ANNALSofFacultyEngineeringHunedoara

InternationalJournalofEngineering

TomeXII[2014]Fascicule4[November]
ISSN:15842673[CDRom,online]
afreeaccessmultidisciplinarypublication
oftheFacultyofEngineeringHunedoara
F.O.ARAMIDE,1,2.K.K.ALANEME,3.P.A.OLUBAMBI,1,2.J.O.BORODE

1,2.

EFFECTSOF0.2Y9.8ZrO2ADDITIONONTHEMECHANICAL
PROPERTIESANDPHASEDEVELOPMENTOFSINTERED
CERAMICPRODUCEDFROMIPETUMODUCLAY

Department of Metallurgical and Materials Engineering, Federal University of Technology, P.M.B. 704,
Akure,NIGERIA
2. African Materials Science and Engineering Network, (AMSEN) a Subsidiary of Regional Initiative for
ScienceEducation(RISE)
3. Applied Microscopy and Triboelectrochemical Research Laboratory, Department of Chemical and
MetallurgicalEngineering,TshwaneUniversityofTechnology,Pretoria,SOUTHAFRICA
1.

Abstract: The effects of the addition of yttria stabilized zirconia and sintering temperatures on the phases
developed and the mechanical properties of sintered ceramic produced from Ipetumodu clay was
investigated. The clay of known mineralogical compositions was thoroughly blended with 2% (vol) yttria,
8%(vol)zirconia.Fromthisandtherawclaystandardsampleswereprepared,firedat1200oCand1300oC.
Thesinteredsampleswerethencharacterizedforthedevelopedphasesusingxraydiffractometryanalysis,
microstructuralmorphologyusingultrahighresolutionfieldemissionscanningelectronmicroscope(UHR
FEGSEM) and various mechanical properties. It was observed that primary mullite and sillimanite were
developed in the samples produced. The samples produced solely from the raw clay could not withstand
1300oC due to stress induced by the transformation from one silica phase to another. This phase
transformation also adversely affected the mechanical properties of the sintered raw clay. The additive
improvedonthemechanicalpropertiesofthesamplesbytheconsumptionofthesilicaphasestoformzircon
phaseinadditionwiththeotherphasesandtheexcesszirconia.Itwasconcludedthatthe samplefiredat
1300oChavetheoptimummechanicalproperties.
Keywords:yttriastabilizedzirconia;sinteringtemperatures;phasesdeveloped;clay;sinteredceramic

1.INTRODUCTION
The word ceramics is a broad name which is applicable in many products. They possess good
corrosionresistanceandabilitytopreservetheirpropertiesatahightemperatureupto1200oC.
Other useful properties that make the ceramic attractive for engineering applications include
excellenthightemperaturestrengthandcreepresistance,goodthermalandchemicalstability,low
thermalexpansioncoefficient,lowtruedensity,wearresistanceandgooddielectricproperties[1
6].Recently,manyresearchershavefocusedtheirinvestigationsonhowtoimprovetheproperties
of ceramics for various applications. Zum Gahr [7], demonstrated that modification of the
microstructure could reduce the friction and the wear of alumina. Likewise in 1996, he showed
thatreducingthegrainsizeofaluminaandzirconiawillsignificantlydecreasethewear[8].
Furthermore Dong et al [9], specified the effect of both single additives (MgO, SiO2, Fe2O3 and
ZrO2) and compound additives on the mechanical and thermal properties of aluminum titanate
ceramics,andfinallypointedoutthatthecompoundadditivesofMgOandFe2O3haveanexcellent
improvementonthestabilityofaluminumtitanate.Jiangetal[10],alsodemonstratedthattherole
of additives can be rationalized in terms of promotion of sintering process, formation of new
phasesandinfluenceonlatticeconstantofaluminumtitanateceramics.
Ebadzadeh and Ghasemi [11], observed that the addition of TiO2 to mulliteZrO2 composites
prepared from different alumina sources results into change of reaction sintering, densification
andmicrostructurewhichcanalternatelyaltertheformationtemperatureandretentionoftZrO2
copyrightFacultyofEngineeringHunedoara,UniversityPOLITEHNICATimisoara

