To cite this version : Lallemant, Lucile and Roussel, Nicolas and
Fantozzi, Gilbert and Garnier, Vincent and Bonnefont, Guillaume and
Douillard, Thierry and Durand, Bernard and Guillemet-Fritsch, Sophie
and Chane-Ching, Jean-Yves and Garcia-Gutierez, Domingo and
Aguilar-Garib, Juan Effect of amount of doping agent on sintering,
microstructure and optical properties of Zr- and La-doped alumina
sintered by SPS. (2014) Journal of the European Ceramic Society, vol.
34 (n° 5). pp. 1279-1288. ISSN 0955-2219
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Effect
of
amount
of
doping
agent
on
sintering,
microstructure
and
optical
properties
of
Zr-
and
La-doped
alumina
sintered
by
SPS
Lucile
Lallemant
a,b,
Nicolas
Roussel
c,
Gilbert
Fantozzi
a,b,
Vincent
Garnier
a,b,∗,
Guillaume
Bonnefont
a,b,
Thierry
Douillard
a,b,
Bernard
Durand
c,
Sophie
Guillemet-Fritsch
c,
Jean-Yves
Chane-Ching
c,
Domingo
Garcia-Gutierez
d,
Juan
Aguilar-Garib
daUniversitédeLyon,CNRS,France
bInsa-Lyon,MATEISUMR5510,F-69621Villeurbanne,France
cUniversitédeToulouse,CNRS-UPS-INPT,CIRIMAT,118routedeNarbonne,31062Toulouse,France
dCentrodeInnovacion,InvestigacionyDesarrolloenIngenierayTecnologica,UANL,CarreteraalAeropuerto,Apodaca,NuevoLeon,Mexico
Received30January2013;receivedinrevisedform5November2013;accepted12November2013 Availableonline2December2013
Abstract
SPS-produceda-aluminasamplesarepreparedfrompowdersdopedwithdifferentamountsofZr4+andLa3+cations.Zr4+cationssegregateat
grainboundaries.m-ZrO2particlesareformedat570butnotat280catppm.Ab-aluminaLaAl11O18structureisfoundat310catppmwhen
thelanthanumgrainboundarysolubilitylimitisexceeded(∼200catppm).100catppmLaissufficienttoblockthediffusionpathacrossgrain boundariesandinhibitgraingrowth.Bothdopingcationsdisturbthegrainboundarydiffusionwhatevertheiramount.Theydelaythedensification athighertemperatureswhilelimitinggraingrowth.Therealin-linetransmittance(RIT)ofa-aluminaisimprovedduetothereducedgrainsize. Nevertheless,increasingthecationamountleadstoanincreaseinporosityoreventheformationofsecondaryphaseparticles,bothdetrimental foropticalproperties.Finally,optimisedamountsofcationof200and150catppmarefoundforLa-andZr-dopedalumina,respectively.
Keywords:Al2O3;Doping;Sparkplasmasintering;Grainsizes;Opticalproperties
1. Introduction
Properties of ceramic materials are governed by their microstructure. Therefore, the best microstructure suitable for a given application should be obtained after sintering. Grain boundariesareknown to playasignificant role onthe microstructureformationduringdensificationandgraingrowth. Inthecaseofalumina,dopingcationswithalargerionicsizethan Al3+(forexampleY3+,La3+,Mg2+)maybeaddedtothepowder beforesintering.Theyshowastrongtendencytoeitherforma solidsolutionwiththealuminaorsegregateatgrainboundaries. Masstransportinthegrainboundaryplaneandgrainboundary mobilityisthereforemodified.1–5Asaresult,thedensification caneither be improvedor hindered dueto ahigher or lower
∗Correspondingauthorat:Insa-Lyon,MATEISUMR5510,F-69621
Villeur-banne,France.Tel.:+33472438498.
E-mailaddress:vincent.garnier@insa-lyon.fr(V.Garnier).
diffusivityatgrainboundaries.3Moreover,thegrainsizeis gen-erallyfineraftersinteringwithsuchdopingagentsduetolower grainboundarymobility.3,6,7Thosedopingelementshavebeen successfullyusedtoobtaintransparentpolycrystallinealumina (PCA).7–12Indeed,becauseofthebirefringentnatureofPCA,a finemicrostructureisrequiredaftersintering13asdemonstrated bythemodeldevelopedbyApetzetal.(Eqs.(1)and(2)). RIT = I2 I1 =(1−RS·exp(−γtot·D)) (1) γtot=γG+γp= 3π 2r∆n2 λ20 + p (4/3)π·r3 p ·Csca,p (2) whereRITistherealin-linetransmittance,I1 andI2the light beam intensitiesbefore andafter travellingthrough a sample having athickness D; Rs the totalnormal surfacereflectance
(=0.14forPCA);γtotthetotalscatteringcoefficient;γGthelight
scatteringcoefficientbygrainboundaries;γpthelight
scatter-ingcoefficientduetoporosity;rtheaveragegrainradius;1n http://dx.doi.org/10.1016/j.jeurceramsoc.2013.11.015
Fig.1.Schematicdrawingof(a)solidsolution,(b)grainboundarysegregation, and(c)secondaryphase(blue)formation.(Forinterpretationofthereferences tocolorinthisfigurelegend,thereaderisreferredtothewebversionofthe article.)
