Improvement of mechanical and optical properties of Na2O–CaO–SiO2 glasses based on dune sand

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Na2O–CaO–SiO2 glasses based on dune sand

Siham Aissou, Nedjima Bouzidi, Laurent Cormier, Eduardo Bonet-Martinez, Djoudi Merabet

To cite this version:

Siham Aissou, Nedjima Bouzidi, Laurent Cormier, Eduardo Bonet-Martinez, Djoudi Merabet.

Improvement of mechanical and optical properties of Na2O–CaO–SiO2 glasses based on dune sand. Boletín de la Sociedad Española de Cerámica y Vidrio, Elsevier, 2018, 57 (6), pp.221-230.

�10.1016/j.bsecv.2018.05.002�. �hal-01973765�

boletín de la sociedadespañola de cerámica y vidrio57(2018)221–230

w w w . e l s e v i e r . e s / b s e c v

Improvement of mechanical and optical properties of Na ₂ O–CaO–SiO ₂ glasses based on dune sand

Siham Aissou

, Nedjima Bouzidi

, Laurent Cormier

, Eduardo Bonet-Martinez

, Djoudi Merabet

aLaboratoiredeTechnologiedesMatériauxduGéniedesProcédés(LTMGP),DépartementdeGéniedesprocédés,FacultéTechnologie, UniversitédeBejaia,RoutedeTargaOuzemour,06000Bejaia,Algeria

bSorbonneUniversité,CNRS,MNHN,IRD,InstitutdeMinéralogie,dePhysiquedesMatériauxetdeCosmochimie(IMPMC),4place Jussieu,F-75005Paris,France

cDepartmentofChemical,Environmental,andMaterialsEngineering.UniversityofJaen,CampusLasLagunillas,s/n,23071Jaén,Spain

a r t i c l e i n f o

Articlehistory:

Received10January2018 Accepted22May2018 Availableonline2July2018

Keywords:

Dunesand Glass Color

KnoopMicrohardness Chemicaldurability

a b s t r a c t

ThisworkaimstodiscussonthecharacterizationofAlgeriandunesandnamedBoussaâda sand(SB)anditssuitabilityforglassindustry.Basedonchemicalandmineralogicalanal- ysesofSBbyXRFandXRD,quartz,kaolinite,calciumcarbonatesandalbitearethemain mineralogicalphasesfound.However,Fe₂O₃contentisrelativelylow(<0.24wt%).Optical propertiesoftheelaboratedglassdeterminedbyUV-VisibleSpectroscopyrevealthatSB

basedglass(GB)presentsbetterlighttransmissionthanindustrialusedsand(ST)basedglass (GT).TheCIEL*a*b*colormeasurementsshowthatthesampleiscolorless.KnoopHardness measurementsindicatethatGTismorehardthanGB.Chemicaldurabilitytestsrevealthat inanacidsolution,G_Bismoreresistant,whereasitismorevulnerableinthepresenceof alkalineandHFsolution.Furthermore,TiO₂additionsinS_B-basedglassimprovetheclarity andtransparencyoftheglasses(fromL*=87.67toL*=91.05with1wt%ofTiO2).Thus,when TiO2 contentincreased,Knoopmicrohardnessenhance(from451to469HKwith0.1wt%

ofTiO2).Anincreaseintheglasschemicaldurabilityofthesamplesinacidicandalkaline solutionsisnoticedwhentraceamountsofTiO₂areaddedtotheglass.

©2018SECV.PublishedbyElsevierEspa ˜na,S.L.U.Thisisanopenaccessarticleunderthe CCBY-NC-NDlicense(http://creativecommons.org/licenses/by-nc-nd/4.0/).

Mejora de los propiedades mecánicas y ópticas de los vidrios de Na

O-CaO-SiO

basados en arena de duna

Palabrasclave:

Arenadeduna Vidrio Color

MicrodurezaKnoop Durabilidadquímica

r e s u m e n

EstetrabajotienecomoobjetivolacaracterizacióndearenadedunaArgelinallamadaarena Boussaâda(SB)ysuidoneidadparalaindustriadelvidrio.Basadoenanálisisquímicosymi- neralógicosdeSBporXRFyXRD,cuarzo,caolinita,carbonatosdecalcioyalbitafueronlas principalesfasesmineralógicasencontradas.Sinembargo,elcontenidodeFe₂O₃esrelati- vamentebajo(<0.24%enpeso).Laspropiedadesópticasdelvidrioelaboradodeterminadas porespectroscopiaUV-Visible.EsteparámetrorevelaqueelvidrioabasedeSB(GB)presenta

∗ Correspondingauthor.

E-mailaddress:[email protected](S.Aissou).

https://doi.org/10.1016/j.bsecv.2018.05.002

0366-3175/©2018SECV.PublishedbyElsevier Espa ˜na,S.L.U.Thisisanopen accessarticleundertheCCBY-NC-NDlicense (http://

creativecommons.org/licenses/by-nc-nd/4.0/).

unamejortransmisióndeluzqueelvidrioindustrialabasedearena(ST)ydevidrio(GT).