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phase in these composites. Moya et al. [12] demonstrated that the microstructure of mullite
zirconiaandaluminazirconiacompositescanbemodifiedbyadditiveslikeCaOandMgO.
Ipetumodu is a town in Osun State, in the southwestern part of Nigeria. The size of the town is
64km2(25sqmi).ThetownistheheadquartersofIfeNorthlocalgovernmentArea.Itislocatedat
anelevationof227metersabovesealevelanditspopulationamountsto164,172.Itscoordinates
are7310Nand4270E.
Variousresearchershaveinvestigatedthepropertiesofthisclaydepositforindustrialapplications
[1316].Butthereisnorecordoftheinvestigationoftheeffectsoftheconcernedadditivesonthe
mechanicalpropertiesandphasedevelopmentofthesinteredceramicproducedfromclaysourced
fromthedeposit.
2.MATERIALSANDMETHODS
2.1.Materials
ClaySamplesusedinthisworkweresourcedfromIpetumodu,OsunStateinthesouthwestern
partofNigeria.HighpurityoxidessuchaszirconiaandyttriaweresuppliedbyF.J.BODMANN&
CO,L.L.C.(TheThermalSprayMaterialsandTechnologiesSource).OakmereBusinessPark,2072
SussexStreet,Harvey,LA70058.
2.2.RawClayPreparation
Theclaysampleswerefirstsoakedinwaterforthreedaystodissolvethedeleteriousmaterialsin
them and at the same time to form slurry. The slurries were then sieved to remove deleterious
materialsandotherforeignsubstances.Thesievedslurrieswerethenallowedtosettledownfor
three days after which the clear floating water was decanted. The dispersed fine clays in water
(clayslurries)werethenpouredintoplasterofParis(P.O.P)mouldsandleftundisturbedforthree
daysinordertoallowtheremainingwaterpresenttodrainoutcompletely.Theresultingplastic
claymassesweresundriedandsubsequentlydriedinalaboratoryovenat110oCfor24hours.The
resultingdriedclaysampleswerecrushedandmilledinaRawwleySussexgrindertoanaverage
particlesizeof300m.
2.3.ChemicalandMineralogicalComposition
ofRawClaySamples
The compounds present in the samples were
determined by xray fluorescence (XRF). The
results obtained are presented in Table 1. The
mineralogical phases present in the samples
were
also
determined
using
xray
diffractometry (XRD). The phases present are

Figure1:XRayDiffractionPattern(PhaseAnalysis)of
reportedinFigure1andTable2.Thechemical
IpetumoduClaySample
composition of the clay samples were
determined using atomic absorption spectroscopy (AAS). The results obtained are presented in
Table 3. Ultrahigh resolution field emission scanning electron
Table1:XRFSemiquantitative
microscope (UHRFEGSEM) equipped with energy dispersive
analysisoftheelementsofraw
claysamples(weight%)
spectroscopy(EDS)wasusedtoexaminethemicrostructureof
Phases
Amount(%)
the clay samples. The observed microstructures are presented
Al2O3
25.03
SiO2
57.482
inFigures2,3,4and5.
Si O2

IP E T U .R D

Ti O2; Si O2

Al ( O H )3; Si O2

200

Ti O2; Al ( O H )3

Si O2

Ti O2; Si O2

Ti O2

Ti O2; Al ( O H )3

Al ( O H )3

100

10

20

30

40

50

60

70

P o s i ti o n [ 2 T h e ta ]

Fe2O3
K2O
MgO
CaO
Na2O
TiO2
Zr
Total

344 | Fascicule 4

9.226
1.259
0.91
0.763
0.372
1.512
0.103
97.1

Table2:XRDResultoftheRawClaySamplesShowing
theQuantityofDifferentPhasesPresent
Phases
Weight(%)
Kaolinite
23.74
Microcline
26.12
Muscovite/Illite
15.02
Plagioclase/Albite
11.28
Quartz
23.84