theaveragerefractiveindexchangebetweentwoadjacentgrains (=0.005forPCA),λ0thewavelengthoftheincidentlightbeam invacuum;pthetotalporosity,rptheaverageporeradiusand
Csca,pthescatteringcross-sectionofonesphericalpore.Stuer
et al.14 recently showed that even ifa highdegreeof poros-ity is present in the sample, there is little effect on the RIT belowacriticalporesize ofabout50nm.Theporosityeffect could thus be overestimated. Concerningthe grainboundary effect,withexperimentsthemodelhasshowngoodcorrelation forgrainsizebetween300nmand3mmforλ=640nm.15 Nev-ertheless, thismodel does notconsidera possiblecorrelation betweengrainboundaryscatteringandgrainorientation.16 How-ever,Choetal.17 haveobservednosignificantgrainboundary misorientationonaluminasamplesdopedwith100catppmZr and500catppmLacomparedwithpuresamples.Ithas there-forebeendecidedtocompareourresultswiththeApetzmodel. In theliterature,the roleof oneparticular dopingelement on densificationandgraingrowthofPCAisgenerallyobservedfor onesinglequantityofthiselement.Nevertheless,thelocationof dopingcationsmaychangedependingontheiramount,resulting indifferentsinteringbehaviourandsodifferentmicrostructures andassociatedproperties:
(A) When the amount of doping agent is below the bulk solubilitylimit,dopingcationsareinsolidsolution homo-geneouslydistributedwithinthegrain(Fig.1(a)).However, thiscaseusuallydoesnothappenasbulksolubilitylimits areverylow(afewhundredppm4)dependingonthedoping agentionicradiiorcharges.
(B) When the amount of doping agent is higher than the bulk solubility limit and lower than the grain boundary solubility limit, the additional cations segregate within a few nanometres18 at the grain boundaries (Fig. 1(b)). The atomicstructural environmentaroundthesegregated dopingcations is similarto thatit would haveinknown secondaryphases.4,19 Moreover,it shouldbehighlighted that,ontheonehand,thegrainboundarysolubilityis sur-facedependenti.e.itdependsonthegrainsizewherefiner grainswillaccommodatealargeramountofdopingagent duetotheirlargersurfacearea.Ontheotherhand,thegrain boundarysolubilityisalsodependentonthegrainboundary planeorientation,4resultinginaheterogeneousdistribution ofthesegregatingareasalongthegrainboundaries. (C) Whenthedopingagentamountexceedsthegrainboundary
solubility limit,secondaryphasesappearatgrain bound-ariesandattriplepointsalongwithalatticediscontinuity betweenthealuminaandthesecondaryphases(Fig.1(c)). Dependingonitscharacteristics(ionicradius,charge,etc.), thedopingelementmaybeinsolidsolution,segregateatgrain boundariesorformsecondaryphases.Thesephasesareoneof thepossible light scattering sourcesinPCA.Their scattering coefficientcanbedescribedbyEq.(3)9andisaddedtothetotal scatteringcoefficientγtotinEq.(2).
γdop=
hppmwidop·ρAl2O3
4/3·Π·rdop3 ·ρdop
·Csca,dop (3)
whereγdopisthelightscatteringcoefficientbysecondaryphase
particles;hppmwidoptheamountofdopingagentinweightppm;
ρAl2O3thetheoreticaldensityofa-Al2O3;rdoptheaverageradius
ofsecondaryphaseparticles;ρdopthetheoreticaldensityof
sec-ondaryphaseparticlesandCsca,dopthescatteringcross-section
ofonesphericalsecondaryphaseparticle.Thus,theformationof secondaryphaseparticlesshouldbeavoidedinordertoimprove opticalproperties, unless theyarehomogeneously distributed alongthegrainboundarieswithalowsizeandarefractiveindex very closetothat of PCA.In the present study, the effectof dopingagentamounton themicrostructure andoptical prop-ertiesof Zr-andLa-doped aluminasinteredbySparkPlasma Sintering(SPS)willbedetermined.BothZr4+andLa3+cations are largerthan Al3+ cations: their ionic radii are 0.72 ˚A and 1.03 ˚A,respectivelyfor6-foldcoordinationcomparedto0.53 ˚A forAl3+forthesamecoordinationnumber.20Zr4+wasfoundto beinsolubleinana-aluminalattice21andthebulksolubilityof La3+isreallylow(∼80catppm22)orevenlower.4Thosedoping agentstherefore haveastrong tendency tosegregateat grain boundaries.Theythuslimitgraingrowthduringsintering17,23 andimprovetheopticalpropertiesofaluminasamples. Never-theless,asfarasweknow,nostudyhasyetbeenperformedto highlighttheroleofthequantityofdopingagent.Thepresent studyaims tocorrelate thedensification behaviour,grainsize aftersinteringandopticalpropertieswiththeamountand loca-tionofLaandZrcationswithinanaluminamatrix.Inaddition, optimisationoftheamountofdopingagentregardingtheoptical propertiesofaluminasampleswillbeperformed.
L.Lallemantetal./JournaloftheEuropeanCeramicSociety34(2014)1279–1288 1281 Table1
ICPmeasurementsondopedaluminapowdersafterfreeze-drying.AP:pure alumina,AZ:aluminaandzirconium,AL:aluminaandlanthanum.
Sample Introduced dopingagent amount (catppm) Measured dopingagent amountafter freeze-drying (catppm) Ratio (mea-sured/introduced) dopingagent amount AP 0 – – Zr-dopedalumina AZ150 250 150 0.6 AZ280 500 280 0.6 AZ570 1000 570 0.6 La-dopedalumina AL40 60 40 0.7 AL100 150 100 0.7 AL200 300 200 0.7 AL310 500 310 0.6 AL670 1000 670 0.7
2. Materialsandmethods
The starting material was a commercial (BA15psh, Baïkowski) high purity a-Al2O3 aqueous slurry (solid con-tent 73.5wt%) with an average particle size Dv50 of 160nm (measured by laser diffraction). The total impurity was less than0.01wt%(14ppmNa,60ppmK,7.1ppmFe,13ppmSi, 4ppmCa)as quotedbythe manufacturer.The dopingagents wereintroducedbyweighingouttherequiredamountofhigh purity(>99.99%)water-solublechloridesalts(Sigma–Aldrich, Germany)ofzirconium(ZrOCl2,8H2O)andlanthanum(LaCl3, 7H2O),addingthemtothealuminaslurryandmixingfor24hby rotationofthecontainer.Theslurrywasfrozeninliquid nitro-genthenfreeze-driedforapproximately48h at−40◦Cunder 0.1mbar (Freeze-dryer: Christ Alpha 2–4) to obtain a pow-der.Thiswasthensievedat500mm. Theamountsof doping agent (cationic ratio [doping elementX+]/[Al3+]) introduced were250,500, 1000catppmfor zirconiumand60,150,300, 500,1000catppmforlanthanum.InductivelyCoupledPlasma (ICP) measurements (Horiba Jobain Yvon Activa) were per-formed to characterise the real amount of dopingagent still present in the powder after freeze-drying and sieving (see Table1).
