[PDF] USING BORON AS AN AUXILIARY FLUX IN PORCELAIN TILE





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USING BORON AS AN AUXILIARY FLUX IN PORCELAIN TILE

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CASTELL6N(SPAIN)

USINGBORON

ASANAUXILIARYFLUXIN

PORCELAINTILECOMPOSITIONS

A.Moreno,J.Garcia-Ten, E. Bou, A.Gozalbo

InstitutodeTecnologfaCeramica.

Asociaci6n

deInvestigaci6ndelasIndustriasCeramicas.

Universitat[aume1.Castell6n.Spain.

J.Simon,S.Cook,M.Galindo

BoraxEuropeLtd.

1.INTRODUCTION

However,theirlarge-scale

oxide(B 2 0 3) consumptionofboronoxide,estimatedat 1.5milliontonsof B 2 0 3 peryear. Boron commercialglasses.Itactsas a fluxandnetworkformer,allowingtheformulationof glasses playsakeyroleas alowtemperaturefluxwhenthealkalinelevelsarelimitedbyother resistance, oxidefacilitatesglazethermalexpansionandmeltingtemperaturefit tothe glazesforceramicfloorandwalltiles,aswellas fortableware,besidesplayingadecisive rolein theformulationoflead-freeglazes.

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CASTELL6N(SPAIN)

lighting,laboratories, medicine,kitchenutensilsor LCDscreens. In applicationsaredueto itsfluxingeffect, astudywasundertakeninthisworkofthe manufacturinglowporosityceramicbodies.

2. OBJECTIVESANDSCOPE

Thisstudyhastwoobjectives:

- To tilebodies, - To quantityofboron.

3. EFFECT OFBORONONTHEBEHAVIOURANDPROPERTIES OF FLOOR TILE

BODIES

firingstonewareandporcelaintilebodies.

Thefollowingaspects

weretackledinthispartofthestudy: suspensionrheologicalbehaviour -behaviourduringthepressingstage behaviourduringfiring

3.1.EXPERIMENTAL

3.1.1Materials

Tables 1 to 3showthebodycompositionsinvolved(redandwhitefiringfloortile

P.GI-78

44, whosestoichiometric

compositionis CaO·MgO·3B 2 0 3

·6H

2 0 .

RawmaterialContent(%)

Moro clay34

Villar I clay32

Villar2 clay32

Table1.Red-firing stoneware

compositionPGR(wt%).

RawmaterialContent(%)

Teruel clay30

English clay

20

Potassiumsodium feldspar30

Lepidolite

20

Table2.White-firing stoneware

compositionPGB(wt%).

RawmaterialContentCOlo)

Ukrainianclay50

Sodiumfeldspar40

Feldspathic sand10

Table3.Porcelain tile composition GP(wt%).

3.1.2Experimentaldevelopment

Conditioningthecompositions and rawmaterials.

Before

Theclaysweredrymilledinahammermillwithanoutputscreenmeshof 1mm,whereas the non-plasticrawmaterialswerewetmilledin aballmillto arejectof 2%ona 75 urn me hydroboracite,intheappropriatepercentages(Tables 1and3)andthenwetmilleduntil the followingrejectswereobtained: redsto newarefloortile: 4-5%at 63urn whitestonewarefloortile: 2-3%at 63urn porcelaintile: 1.0-1.5%at 40 urn

Rheologicalbehaviour

suspensionswasstudied bydeterminingthedeflocculationcurves.Tocarryoutthistest, suspensions were partssodium metasilicate(SMT)andonepartsodiumtripolyphosphate(STPP). The mea suringinstrumentusedwasaGallemkampviscometerwitha no. 30torsionwire. Int hesetests,the solidscontentofthesuspensionswaskeptconstantforeachtype valueswere 68%forthePGRcompositions,72%forthePGBcompositionsand67%for theGP compositions.

P.GI-79

til'QUALICQJl.,2000

Behaviourduring thepressingstage

CASTELL6N(SPAIN)

moisturecontentof 5.5 %(drybase)anddifferentpressingpressureswhichvaried accordingtothetypeofbody.

Thetest

specimensweredriedtoconstantweightat 110°C inanelectriclaboratory immersionmethod.

Behaviourduring thefiringstage

ofthisvariable.

Firing

tookplaceinanelectriclaboratorykilnwitha fastfiringcycleando-min outbyforcedconvection.