80

Quartz

Hematite

Mullite

Sillimanite

Pseudob
rookite

Iron(III)
Niobium
Oxide
(1/1/4)

Rutile

Aluminium
Niobate(V)

Zircon

mZrO2

Cristobalite

LOI
11.64

Samples

ANNALS of Faculty Engineering Hunedoara International Journal of Engineering

Table3.ChemicalCompositionofRawClaySamples(%)
Samples
SiO2
Al2O3
Fe2O3
TiO2
CaO
MgO
Na2O
K2O
RawClay
54.82
25.90
1.44
2.08
0.12
0.15
0.2
1.57
Table4.XRDResultoftheSinteredCeramicSamplesRT1,FT1andFT2Showing
theQuantityofDifferentPhasesPresent

RT1
FT1
FT2

14.1
8.16
1.96

9.26
4.72
3.96

42.51
7.37
10.97

6.63
16.07
18.38

4.63
1.26
1.12

0
0.42
0.78

0.54
0.45
1.39

0
1.91
2.53

0
4.12
23.19

0
42
28.8

22.3
13.52
6.92

2.4.PreliminaryTestingofSinteredRawClay
TheclaysamplefromIpetumoduwasfirstmilledin
ahighenergyplanetaryballmillat300rev/minfor4
hour to obtain average particle size of 75m.
Standard dimensions test samples were produced
from the milled clay; for phase analysis and
SEM/EDS analysis and mechanical properties by
compacting in a stainless steel mold using a load of
750 MPa. The green compact were then sintered
(fired)at1200oCand1300oC(T1andT2respectively)
heldforanhour,inanelectricfurnace.Thesamples
were designated as R The sample sintered at
o
1200 C were subjected to various tests such as
Figure2.TypicalSEM/EDSmicrographsof determinationofthephasesdevelopedinthesample
RawClaySampleshowingthemorphologyof due to sintering using XRD and bulk density,
themineralanditschemicalcomposition
apparentporosity,coldcrushingstrengthmodulusof
elasticity, and absorbed energy. The results obtained are shown in Tables 4 and 5 for XRD and
mechanicalpropertiesrespectively.

(a)
(b)
Figure3.TypicalSEMmicrographsofSampleRT1showingitsmorphologyandcracks(a)BackScattered
Imageand(b)SecondaryElectronImage

X
(a)
(b)
Figure4.TypicalSEMmicrographsofSampleFT1showingitsmorphology(a)BackScatteredImageand(b)
SecondaryElectronImageX=PhasewithZrO2,whileZ=phasesofsinteredclay

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X
Y
Z
(a)
(b)
Figure5.TypicalSEMmicrographs(BackScatteredImage)ofSampleFT2showingitsmorphology(a)Back
ScatteredImageand(b)SecondaryElectronImage.X=PhasewithZrO2,Y=Zirconphase,whileZ=phasesof
sinteredclay

2.5.PowderBlending
ThemasspercentofthecompositionbelowwascomputedusingEquations(1)and(2)usingthe
densities in Table M2 and the individual powders volume fraction in each composition. The
powderswereweighedperbatchof50.00gonasensitiveelectronicweighingbalancetofive(5)
decimalplaces.Theindividual(batch)compositionwasthoroughlymixedinaTurbulaMixerfor
18hoursataspeedof72rev/min.ThecompositionsoftheblendedsampleswereshowninTable
M1.
TableM1.TheCompositionsofSamplesproducedfrom
blendedpowdersusedfortheExperimentalInvestigations
Designation RawClay Zirconia(ZrO2) Yttria(Y2O3)
(Vol.%)
(Vol.%)
(Vol.%)
F
90
9.8
0.2