As can be seen from Table 1, a constant ratio of doping cationsiseliminated duringthedryingstep.Thissuggestsan equilibriumbetweenthe dopingcationspresent atthe surface of alumina particles and thosepresent within the slurry.All amounts of doping agent given hereafter will refer to those measuredbyICPafterfreeze-drying.
Thefreeze-driedpowdersweresinteredbySPS(HPD25/1, FCTSystem,Rauenstein,Germany)withoutanythermal pre-treatment. Indeed, this avoids large agglomerates within the powder beforedensification.11 The sinteringcycle was previ-ouslyoptimisedtoobtainpuretransparentPCAsamples.11,24It includesauni-axialpressureof80MPaappliedthroughoutthe cycle,rapidheatingto800◦C,aheatingrateof10◦C/minfrom 800◦Cto1100◦Cfollowedbyslowerheating(1◦C/min)upto
Fig.2.RITs640nmofZr-dopedaluminasamplessinteredatTf=1280◦Cand
1300◦Cfordifferentamountsofdopingagent.
thefinalsinteringtemperature(Tf)inordertoremovethe resid-ualporosity.11,24–26Rapidcoolingendsthecycle,interruptedby a10-minperiodat1000◦Ctoreleasetheresidualstresses.25,26 Thefinalsinteringtemperaturewasoptimisedforeachkindof dopedsampleintherangeof1230–1330◦Cinordertoobtainthe bestopticalproperties.Thesinteringtemperaturewasmeasured 3mmfromthesamplewithanopticalpyrometerfocusedonthe non-throughhole(3mmdiameter)ofagraphitedie.Then,the 20mmdiametersampleswerecarefullymirror-polishedonboth sidesusingdiamondslurries(downto1mm).Thetransparency inthecentreofthepellet(spotsize=5mm×2mm)was evalu-atedbyaRITmeasurement(JascoV-670),asitonlytakesinto account theunscatteredlight throughthe sample(i.e.the real transmittedlight).To ensurethat onlytheRITwasmeasured, ashieldwithanappropriateaperturewas placedbetweenthe sampleandthedetectorinordertohidelightscatteredbymore than0.5◦.Forcomparisonpurposes,alltheRITvaluesgivenin thispaperareevaluatedforλ0=640nmandEq.(4)allowsthe RITtobeobtainedforthesamethicknesst2=0.88mm: RIT(t2)=(1−RS)
RIT(t1) 1−RS
t2/t1
(4) whereRSisthetotalnormalsurfacereflectance(=0.14forPCA)
andRIT(ti)istheRITforasamplethicknessti.
An SEM ZEISS Supra55 was used to investigate the microstructure of thesamples. Grainsizes wereevaluatedon fracture surfaces and a factor of 1.22 was applied to obtain a revised grain size.10,13 The presence of secondary phases was determinedusing X-raydiffractometry(XRDBruker D8 Advance)andtheirlocationwascharacterisedbytransmission electron microscopy(TEM)observations (TEMTitan G2 60-300andTEMJEOL2010F).
3. Resultsanddiscussion
3.1. Zr-dopedalumina
3.1.1. Opticalproperties
Zr-dopedpowdersweresinteredatdifferentTf:1230,1250,
1280,1300and1330◦C.ThehighestRITs
640nmwereobtained atTf=1280and1300◦CandtheseresultsarepresentedinFig.2.
DopingwithZr4+cationsenablesustoincreasetheRIT640nm ofaluminasamplesduetoareducedgrainsize(Fig.3).
1282 L.Lallemantetal./JournaloftheEuropeanCeramicSociety34(2014)1279–1288
Fig. 3.Average grain sizes of Zr-doped alumina samples sintered at
Tf=1280◦Cand1300◦Cfordifferentamountsofdopingagent.
For both temperatures, the best RITs640nm (45±1% and 48±1%forTf=1280and1300◦C,respectively)areobtained
for thelowestZr4+dopingamount(AZ150).However,Fig.3 indicatesthatthe lowertheamountofZr4+ doping,thelarger thegrainsize.Forexample,at1300◦C,theRIT640nmdecreases byabout5%betweenAZ150andAZ570whereasthegrainsize decreases from0.59±0.13mmfor AZ150 to0.44±0.13mm forAZ570.
Inthesameway,thehighestRIT640nmisalwaysobtainedat
Tf=1300◦Cfor agivenamountofdopingagent whereasthe
grainsizeislargeratthistemperature.Infact,themodel(Eqs. (1)–(3))indicatesthattheRITshouldbehigherforlowergrain sizeunless porosity or secondaryphaseparticles arepresent. TEMobservationsarethusperformedtoexplainthehigherRIT atlargergrainsize.