Bulkdensity,linear

specimens.Bulk fortwohoursinboilingwater.

Evolutionofcrystallinephasesduringfiring

phasesduringfiring,9.5 wt% ofHydroboracitewasaddedtotheporcelaintile composition.This Test

GPHB,following

compositionwithouthydroboracite(GP) inordertohavereferencespecimens. thediffractogramswiththeJCPDS files forpurecrystallinephases.Tostudytheevolution

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CASTELL6N(SPAIN)

3.2 RESULTSOBTAINEDANDDISCUSSION

Rheologicalbehaviour

Figures1, 2and3showtheinfluenceofhydroboraciteonthebehaviourofthe compositionsshiftedthecurves morehydroboracitetoachieveworkingviscosity.Thiseffectappearedto bemore pronouncedinthewhitebodycompositions,as inthesecompositionsitwasnecessaryto raise theamountofdeflocculantby 0.5%,whereasthedeflocculantincreasefortheredbody compositionswasonly0.2%.Ontheotherhand,it isworthpointingoutthattheaddition flocculants I1J,thereforerequiringtheadditionof agreaterquantityofdeflocculant J, theboroniondid [OPGR--I·

1.10.90.7

?PGB+O.9%HB

0.50.34000

3500
3000
2500
2000
1500
1000
500
0

0.\1.51.31.1

4000
3500
3000
2500
i 2000
1500
1000
500
0 0.5

0.70.9

Figure1.Deflocculationcurvesof

the redbodycompositions.Figure2.Deflocculationcurvesof thewhite bodycompositions.

Behaviourduring thepressingstage

Fig. 4plotsthecompactiondiagramsofthedifferentcompositions.Bulkdensity rosein allthestudiedcompositionsasappliedpressureincreased,theexperimentaldata inthesetypesofcompositions.

[1]PUGH,R.J.;BERGSTROM,L.Surfaceandcolloidchemistry in advancedceramicsprocessing.NewYork:MarcelDekker,1994.

[2] REED,J.5.Principlesofceramicprocessing.2nded.NewYork:JohnWiley, 1995. [3]

HOWLES;J.A.EffectsofBoronCompoundIncorporationinto a WhitewareBody,February,1999,mastersthesis,AlfredUniversity,

pp14-31Carty

[4]ROSSINGTON,K.R.;CARTY,W.M.TheEffectsof IonicConcentrationon the Viscosity of aClay-BasedSystem;1998,Ceramic

EngineeringScienceProceedings,vol 19, no. 2.,pp65-76.

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til"QUALIC02.,2000

CASTELL6N(SPAIN)

Deflocculantcontent(%)

Figure3.Deflocculationcurvesof

the porcelaintilecompositions.

2.20,------------------,

1000600

-PGR ---PGB -GP 300

Pressure(kg/cmz)

r-OSTD-i

I0STD+0.9%HBI

I.70

1002.10

Figure4.Compactiondiagrams.

1.80 E 2.00 c "Cl ,.:,c '31.90 CQ

1.00.80.60.4

4000
3500
3000
=:2500 'Cij 2000Q
(j CI) 1500
1000
500
0

0.0 0.2

Behaviourduring thefiring stage

Figs. 5, 6and7presentthevitrificationdiagramsofthecompositions.Inthese For thecompositions andthereforeallowsthefiringtemperaturefortheseproductsto be reduced. 6 6 -PGR ----PGR+O.9%HB

Absorption(%)i

14 12 10'i c .e Q.. ,Q 4 2

11751100 1125 1150

Temperature(OC)

1075

0+-----+----+-----+----+------+---+0

10501200

Figure5.Vitrificationdiagramsof thered-firingstonewarefloortilecompositions.

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Thesediagramswereusedto calculatethefiringtemperatureatwhichthefloortile speci mensattainedworkingwaterabsorption.Avalueof 4%waterabsorption(WA)was adoptedforthered-firingcompositions(T 4) andavalueof 2%forthewhite-firing compositions(T 2) . lin earshrinkage (LS)andbulkdensity(Dap).Tables4and5setouttheresults.Thetables also includethe shrinkage-temperaturecurveslopes/T) atworkingtemperature, rectangularity._ 14 12 10 2 6 4 8 1180
--FGB -----FGB+O.9%HB

1160110011201140

Temperature("C)

0 1200
Figure6.Vitrificationdiagramsofthe white-firingstonewarefloor tilecompositions.