TableM2.DensitiesofVarious
Componentsused
Oxide/Clay Claya
ZrO2b
Y2O3b
Density
1.20
5.68
5.01
(g/cm3)

If

(1)
Mt=Vclcl+VZrzr+VYY
whereVcl, VZr, andVY arerespectivelythevolumefractionofclay,ZrO2andY2O3,cl, Zr andYare
respectivelythevolumefractionofclay,ZrO2andY2O3,andMtisthetotalmasscontributionofall
thecomponents.AndifMisthemassofeachbatch,thenthemasscontributionofeachcomponent
couldbecalculatedfrom:
Mc= V cQc xM

(2)
Mt

Mcisthemasscontributionofacomponentinabatch(clayorZrO2orY2O3),Vc,ctherespective
volumefractionanddensityofthecomponent.
The resulting homogenous powder mixtures were compacted uniaxially into standard sample
dimensions for cold crushing strength, bulk density, porosity measurements and thermal shock
resistance. The samples were compressed uniaxially using 750 Mpa compaction load inside a
standard stainless steel die. The resulting green compacts were fired at 1200oC (for FT1) and
1300oC(forFT2)inanelectricfurnace.Thesinteredsampleswerethencharacterizedfor various
mechanicalpropertiesasdescribedbelow:
aDeterminedinthelaboratory
bProvidedbythesupplier
2.6.Testing
2.6.1.ApparentPorosity
Test samples from each of the ceramic composites were dried for 12 hours at 110C. The dry
weightofeachfiredsamplewastakenandrecordedasD.Eachsamplewasimmersedinwaterfor
6hrstosoakandweighedwhilebeensuspendedinair.TheweightwasrecordedasW.Finally,
the specimen was weighed when immersed in water. This was recorded as S. The apparent
porositywasthencalculatedfromtheexpression:

p= ( W - D) x100% (3)
( W - S)

TheresultsobtainedarepresentedinTable5.
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Table5:MechanicalPropertiesofSamplesRT1,FT1andFT2
ThermalShock
Bulk
ColdCrushing
Youngs
Apparent
Absorbed
Samples
Resistance
Density
Strength
ModulusE
Porosity(%)
Energy(J)
(cycles)
(g/cm3)
(N/mm2)
(N/mm2)
RT1
FT1
FT2

+30
+30
+30

22.70
17.50
15.40

1.95
1.87
2.06

1833.3
4409.00
8447.00

0.4320
1.2919
4.1753

21363
55208
64994

2.6.2.ColdCompressionStrength,ModulusofElasticityandAbsorbedEnergy
Coldcompressionstrengthtestistodeterminethecompressionstrengthtofailureofeachsample,
anindicationofitsprobableperformanceunderload.Thestandardceramicsamplesweredriedin
an oven at a temperature of 110C, allowed to cool. The cold compression strength tests were
performedonINSTRON1195atafixedcrossheadspeedof10mmmin1.Sampleswereprepared
according to ASTM C13397 (ASTM C13397, 2003) and cold crushing strength, modulus of
elasticity and absorbed energy of standard and conditioned samples were calculated from the
equation:

CCS= LoadToFracture (4)

SurfaceAreaOfSample

TheresultsobtainedarepresentedinTable5.
2.6.3.BulkDensity
Thetestspecimensweredriedat110Cfor12hourstoensuretotalwaterloss.Theirdryweights
weremeasuredandrecorded.Theywereallowedtocoolandthenimmersedinabeakerofwater.
Bubbleswereobservedastheporesinthespecimenswerefilledwithwater.Theirsoakedweights
weremeasuredandrecorded.Theywerethensuspendedinabeakeroneaftertheotherusinga
slingandtheirrespectivesuspendedweightsweremeasuredandrecorded.Bulkdensitiesofthe
sampleswerecalculatedusingtheformulabelow:

bulkdensity= D (5)
( W - S)