3.1.2. TEManalysis
Inatransmissionelectronmicroscope,HAADF(HighAngle AnnularDarkField)imagesarehighlysensitivetovariationsin theatomicnumberofatomsinthesample(Z-contrastimages). As the atomic number of Zr (Z=40) is higher than that of Al(Z=13),brightcontrasts inHAADF images mayindicate thepresenceofZr4+ cationswithinthealuminamatrix.Thus, HAADFobservationsandEDXspectroscopywereperformed onAZ570samplessinteredatTf=1300◦C(Fig.4(a)).Theresult
indicatesthat noZr4+ cations are locatedwithin the alumina grains.Thewhite graincorresponds toatopologicalcontrast. Onthecontrary,Zr4+cationsaresegregatedalonggrain bound-ariesasindicatedbythebrightcontrastandEDXspectroscopyin
Fig.4.HAADFobservationsandEDXmeasurementsofAZ570samplesinteredatTf=1300◦C(a)globalview,(b)zoomofthegrainboundaries,and(c)secondary
L.Lallemantetal./JournaloftheEuropeanCeramicSociety34(2014)1279–1288 1283
Fig.5.XRDmeasurementsofAZ280(bottomleft)andAZ570(topleft)samples sinteredatTf=1280◦CandAL670(right)samplesinteredatTf=1330◦C
(m-ZrO2:ICDD37-1484;LaAl11O18:ICDD33-0699,Al2O3:ICDD46-1212).
Fig.4(b).Finally,secondaryphaseparticlesarealsosometimes foundattriplepoints(seeFig.4(c)).
Thesesecondaryphaseparticles(Fig.4(c))areresponsible forthereflectionofmonocliniczirconia(m-ZrO2)inXRD mea-surements(Fig.5).Asm-ZrO2reflectionappearsonlyonAZ570 samples(Fig.5)andnotforloweramountsofdopingagent,this suggeststhatsecondaryphaseparticlesofm-ZrO2areformed atasufficientlyhighZrconcentration.Forloweramounts,Zr4+ cationsareonlysegregatedalonggrainboundaries.
TheseresultsareingoodagreementwithastudybyWang et al.19 who reported that for a doping agent amount of 100catppmZr,theZr4+cationssegregatedalonggrain bound-arieswithoutsecondaryphaseformation.Itiswellknownthat Zr4+cationsareinsolubleinana-aluminalattice.21However,it isinterestingtopointoutthatthegrainboundarysolubilitylimit ofZr4+cationsbeforetheformationofsecondaryphase parti-clesisquitehigh.Forgrainsizesaround450nm,thisamountis thusbetween280and570catppmZr.
SegregationofZr4+cationsalonggrainboundariesexplains whythe grainsize issmaller for agreater amountof doping agent (Fig. 3). Indeed, grain growthmechanisms induce dif-fusionacrossthegrainboundaries.Suchdiffusionishindered bythepresenceofimpurities,suchassegregatedZr4+cations. Moreover,impuritiesleadtoasolutedragphenomenonthat dis-turbsthegrainboundary mobility, allthemoreas thedoping agentamountincreases.27Thismeansthatgraingrowthwillbe moresignificantatsmallamountsofdopingagent.ForAZ570 samples,thepresenceofsecondaryphaseparticleswillinducea pinningeffectthatwillbeaddedtothesolutedragphenomenon topreventgraingrowth.
Concerningtheinfluenceofmicrostructureonoptical prop-erties, two behaviours have to be considered depending on whethersecondaryphaseparticlesarepresentornot.ForAZ150 and AZ280, XRD measurements indicate that no secondary phaseparticlesareformed. Thissuggeststhat lightscattering onlydepends on grain size andporosity (Eqs. (1)–(3)). This assumptionimpliesthat thesegregationof Zr4+ cationsalong grainboundaries does not contribute tolight scattering. This hasbeendemonstratedbyBernard-Grangeretal.9,10who suc-ceededinobtainingtransparentPCAdopedwithMg2+,Ti4+and Ca2+/Ti4+.Intheirstudies,thedopingcationsonlysegregated
Fig.6.ComparisonofRITs640nm ofAZ150andAZ280samplessinteredat
Tf=1280◦Cand1300◦Cwiththeoreticalmodels(λ0=640nm,D=0.88mm,
φp=100nm).
alonggrainboundarieswithoutsecondaryphaseparticle forma-tion andtheRITmeasurementsinthevisiblerangepresented agoodcorrelationwiththetheoreticalcurvesobtainedwiththe Apetz model (Eqs. (1) and(2)).That is whyfor AZ150 and AZ280,onlyscatteringduetoporosityandfromgrain bound-ariesisconsidered.
Transparencyrequiresnoporosityorsuchalimitedamount thatitcouldnotbemeasuredbytheclassicalArchimedemethod. However,asmeasuredgrainsizesarebetween300nmand3mm and no secondary phase particlesare formed on AZ150 and AZ280 samples,itispossibletocompare ourresultswiththe theoreticalmodeldevelopedbyApetz(Eqs.(1)and(2)). Theo-reticalcurves(Fig.6)werecalculatedfora100nmporesizeas itisthelargestporesizewhichcanbeobservedbyTEM(Fig.4). Moreover,thiscorrespondstothecriticalporesize.14
Asthegrainsizeislargerat1300◦Cthan1280◦C(Fig.3), thismeansthatthelowertransparencyobtainedat1280◦C com-paredto1300◦Ccanbeexplainedbygreaterporosity(Fig.6). Thus, at 1280◦C, the densification is not yet complete and somecriticalporosity(>50nm14)isstillpresent,affectingthe RITs640nm.HigherRITs640nmarethusobtainedat1300◦Cfor allamountsofdopingagent(Fig.2).Atthistemperature,the densificationissufficienttolimitthepresenceofporeswitha limitedgraingrowth.Lightscatteringbybothporesandgrain boundariesisthenlimited.11Moreover,foragiventemperature, theRITs640nmofZr-dopedsamplesdecreasewiththeincrease in amount of dopingagent (Fig. 2). This decrease is dueto theincreaseinporosity,asshowninFig.6,indicatingdifferent densificationbehaviours.
ForAZ570,m-ZrO2particlesarefoundwithinthealumina matrix (Figs. 4(c) and 5) which will also contribute to light scattering(Eq.(3)).