2.4414

--GP 2.40 ----.GP+O.9%HB 12 10 E 2.36 '-I c Q. 0 2.32 r-. .tij c 6 .c ="Qr-. -a 2.28 QQ4 2.242

2.20.·0

11201140 116011801200 1220 1240

Temperature("C)

Figure7.Vitrification diagrams oftheporcelain tile compositions. T 4 (OC)WA(%)LS(%)Dap(g/cnr') II

PGR11434.06.02.3500.055

II

PGR+0.90HB 11374.06.02.3360.045

Table4.Propertiesof thered-firing stonewarefloortile compositionswith4%waterabsorption. T 2 (OC)WA(%)LS(%)Dap (g/crrr')

PGB11792.07.12.2920.031

PGB+0.90 HB 11552.07.32.2840.027

Table5.Propertiesof thewhite-firingstonewarefloortile compositionswith2%waterabsorption.

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e-2 0 0 0

CASTELL6N(SPAIN)

Itcan beobservedthatforbothproducts,addinghydroboraciteloweredthe

6°C,whereasfor thewhitebodycompositionsthereductionwasmuchhigher,between

20and25°C.

temperatures. shrinkageortheshrinkage-temperaturecurveslopes/T) as canbeinferredfrom

Tables 4

didnotalter sizestabilityofthespecimens(thetendencyofsizeandrectangularity problemstoappear). For theporcelaintilecompositions,thetemperatureatwhichmaximumdensification (T max) wasreachedwastakenas theworkingtemperature.Thevalueofthistemperature andthepropertiescorrespondingto theporcelaintilespecimensarepresentedin Table 6.It can beobservedthatthehydroboraciteadditionloweredtheworkingtemperaturebyabout closed.Inprinciple,thissuggests thatthestainresistanceof thepolishedspecimensshould notdeteriorateonaddinghydroboraciteat thetestedpercentage. Itshouldbepointedoutthatthefiringrange(I) inwhichthespecimenspresent isheldwithoutdecreasingmorethan0.01 g/ ern"inrelationtothemaximum. T max (OC)WA(%)LS(%)Dap(g/cnr')PI*10 s(ern ")I(OC)

IIGP1198 0.0 7.82.4103.624

II

GP+0.90HB 1178 0.0 7.92.4065.122

Table6.Porcelaintilespecimenpropertiesat maximumdensificationtemperatures.

Evolution of crystallinephases

theX-ray absorptioneffect, asthehydroboracitecoefficientofmassabsorptionismuch lowerthanthatofthematrixinwhichit isfound. Thereflectionintensity(peaks)of acrystallinephasein asampledependsonthe [5]BROCKER; FER ADEZ,].M.Physiknlisch-chemischeuntersuchugenillsystem8 2 0 3 -5i0 2.

Glastechn.Ber.39. (1966)6,283-293.

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QUALIC02..2000

Onlyquartz, albiteandmulliteweredetectedinthefiredspecimens. Thepeaks correspondi ngto theclayminerals(illiteandkaolinite)werenotdetectedowingto the deco mposition thatthesemineralsundergoatrelativelylowtemperatures "1000°C). Itcanbe observed inFigure 8thatsodium feldspar (albite)gradually meltedduring the firi ngoftheporcelaintile(GP) athightemperatures(>1000°C), formingaliquid phase,untilit practicallydisappearedinthecompositionat 1200°C.Quartzalso dissolvedat asl increasedat hightemperaturesowingtotheriseinliquid-phasecontentanddecreasein viscosity,whichfacilitated dissolution.Mullite wasalsoformedin risingproportionsat the tested t emperatures.

Theaddition ofh

in the whole temperaturerange,indicatingaconsiderableriseinthedissolutionrateof these differ ences stemfrom B 2 0 3 2000
'--'-------'X------------"------4." -'-••_-'-1:1 .........----Quartz ___4,Albite o.'" -Mullile 5

1200115011001050Green

o0 1250

Temperature(0C)

Therefore, although theadditionof B

2 0 3 didnotmodifythecrystallinephases existi nginthe firedproduct,itvariedtheirproportions.Table7showsthepeakareas corresponding tothe phasesdetectedateachcomposition's working temperature,1198°C for presenceofboronin thestartingcompositionreducedtheamountofquartzandmullite dueto thecapabilityoftheformedliquidphasetodissolvebothmineralsinthemelt.On dis solutionmechanism.

GP(1198°C)GPUB(1084°C)

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