where:D=Weightofdriedspecimen,S=Weightofdriedspecimensuspendedinwater,andW=
Weightofsoakedspecimensuspendedinair.TheresultsofthisarepresentedinTable5.
2.6.4.ThermalShockResistance
Eachsampleoftheclay/sawdustblendwasplacedinanelectricallyheatedfurnacetoattainthe
testtemperatureof1000Cforover3hours.Eachsamplewasthenwithdrawnfromthefurnace
andheldfor10minutes.Theprocedurewasrepeateduntilanappearanceofacrackwasvisible.
Thenumberofcyclesnecessarytocauseacrackwasrecordedforeachofthesamplesandtakenas
ameasureofitsthermalshockresistance.
2.7.Analysis
2.7.1.QualitativeandQuantitativeXRD
ThesampleswerepreparedforXRDanalysisusingabackloadingpreparationmethod.Theywere
analysed using a PANalytical XPert Pro powder diffractometer with XCelerator detector and
variable divergence and receiving slits with Fe filtered CoK radiation. The phases were
identifiedusingXPertHighscoreplussoftware.Graphicalrepresentationsofthequalitativeresult
followbelow.Therelativephaseamounts(weights%)wereestimatedusingtheRietveldmethod
(Autoquan Program). Amorphous phases, if present were not taken into consideration in the
quantification.TheresultsobtainedarepresentedinFigure2andTables2and4.
2.7.2.ScanningElectronMicroscopy

Morphology and microanalysis of the clay and composite samples were determined using ultra
high resolution field emission scanning electron microscope (UHRFEGSEM) equipped with
energy dispersive spectroscopy (EDS). The pulverized clay samples/sintered ceramic composite
sampleswerepreviouslygoldcoated.Thesampleswerestudiedusingultrahighresolutionfield
emission scanning electron microscope (UHRFEGSEM) equipped with energy dispersive
spectroscopy (EDS). Particle images were obtained with a secondary electron detector. The
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SEM/EDSmicrographsofthepowderclayandthevarioussinteredceramicsamplesareshownin
Figures2to5.
2.7.3.ChemicalAnalysis
(a)XRayFluorescence(XRF)ThemajorelementsweredeterminedbyXrayfluorescencewith
anARL9800XPspectrometer.Thepulverizedclaysamplesweremixedwithlithiumtetraborate
forchemicalanalysis.Theignitionlosswasmeasuredbycalcinationsat1000C.TheXRFresultis
showninTable1.
(b)AtomicAbsorptionSpectroscopy(AAS)Thechemicalanalysisoftheclaysampleswasalso
carried out using atomic absorption spectrophotometry (AAS) method with Spectra AA 220 FS
Machine.ThepercentagecompositionsofthevariousconstituentswerethenrecordedinTable3.
3.RESULTSANDDISCUSSION
3.1.PhaseDevelopmentandMechanicalPropertiesoftheSinteredRawIpetumoduClay
Tables 4 and 5 shows respectively the phases developed in the samples RT1/1, FT1/1 and FT2/1
andthemechanicalpropertiesofsamplesRT1/1,FT1/1andFT2/1.Figure3showsthemicrographs
ofthesampleRT1/1.
3.1.1.PhaseDevelopmentintheSinteredRawIpetumoduClay
FromTable4thephasesdevelopedintheceramicsampleproducedfromtherawIpetumoduclay
andsinteredat1200oC(RT1/1)areclearlyshown.ComparingthiswiththeXRDresultsshownin
Table2thetotalsilica(quartz)intheclayis23.84%,butinthefiredsample,thetotalsilica(quartz
andcristobalite)is36.4%.Theexcess/extrasilicacomesfromthemullitizationprocess.Moreover,it
isobservedthatthesampleRT1/1containsmulliteandsillimaniteaslistedabove,comparingthese
withTable2,itisobservedthattheclaysamplecontains23.73%kaoliniteandabove37%feldspar.
When kaolinite is fired, the following transformations occur in its structure: The dehydration of
kaolinite completes by ~150oC, followed by dehydoxylation at ~420660C and its structural
breakdown occurs in the temperature range ~800900oC, depending upon the particle size and
amount and type of the impurities present. The kaolinite in the Ipetumodu clay (Table 2)
containing 23.84% quartz, 15.02% muscovite/illite (and about 37% feldspars) dehydroxylates to
metakaoliniteat~420660Cdependingonthetypeandamountofimpuritiespresent[17,18,19]
via