3.1.3. Sintering
Asdiscussedabove,samplesdopedwithdifferentamountsof Zr4+cationsmayhavedifferentsinteringbehaviours.The den-sificationratesofthedifferentpowderssinteredatTf=1280◦C
are showninFig.7 andarecomparedwiththe purealumina freeze-driedpowdersinteredusingthesamesinteringcycle.
1284 L.Lallemantetal./JournaloftheEuropeanCeramicSociety34(2014)1279–1288
Fig.7.Densificationrateoffreeze-driedaluminapowderspureordopedwith differentamountsofZr4+cations.
AscanbeseenfromFig.7,dopingaluminapowderswith Zr4+ cations delays the densification at higher temperatures whatever the amount of doping agent. Moreover, increasing thedopingagentamountalsotendstodelaythedensification at higher temperatures evenif thiseffect isless pronounced. Indeed,thedensificationofAPstartsat850◦C,comparedto930, 960and1000◦CforAZ150,AZ280,andAZ570,respectively. Thehigher densificationratesareobtained at1050,1060and 1070◦CforAZ150,AZ280,andAZ570,respectively,compared to1000◦Cforpurealuminasamples(AP).
SegregatedZr4+ cationsalong grainboundariesfavour the presence of aluminiumvacanciesattheir vicinitytopreserve electrical neutrality. Consequently, diffusion mechanisms of Al3+cationsalongthesegrainboundariesshouldbefavoured. Some authors28–31 have proved that the densification of a-aluminabySPSiscontrolledbygrainboundary diffusionbut the rate controlling species are not known for certain. Cur-rently,nostudieshavebeenabletoascertainwhetheraluminium grainboundarydiffusionisgreaterorsmallerthanoxygengrain boundary diffusion.32 Thismeansthat the promotionof Al3+ cations diffusionmechanisms maynot improvethe densifica-tionofa-aluminaiftheratecontrollingspeciesareO2−anions. Inourstudy,segregatedZr4+cationsatgrainboundariesdelay thedensificationathighertemperatures.AccordingtoYoshida,2 thesubstitutionofanAl3+cationbyaZr4+cationincreasesthe ionicbondingstrengthbetweenAl3+cations andO2−anions. It thus slows downthe grainboundary and latticediffusions ofbothspecies(grainboundariesaretheoriginofdiffusionin bothcases).Asaresult,thedensification isdelayed athigher temperatures.
Finally,asthedensificationofsamplesdopedwithagreater amountofZr4+cationsismoredifficult(slightdelayathigher temperatures),thiscouldexplainwhythesesamplesshowmore porosityaftersinteringandthusreducetransparency.
3.2. La-dopedalumina
3.2.1. Opticalproperties
La-dopedpowdersweresinteredatdifferentTf:1230,1250,
1280,1300and1330◦C.ThehighestRITs
640nmwereobtained atTf=1250,1280and1300◦Candtheseresultsarepresented inFig.8.
Fig. 8.RITs640nm of La-doped alumina samplessintered at Tf=1250◦C,
1280◦Cand1300◦Cfordifferentamountsofdopingagent.
Fig. 9.Average grain sizes of La-doped alumina samples sintered at
Tf=1250◦Cand1280◦Cfordifferentamountsofdopingagent.
DopingwithLa3+cationsenablesanincreaseintheRIT640nm ofaluminasamplesduetoareducedgrainsize(Fig.9). More-over,RITs640nm of samplessintered at1250and1280◦Care verysimilar.ThisisingoodagreementwithworkbyRoussel etal.33 whofoundthatdopingPCAwithLa3+cationsenables hightransparencytobeobtainedoveralargerangeofsintering temperatures.
Interestingly,addingLa3+cationsabove100catppmhasno additionaleffect onthe grain size whichremains constantat around0.35mmand0.45mm,at1250◦Cand1280◦C, respec-tively.AsγG,thelightscatteringcoefficientbygrainboundaries,
dependsonlyongrainsize(Eq.(2)),thismeansthatthe differ-encesbetweentheRITs640nmof samplessinteredatthe same temperatureareduetoeitherporosity(γP)orsecondaryphase
particles(γdop)(Eqs.(1)–(3)).TEMobservationscouldhelpus
clarifythispoint.
3.2.2. TEManalysis
TheatomicnumberofLa(Z=57)ishigherthanthatofAl (Z=13).HAADFobservationscanthusbeperformedto indi-cate the presence of La3+ cations within an alumina matrix. SuchobservationswereperformedwithEDXspectroscopyon samples doped with different amounts of La3+ cation. They revealedthatnoLa3+cationsarelocatedwithinaluminagrains (Fig.10(a)).Lanthanumsegregationisfoundalonggrain bound-aries(Fig.10(c)).Moreover,secondaryphaseparticlesareonly formedfor the highestLa-doped samplesAL310 andAL670 (Fig.10(b and c)). Thismeans that the La3+ grain boundary
L.Lallemantetal./JournaloftheEuropeanCeramicSociety34(2014)1279–1288 1285
Fig.10.HAADFobservationsandEDXspectroscopyof(a)AL200,(b)AL310,and(c)AL670samples.ArrowsindicatetheEDXanalysispoint.
Table2
Atomicratiosoftheelementspresentwithinalanthanum secondaryphase particle.
Element Atomicratio(%)
Carbon 1.29±0.06
Oxygen 56.36±0.33
Aluminium 37.53±0.25
Chlorine 2.83±0.07
Lanthanum 1.97±0.18
solubilityisbetween200and310catppmLafora400nmAl2O3 grainsize.
