespondingpoledsample(Fig.
5).
ThiscanbeclearlyconrmedbythecorrespondingP-Eloopofthequenchedsamplewhichwasrstsubjectedtoelectriceldcyclingandthenbeingagedat150°Cfor3days,asshowninFig.
6(b).
Anobviouslyasym-metricP-Eloopindicatesthepresenceofaninternalbiaseldalongthedirectionofthepolingelectriceld.
Aschematicillustrationwasproposedtoexplainthepolarizationresponseduringtheapplicationofanelectriceldforthex=0.
51ceramicwithdierentinitialstates,asshowninFig.
7.
Asknown,thedefectdipolesshouldrandomlydistributeintheparaelectricphaseaboveTc,asshowninFig.
7(a).
Therandomlydistributeddefectdipoleswouldbefrozeninthedomainsafterwater-quenching.
Therefore,thedirectionofdefectdipolesisinconsistentwiththatofthepolarizationvector,suchthatthedomainswouldswitchfreelyinaccordancewiththeappliedeld(Fig.
7(b1)-(b3)),resultingintypicalferroelectricfeaturewithasaturatedP-Eloop(Fig.
6(b)).
Eventhoughgoodpie-zoelectricresponsecanbeachievedinthequenchedsampleafterelectriccycling,arelativelylowQmwasachievedowingtoitsfragiledomainstate.
However,randomlyorientateddefectdipolesareinametastablestatebelowTc.
Thedefectdipoleformedbetweenions(Mn2+/Mn3+)andO2-vacanciestendstoalignalongthespontaneouspolarizationdirectiongradually,anditssymmetrywouldbeconsistentFig.
4.
(a)P-Eloopsand(b)d33,kp,Qmandε33T/ε0forfurnace-cooledsampleswithx=0.
51poledunder5kV/mmatdierenttemperatures.
Fig.
5.
Room-temperature(a)d33,kp,Qm,(b)ε33T/ε0andtanδvaluesforthefurnace-cooled0.
95PZxT1x0.
05BMTceramicsafterbeingpoledunder5kV/mmat150°Cfor15min.
Fig.
6.
Room-temperatureP-Eloopsforthe(a)furnace-cooledand(b)quenched0.
95PZxT1x0.
05BMTceramicsaswellasthequenchedx=0.
51samplewhichsuf-feredfromagingat150°Cfor3daysafterelectriceldcycling,and(c)compositiondependenceofd33,kpandQmvaluesafterthemeasurementoftheP-Eloopforthequenchedsamples.
B.
Zhangetal.
CeramicsInternational44(2018)5453–54585456withthecrystalsymmetryduringaslowcoolingprocess(Fig.
7(c1))oranagingprocess(suchasFig.
7(b3)to(d3))[19,20],causingapinningeectonthedomains.
Accordingly,thedefectdipolesprovideare-storingforcetoswitchbackthedomainsaftertheelectriceldisre-moved(Fig.
7(c1)-(c3)),inducingapinchedP-Eloop.
Bothofthedo-mainsanddefectdipolesalignalongtheelectricelddirectionduringthepolingprocessathightemperatures(Fig.
7(d1)-(d3)),resultinginastablytexturedpolarizationstate.
Therefore,excellentpiezoelectricpropertiesaswellashighQmvalueareachievedsimultaneously.
4.
ConclusionsAnewlow-temperaturerable0.
95PZxT1x0.
05BMTpiezo-electricceramicwasstudiedintermsofthemicrostructure,phasestructure,dielectric,piezoelectricandferroelectricproperties.
Theternarysolidsolutionceramicscanbewelldensiedatarelativelylowtemperatureof~1120°C,whichisabout150°ClowerthanthatoftraditionalPZT-basedhigh-powerpiezoelectricceramics.
AgradualevolutionfromferroelectricTphasetoRphasewasfoundwithen-hancingZr/Tiratio.
Optimumdielectricandelectromechanicalprop-ertiesofd33=275pC/N,ε33T/ε0=1226,kp=0.
53,tanδ=0.
66%,Qm=1164andTc=341°CwereachievedintheMPBcompositionwithx=0.
51.
Theeectofpolingconditionsonthepiezoelectricandelectromechanicalpropertieswasexplainedbymeansoftheinteractionmodelbetweenthedefectdipoleandpolarizationvector.
Theexperi-mentalresultssuggestthat0.
95PZxT1x0.
05BMTpiezoelectriccera-micsshouldhaveagreatpotentialforhigh-powerapplications.
AcknowledgementsThisworkwassupportedbytheNationalNaturalScienceFoundationofChina(GrantNo.
51472069).
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