Si2Al2O5(OH)4420660CAl2O3*2SiO2+2H2O(6)
which involves the combination of two OH groups to form H2O and oxygen which remains
incorporatedinmetakolin.Atabout900C,metakaolinitedecomposestoamorphousSiO2and
Al2O3typespinelvia
Al2O3.2SiO2900CAl2O3+2SiO2

(7)
Al2O3typespinelandSiO2recrystallizeintomulliteattemperaturesabove1100Cvia
3Al2O3+2SiO2>1100C3Al2O3.2SiO2
(8)
Srikrishna,etal[20],reportedtheformationofasinglephase(withcompositionclosetomullite)
and excess SiO2 at 900C. Thus the formation of mullite begins at temperatures >900C and the
processcontinuestill1000C
FromtheTable4,itisobservedthattheamountofmullitedevelopedintheRT1is42.51%.Thisis
not unconnected with the presence of hematite and rutile in the raw clay on one hand and the
presenceoffeldsparontheotherhand.
Differentauthorshavedemonstratedthatmullitizationcanbeincreasedbycatalyticionssuchas
Fe3+andTi4+[21,22].ThesemetallicionshelpinmulliteformationbyreplacingtheAl3+ionsinthe
glassstructureduringfiring.ThepresenceofsmallamountsofFe3+andTi4+inkaolinmodifiesthe
chemical composition of the ceramic bodies and therefore the sintering behaviour which in the
caseofporcelainischaracterizedbymullitization.ItcanbeobservedfromTable3thatthesintered
sampleRT1contains4.63%pseudobrookiteand0.54%rutilewhichareoxidesofironandtitanium.
The phenomenon of mullitization is also influenced by the grade of feldspar which particularly
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affectstheformationofsecondarymullite.Thequalityoffeldsparisdeterminedbytheamountof
orthoclase and albite. Nowadays, mixed feldspars are considered suitable fluxing agents for
porcelain manufacture since they develop a very viscous liquid phase that embeds the new
forming crystals and part of the residual crystals present in the microstructure, enhancing the
densification process [23, 24]. However, from the SEM images of the sample RT1, the mullite
needles could not be seen (Figure 2). The mullite in the RT1 as seen the Table 3 is the primary
mulliteasexplainedinthefollowingparagraphs.Mulliteformedfromkaolinclayaloneistermed
primary mullite whereas that formed from reaction with an alkali flux is termed secondary. In
vitrifiedtriaxialporcelainsoftheclayfeldsparflintcomposition,mullitecrystalsoftwoorthree
distinctivemorphologieshavebeenreported[2531].
Apartfromtheshape,thecrystalscanalsobedifferentiatedbytheirsizeandaspectratio[31],and
bythechemicalcompositionthatchangesfromthenonstoichiometric2:1ofprimarymullitetothe
stoichiometric 3:2 of seconday mullite [29] on heating to temperatures higher than 1400C in
triaxialcompositions.
Primary mullite of composition close to 2:1, forms only from clay relicts of mostly kaolinite
(Al2O3.2SiO2.2H2O) at 11001150C as small crystals of <0.5m or <0.1m in size. Scaly crystals