EDXspectroscopywithinasecondaryphaseparticlereveals the presence of lanthanum, aluminium,oxygen andchlorine. Chlorineisduetothelanthanumchloridesaltusedasthe pre-cursorfordoping.Theatomicratiosofthesedifferentelements aregiveninTable2.Forthisestimation,thepeakswerefirst iden-tifiedbeforesubtractingthebackgroundofthespectrum.Then, theCliff–Lorimermethodwasusedtocorrelatetheintensityof thesignalwithelementconcentration.Finally,itwasassumed thatthesummationofallcalculatedconcentrationsisequalto1. Basedontheseresults,thesecondaryphaseissupposedtobea
b-aluminaLaAl11O18structureastheatomicratiosarecloseto thoseinsuchastructure(3.4%La,36.6%Aland60%O).Itis alsoinagreementwithXRDresultsobtainedonAL670(Fig.5). As for Zr4+ cations, the presence of La3+ cations atgrain boundaries hinders diffusion across these boundaries. More-over,thesolutedrageffectpreventstheirmobility.27From0to 100catppm,thosephenomenareducethegrainboundary mobil-ityallthemoreastheamountofdopingagentincreases.Above 100catppm,grainsizeisconstant(Fig.9).Thissuggeststhat thediffusionacrossgrainboundariesisblockedandthatneither anadditionofsegregatedcationsnortheformationofsecondary phaseparticleswillfurtherinhibitgraingrowth.
Concerningtheinfluenceofmicrostructureonoptical prop-erties when no secondaryphaseparticlesare formed (for the samples AL40,AL100 and AL200),onlythe degree of light scatteringduetograinsizeandporosityhastobeconsidered. Theresultsarethuscomparedwiththetheoreticalmodel devel-opedbyApetz(Eqs.(1)and(2)).Theoreticalcurves(Fig.11) werethereforecalculatedfora100nmporesizeasitisthelargest poresizeobservedbyTEM(Fig.10).
Increasing theamountoflanthanumreducesthegrainsize butatthesametimeitdoesnotallowabetterdensificationto
1286 L.Lallemantetal./JournaloftheEuropeanCeramicSociety34(2014)1279–1288
Fig.11.ComparisonofRITs640nmofAL40,AL100andAL200samplessintered
atTf=1250◦Cand1280◦Cwiththeoreticalmodels(λ0=640nm,D=0.88mm,
φp=100nm).
Fig. 12.Theoretical curves of RIT640nmversus thediameter of LaAl11O18
particlesfordifferent amountsofdoping agent(λ0=640nm, D=0.88mm,
φG=450nm,φp=100nm,p=0.01%).
beobtainedbecausetheporosityisgreater(0.03%).Thestudy of the sintering behaviour of La-doped samples will thus be discussedinthenextsection.
For samples dopedwith a larger amount of La3+ cations (AL310 and AL670), b-alumina LaAl11O18 particles are observed(Fig.10(bandc)).Duetoitsdifferentrefractiveindex comparedtoalumina(about1.7834and1.76forLaAl11O18and a-alumina,respectively),theLaAl11O18phasecaninducelight scattering(Eq.(3)).Forexample,at1280◦C,theRIT
640nmvalue decreasesfrom50±1%to43±1%betweenAL310andAL670 samples.Thisdecreaseoccurswithoutgraingrowth.The con-tribution of the secondary phase particles to thisdecrease is evaluatedinFig.12.Theoreticalcurveswerecalculatedfora grainsizeof450nmasitcorrespondstothatobtainedfor sam-plessinteredatTf=1280◦C.Theporesizewasfixedat100nm
as itisthelargestporesizeobservedbyTEM.Moreover,the largestsecondaryphaseparticlesobservedbyTEMarearound 100nm forbothsamples. Accordingtothe Apetzmodel, the residualporosityshouldbearound0.01%,whichislowerthan theonefoundonlessdopedsamples(0.03%).Alvarez-Clemares etal.35haveshownthatceriumoxidesecondaryphaseparticles are locatedatgrainboundariesandtriplepointswithinPCA, closingtheporesusuallylocatedatthesepositions.Wecanthus assumeanequivalentbehaviour ofb-alumina particleswhich
Fig.13.Densificationrateoffreeze-driedaluminapowders,pureordopedwith differentamountsofLa3+cations.
werealsolocated attriplepoints. That iswhytheporosityis lowerforsampleshavingsecondaryphaseparticles.
3.2.3. Sintering
Freeze-driedpowdersdopedwithdifferentamountsofLa3+ cationsweresinteredbySPSatTf=1280◦C.Thedensification ratesofthedifferentpowdersareshowninFig.13.
AscanbeseenfromFig.13,thedensificationbehaviourof slightlydopedsamples(below100catppm)issimilartothatof undopedsamples.Wecanthusinitiallyassumethattheamount ofLa3+cationsislowerthantheirbulksolubilitylimit(no seg-regatedcationsalongthegrainboundaries)sincedensification iscontrolledbygrainboundarydiffusionmechanisms. Never-theless,Fig.9 showsthatthe grainsizeisalreadydecreasing fordopingamountsas lowas 40catppm, suggestingthat the dopingagentisalreadysegregatedatthegrainboundariesand isactiveinlimitinggraingrowth.Therefore,itisasthoughthe lanthanumbulksolubilitylimit isbelow40catppm,as calcu-latedbyGalmarini,4evenifbelow100catppmsegregatedLa3+ cationshavenodetectableeffectsonthedensificationbehaviour of alumina samples. Above 100catppm, the densification of La-dopedsamplesisdelayedathighertemperatures.The densi-ficationofAPstartsat850◦C,comparedto940,990and1010◦C forAL200,AL310,andAL670,respectively.Thehigher densi-ficationratesareobtainedat1050,1070and1090◦CforAL200, AL310andAL670comparedto1000◦Cforpurealumina sam-ples (AP). This is due to the larger amount of La3+ cations alonggrain boundariesor attriplepointsthat hinder the dif-fusionmechanismsresponsiblefordensification.However,too manysegregatedLa3+cationsmayhinderporosityreductionat theendofsinteringthusexplainingwhyAL40andAL100have asimilardensificationrateprofilebuttheporosityaftersintering isfoundtobegreaterforAL100samples(Fig.11).
3.3. OptimisedZrandLadopingconditions
ObtainingtransparentPCAsamplesisallaboutfindingthe bestcompromisebetween grainsize,porosity andamountof dopingagent.Thepresenceofsecondaryphaseparticlesor sig-nificantsegregationalonggrainboundarieshastobeavoidedas eitherclearlydecreasetransparency(Fig.12).Asmallamount ofdopingagentisthuspreferredbecauseitenablesareduction
L.Lallemantetal./JournaloftheEuropeanCeramicSociety34(2014)1279–1288 1287 inthegrainsizewithoutsecondaryphaseformation.Moreover,
samplesdopedwithdifferentagentsofdifferentnatureand/or amount couldlead tosimilar RIT640nm valuesproviding that thesinteringcycleisadapted.Forexample,AZ280andAL40 bothleadtoRIT640nm∼44±1%buttheir sintering tempera-tures are different (Tf=1300◦C and 1280◦Cfor AZ280 and
AL40,respectively).
Finally,the optimisedcationamountsfor transparencyare foundto be150 and200catppmfor Zr-and La-doped sam-ples,respectively.ThehighestRIT640nmof53±1%obtainedin thisstudyforAL200samplessinteredatTf=1250◦Cis
equiva-lenttotheoneofStuerfor225catppmLa-dopedalumina7also obtained with freeze-dried powders. Nevertheless, this value also correspondsto theone obtained inourprevious study24 onthegreenbodyprocessingoptimisationforpurea-alumina beforesinteringbySPS.Thus,combiningthebeneficialeffects ofthegreenbodyparticlepackingoptimisationandtheaddition ofthegoodamountofgraingrowthinhibitorinafineralumina powderwillagainimprovetheopticalpropertiesofa-alumina sinteredbySPSupto71% RIT640nmasdemonstratedinRef. 33.
4. Conclusions
Theeffectofamountofdopingagentonmicrostructureand opticalpropertiesofZr-andLa-dopedaluminahasbeen inves-tigated.BothZr4+andLa3+aregraingrowthinhibitorsandthus enabletheopticalpropertiesofsparkplasmasinteredalumina tobeincreased.Moreover,bothdopingcationsareinsoluble(or nearly) inthe a-alumina latticeand disturbthe grain bound-arydiffusion.Densificationisthusdelayedandoccursathigher temperatures.
Zr4+ cations segregateat grainboundaries for amountsof dopingagentashighas280catppmwithagrainsizeof450nm. At 570catppm, a few particles of monoclinic zirconia are formed.TheoptimisedamountofZr4+ cationstoobtain trans-parentPCAisaround150catppmevenifthegrainsizeisnot thefinest,becausenosecondaryphaseparticlesareformedand thedensificationiseasierthanforhigherdopingamounts(slight delaytowardshighertemperatures).AmaximumRIT640nmof 48±1%isfoundforsinteringatTf=1300◦C.
La3+cationsfirstsegregateatgrainboundariesbefore form-ingb-aluminaLaAl11O18particlesat310catppmLaforagrain sizeof 450nm.Nevertheless, 100catppmofsegregated La3+ cations are sufficient toblock thediffusion pathacross grain boundaries.Asaresult,thegrainsizeofLa-dopedsamplesis constantforhigherthan100catppmLa3+.
Forbothdopingagents,thereduction inopticalproperties (transparency)isattributedtoanincreaseintheporositywhen nosecondaryphaseparticlesareformed.Aftertheformationof asecondaryphase,thoseparticlescontributetolightscattering; themoreparticlestherearethemorescatteringisobserved.
Finally,thehighestRIT640nmof53±1%isobtainedwhen dopingwith200catppmofLa,thoughitcanstillbeimproved byoptimisingthegreenbodyprocessing.33
Acknowledgements
ThisworkispartoftheCeraTRANSproject.Wewouldliketo thanktheANR(FrenchNationalResearchAgency)forits finan-cialsupport.WewouldalsoliketothankSandrineTrombertand LionelBonneaufromBaïkowskifortheirhelpinsample char-acterisation.OurfinalthanksgototheCLYM(CentreLyonnais deMicroscopie:www.clym.fr)–supportedbytheCNRS,the “GrandLyon”andtheRhône-AlpesRegion–foruseoftheJEOL 2010Fmicroscope.
References
1.YoshidaH,IkuharaY,SakumaT.Vacancyeffectofdopantcationonthe high-temperaturecreepresistanceinpolycrystallineAl2O3.MaterSciEng
A2001;319–321:843–8.
2.YoshidaH,IkuharaY,SakumaT.Grainboundaryelectronicstructurerelated tothehigh-temperature creepresistancein polycrystallineAl2O3.Acta
Mater2002;50(11):2955–66.
3.YoshidaH,HashimotoS,YamamotoT.Dopanteffectongrainboundary diffusivityinpolycrystallinealumina.ActaMater2005;53(2):433–40. 4.GalmariniS,AschauerU,TewariA,AmanY,VanGestelC,BowenP.
Atomisticmodelingofdopantsegregationina-aluminaceramics:coverage dependentenergyofsegregationandnominaldopantsolubility.JEurCeram Soc2011;31(15):2839–52.
5.SwiatnickiW,Lartigue-KorinekS,LavalJY.Grainboundarystructureand intergranularsegregationinAl2O3.ActaMetalMater1995;43(2):795–805.
6.VoytovychR,MacLarenI,GülgünM,CannonR,RühleM.Theeffect ofyttriumondensificationandgraingrowthina-alumina. ActaMater
2002;50(13):3453–63.
7.StuerM,ZhaoZ,AschauerU,BowenP.Transparentpolycrystallinealumina usingsparkplasmasintering:effectofMg,YandLadoping.JEurCeram Soc2010;30(6):1335–43.
8.KrellA,BlankP,MaH,HutzlerT,VanBruggenMPB,ApetzR. Transpar-entsinteredcorundumwithhighhardnessandstrength.JAmCeramSoc
2003;86(1):12–8.