forming at lower temperatures are the direct product of clay minerals, and have a characteristic
cuboidal shape as observed under the TEM. Comer [32], found that primary mullite crystals in
vitrified kaolin, although of the characteristic needle shape, were less than 1 m long. From the
crystalsizealone,TEMobservationssuggestedthattheyweresimilartoprimarymullite(ofscaly
appearance)andsecondarymullite(ofgranularshape)[25,2734].
Furthermore,mullitecrystalsproducedinclayfeldsparrelictsaresecondarymullitewithseveral
morphologies,suchasthegranular,cuboidal[29,30,31,35],acicular,orneedlelike[25,35].Iqbalet
al.[29,30]furtherdefinedsecondarymulliteinthefineclay,feldspar,andquartzmatrixbasedon
the aspect ratio [30, 31]. They were observed from both model and commercial [31] triaxial
porcelainsvitrifiedattemperaturesabove1400C.
3.1.2.MechanicalPropertiesoftheSinteredRawIpetumoduClay
ItisobservedfromTable5thatthesinteringtemperaturehasadirectimpactofthethermalshock
resistance of the raw clay. The higher the sintering temperature the better the thermal shock
resistance of the sample. This is expected, as the samples were initially prepared/fired at higher
temperature than the temperature at which the thermal shock resistance tests were carried out.
From the same table, the cold crushing strength (CCS), Youngs Modulus (E), absorbed energy,
apparentporosityandbulkdensityofthesamplepreparedfromtherawsample(RT1)alonewere
observedtobe1833.3N/mm2,21363N/mm2and0.432J,22.70%and1.95g/cm3respectively.
3.2.PhaseDevelopmentintheSinteredSamplesFT1andFT2
FromTable4thephasedevelopmentinthesamplesFT1andFT2areclearlyseen.AtT1(1200oC),
it is observed that the sample contains 8.16% quartz, 4.72% hematite, 7.37% mullite, 16.07%
sillimanite,1.26%pseudobrookite,0.42%FeNbO4,0.45%rutile,1.91%AlNbO4,4.12%zircon,42%
mZrO2, and 13.52% cristobalite. Increasing the sintering temperature to T2 (1300oC), the phases
observedinthesamplesare;1.96%quartz(reduction),3.96%hematite(reduction),10.97%mullite
(increase), 18.38% sillimanite (increase), 1.12% pseudobrookite (reduction), 0.78% FeNbO4
(increase),1.39%rutile(increase),2.53%AlNbO4(increase),23.19%zircon(increase),28.8%mZrO2
(reduction),and6.92%cristobalite(reduction).
It is observed that there were reductions in the amount of quartz, cristobalite phases (which are
silica)andmZrO2,inthesampleat1300oC,FT2(whencomparedwiththesampleat1200oC,FT1).
Conversely,itisobservedthattherewasanincreaseintheamountofzirconphaseinthesample
FT2 when compared with the amount in FT1 (compare Figures 4 and 5). This is because as the
sintering temperature is increased from 1200oC to 1300oC the silica and the zirconia acquired
enoughenergyforthefollowingsolidstatereaction:
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ZrO2(s)+SiO2(s)ZrSiO4(s)