9.Bernard-GrangerG,GuizardC.InfluenceofMgOorTiO2dopingonthe
sin-teringpathandontheopticalpropertiesofasubmicronicaluminamaterial.
ScrMater2007;56(11):983–6.
10.Bernard-GrangerG,GuizardC,AddadA.InfluenceofCo-dopingonthe sin-teringpathandontheopticalpropertiesofasubmicronicaluminamaterial.
JAmCeramSoc2008;91(5):1703–6.
11.RousselN,LallemantL,DurandB,GuillemetS,ChaneChingJY,Fantozzi G,etal.Effectsofthenatureofthedopingsaltandofthethermal pre-treatmentandsinteringtemperatureonsparkplasmasinteringoftransparent alumina.CeramInt2011;37(8):3565–73.
12.StuerM,ZhaoZ,BowenP.Freezegranulation:powderprocessingfor transparentaluminaapplications.JEurCeramSoc2012;32(11):2899–908. 13.ApetzR,VanBruggenMPB.Transparentalumina:alight-scatteringmodel.
JAmCeramSoc2003;86(3):480–6.
14.StuerM,BowenP,CantoniM,PecharromanC,ZhaoZ.Nanopore char-acterization,opticalmodelingoftransparentpolycrystallinealumina.Adv FunctMater2012;22:2303–9.
15.KimBN,Hiraga K,MoritaK,YoshidaH,KagawaY.Lightscattering inMgO-dopedaluminafabricatedbysparkplasmasintering.ActaMater
2010;58(13):4527–35.
16.PecharromanC,Mata-OsoroG,DaazLA,TorrecillasR,MoyaJS.On the transparency of nanostructured alumina: Rayleigh-Gans model for anisotropicspheres.OptExpress2009;17(8):6899–912.
17.ChoJ,WangCM,ChanHM,RickmanJM,HarmerMP.Astudyof grain-boundarystructureinrare-earthdopedaluminasusinganEBSDtechnique.
JMaterSci2002;37(1):59–64.
18.BruleyJ,ChoJ,ChanHM,HarmerMP,RickmanJM.Scanning transmis-sionelectronmicroscopyanalysisofgrainboundariesincreep-resistant
1288 L.Lallemantetal./JournaloftheEuropeanCeramicSociety34(2014)1279–1288
yttrium-andlanthanum-dopedaluminamicrostructures.JAmCeramSoc
1999;82(10):2865–70.
19.WangCM,Cargill GS,ChanHM, HarmerMP.StructureofYandZr segregatedgrainboundariesinalumina.InterfaceSci2000;8(2):243–55. 20.Shannon R. Revised effective ionic radii and systematic studies of
interatomic distancesin halidesand chalcogenides.ActaCrystallogrA
1976;32:751–67.
21.Djuricic B, Pickering S, Glaude P, McGarry D, Tambuyser P. Ther-malstabilityoftransitionphasesinzirconia-dopedalumina.JMaterSci
1997;32(3):589–601.
22.ThompsonAM,SoniKK,ChanHM,HarmerMP,WilliamsD,ChabalaJ, etal.Dopantdistributionsinrare-earth-dopedalumina.JAmCeramSoc
1997;80(2):373–6.
23.FangJ,ThompsonAM,MartinPH,HelenMC.Effectofyttriumand lan-thanumonthefinal-stagesinteringbehaviorofultrahigh-purityalumina.J AmCeramSoc1997;80(8):2005–12.
24.LallemantL,FantozziG,GarnierV,BonnefontG.Transparent polycrys-tallinealuminaobtainedbySPS: greenbodiesprocessing effect.J Eur CeramSoc2012;32(11):2909–15.
25.KimBN,HiragaK,MoritaK,YoshidaH.Sparkplasmasinteringof trans-parentalumina.ScrMater2007;57(7):607–10.
26.Kim BN,Hiraga K, MoritaK,Yoshida H.Effectsof heating rate on microstructureandtransparencyofspark-plasma-sinteredalumina.JEur CeramSoc2009;29(2):323–7.
27.Kang SJL. Sintering densification, grain growth & microstructure. Butterworth-Heinemann;2005.
28.LangerJ,HoffmannMJ,GuillonO.Directcomparisonbetweenhot press-ingandelectricfield-assistedsinteringofsubmicronalumina.ActaMater
2009;57(18):5454–65.
29.SantanachJG,WeibelA,EstournesC,YangQ,LaurentC,PeigneyA.Spark plasmasinteringofalumina:studyofparameters,formalsinteringanalysis andhypothesesonthemechanism(s)involvedindensificationandgrain growth.ActaMater2011;59(4):1400–8.
30.AmanY,GarnierV,DjuradoE.Sparkplasmasinteringkineticsofpure a-alumina.JAmCeramSoc2011;94(9):2825–33.
31.DemuynckM,ErauwJP,VanderBiestO,DelannayF,CambierF. Densi-ficationofaluminabySPSandHP:acomparativestudy.JEurCeramSoc
2012;32(9):1957–64.
32.HeuerA.Oxygenandaluminumdiffusionina-Al2O3:howmuchdowe
reallyunderstand?JEurCeramSoc2008;28:1495–507.
33.RousselN,LallemantL,ChaneChingJY,GuillemetS,DurandB,Garnier V,etal.Highlydense:transparenta-Al2O3ceramicsfromultrafine
nanopar-ticlesviaastandardSPSsintering.JAmCeramSoc2013;96(4):1039–42. 34.YamashitaI,TsukumaK,KusunoseT.TranslucentAl2O3/LaAl11O18
com-posite.JAmCeramSoc2009;92(9):2136–8.
35.Alvarez-ClemaresI,Mata-OsoroG,FernandezA,Lopez-EstebanS, Pechar-romanC,TorrecillasR,etal.Ceriadopedaluminabysparkplasmasintering foropticalapplications.JEurCeramSoc2012;32(11):2917–24.