(9)
Thisaccountsforthereductioninthequartz,cristobaliteandmZrO2phasesandtheincreasein
thezirconphaseasstatedabove.Thechangesobservedintheotherphasescouldbeexplainedas
duetothecontributionoftheproductofthesolidstatereactionofequation(9)intheweight(%)of
the sample. From the Table 3, the total weight percent consumed as a result of the solid state
reaction is 26% but the weight percent increase observed in the zircon is just 19.07%. There is a
deficitof6.93%whichwillleadtochangeinthepercentagecontentsofotherphases.
3.3.MechanicalPropertiesoftheSinteredSamplesFT1andFT2
Table5showsthemechanicalpropertiesofthesinteredsamples.Itisobservedthattheapparent
porosity of the sample at 1200oC (FT1), is 17.50%. As the sintering temperature is increased to
1300oC(FT2),theapparentporosityreducedto15.40%.Thiscouldbeexplainedthatincreaseinthe
sinteringtemperatureallowedformoredensificationtotakeplacetherebyallowingmoreporesto
befilledbytheliquidphasepresentattheconcernedtemperaturetherebyreducingtheporosityof
thesample.Itisalsoobservedthatthebulkdensityofthesampleat1200oC(FT1),is1.87g/cm3,as
thesinteringtemperatureisincreasedto1300oC(FT2),theapparentporosityreducedto2.06g/cm3.
Thisbehaviorisalsoduetothereducedporosityofthesampleasexplainedabovewhichleadto
increase in the amount of matter in the sample per unit volume. Furthermore, it is observed at
1200oC(FT1)thatthecoldcrushingstrength(CCS),absorbedenergyandtheYoungsmodulusare
respectively 4409 N/mm2, 1.2919 J and 55208 N/mm2. Moreover, as the sintering temperature is
increasedto1300oC(FT2),thecoldcrushingstrength(CCS)increasedto8447N/mm2,theabsorbed
energyalsoincreasedto4.1753Jsimilarly,theYoungsmodulusalsoincreasedto64994N/mm2.
Thereasonforthisisthatthebulkdensityofthesampleincreasedwiththesinteringtemperature
(consequent to reduction in the apparent porosity of the samples with increased sintering
temperature),whichmeansthattheremorematterinthesampletobeartheappliedload[13,19,
36].Similarly,fromFigures4(b)and5(b),itisclearlyobservedthatthecracksobservedinsample
FT1(Figure4a)duetothephasetransformationfromonesilicaphasetoanother,werecompletely
sealedoffbythezirconphaseinsampleFT2(Figure5b).Thisisalsoresponsiblefortheimproved
mechanical property of FT2 when compared with FT1. The thermal shock resistances of the
samples were observed to be more than 30 cycles. This is due to the fact that the samples were
earliersinteredathighertemperaturethanthetemperatureatwhichthetestwascarriedout.
3.4.ComparisonoftheMechanicalPropertiesofSinteredSampleRT1/1withFT1/1andFT2/1
ComparingthemechanicalpropertiesofsampleRT1/1withthoseoftheFT1/1andFT2/1,itwas
observed that the addition of 10% volume of yttria stabilized zirconia improved the mechanical
properties of the sample. It is noted from Table 4 that sample RT1/1 contains 14.1% quartz and
22.3%cristobalite,FT1/1contains8.16%quartzand13.52%cristobalitewhileFT2/1contains1.96%
quartz and 6.92% cristobalite. These phases have marked differences in their thermal expansion
coefficients and the glass matrix. During cooling from the sintering temperature to room
temperature, the marked differences in thermal expansion results in internal residual stresses
whichadverselyaffectsthestrengthofthesample[37].SampleRT1/1hasthehighestamountof
quartz and cristobalite, followed by FT1/1 while the least amount of the mentioned phases were
observedinFT2/1.ThisexplainedwhythesampleRT1/1hasverylowstrength,whencompared
withtheothertwosamplesandwhythestrengthofFT1/1isabouthalfofthatofFT2/1.Thisisalso
thereasonwhythesampleRT2/1cracked/failedandcouldnotbefurtherworkupon.
4.CONCLUSION
Itcanbeconcludedthat:
9 DuetophasetransformationofthesilicacontentoftheIpetumoduclayfromonesilicaphaseto
anotherduringsintering,themechanicalpropertiesoftheceramicproducedfromitsinteredat
1200oCisverylowandcouldnotwithstandafiringtemperatureof1300oC;
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9 Addition of 2% (vol) yttria, and 8% (vol) zirconia resulted into depletion of the silica phases,
formation of zircon phase and excess zirconia in addition with other phases improved on the
mechanicalpropertiesofthesamplesfiredat1200oCand1300oC
9 Theoptimummechanicalpropertiesisobtainedinthesamplesfiredat1300oC
Acknowledgements
Theauthorswishtoacknowledgethefollowingorganizationsfortheirsupport.TheyareRegionalInitiative
inScienceEducation(RISE),ScienceInitiativeGroup(SIG)andAfricanMaterialsScienceandEngineering
Network(AMSEN).

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