LasmedicionesdecolorCIEL*a*b*muestranquelamuestraesincolora.Lasmediciones dedurezaKnoopindicanqueGTesmásduroqueGB.Laspruebasdedurabilidadquímica revelanqueensoluciónácida,GBesmásresistente,mientrasqueesmásvulnerableen presenciadesolucionesalcalinasydeHF.LasadicionesdeTiO2alvidrioabasedeSBmejoran laclaridadytransparenciadelosvidrios(deL*=87.67aL*=91.05con1%enpesodeTiO2).

Además,seobservóunaumentodeladurabilidadquímicadelasmuestrasensolución ácidayalcalinacuandosea ˜nadieroncantidadesdeTiO_2.

©2018SECV.PublicadoporElsevierEspa ˜na,S.L.U.Esteesunart´ıculoOpenAccessbajo lalicenciaCCBY-NC-ND(http://creativecommons.org/licenses/by-nc-nd/4.0/).

Introduction

Algeriapossesseslarge depositsofsiliceousraw materials, particularlyinthewestofthecountry,wheretheyarelinkedto thedepositsofwindsands.Itismainlythesedepositsthatare exploitedfortheglassproduction.Thesepotentialresources ofsiliceousmaterialsareveryimportantbecauseoftheirdis- tribution,extensionanddiversity[1].

TheTebessa-treatedsilicasand,EastofAlgeria,isexploited asrawmaterialinflatglassindustry.However,thedemand forthisrawmaterialisimportantthattheglasscompanies areforcedtoimportit fromabroad,especiallyfromFrance (Fontainebleau)tosatisfythedemand.

SeveralresearchprojectsvaluingAlgeriandunesandsin thefieldofconstructionarecarriedoutintherecentyears.

Therefore,thedevelopmentofinsulatingmaterialsbasedon Ouargla’ssand [2] andthe valorization ofDjelfaand Bous- saâdasandsinCementindustrytoimprovetheperformance ofconcretewere theonlyapplicationsofthesesands[3–5].

However,investmentsinthesesiliceousnaturalresourcesare belowexpectedlevelsduetothelackofdetailedstudieson theirphysicochemicalcharacterization[6],whichlimitsdevel- operstofocusontheexploitationofthesesiliceoussandsin glassindustryandtoprovidesolutionstotheproblemsofsand supply.

Thesilica content and the particle sizedistribution are nottheonlycriteriaforthesuitabilityofsandsfortheglass industry. Most of the time, silica contains trace metallic impurities which affect the process of production as well asthepropertiesoftheelaboratedglasses[7–9].Oneofthe most common and undesirable impurity is iron either in ferrous(Fe²⁺)orferric(Fe³⁺)state.Thisimpuritydramatically influencestheoptical,colorimetric andmechanicalproper- tiesofglasses[10,11].Besides,thepresenceofalumina(clay fraction) yields devitrification phenomena in the glasses.

Innumerable researcheshave been carried out to optimize and improve processes for purification and treatment of sands such as attrition, flotation, washing and magnetic separation [12–14]. Another alternative or complementary operation to these purification processes is carried out at theleveloftheglassformulationsandthisbyaddingsmall amounts of transitions metal oxides which influence the red/ox state of the iron impurity thus eliminating their undesirableeffects on the glasses colorimetric and optical properties[15].Forexample,TiO2additioninsmallamounts

to the glass composition influencesthe equilibriumof the Fe³⁺/Fe²⁺,leadingtoanimprovementinthecolorimetricand opticalpropertiesofglasses[10,16].Thisadditionalsoinflu- encesthemechanicalandthermo-mechanicalpropertiesof glassesbyreinforcingthevitreousmatrix[10,17,18].TiO2con- tainingglassesalsopossessgoodchemicaldurabilitytoacid attack[19].

Fromthisperspective,thisworkdealswiththecharacter- izationofthedunesandofBoussaâdalocatedinSouthEast ofAlgeria.Itsvalorizationinthedevelopmentofsoda-lime- silica glassesisthefirstobjective ofthiswork.Anattempt toimprovethecolorimetric,opticalandchemicaldurability oftheglassesproducedbyaddingTiO₂ atvariableamounts to the glass compositions is the second objective of this work. For thesepurposes six glass compositions with and without TiO2 additionare prepared.They are denoted GBx, with x=1,2, 4, 6and 10 corresponding to0.1, 0.2, 0.4,0.6 and1wt%ofTiO₂added,respectively.Onesample(G_T)with Tebessasand,usedinlocalglassindustry,isalsopreparedfor comparison.

Experimental part

Thelocalmaterialsusedinthisworkare:Thedunesandof Boussaâda (SB),Tebessasand (ST)usuallyusedinthe glass industryandnaturaldolomite(D)[MgCa(CO₃)₂].

TheSBsandisasampletakenintheareasituatedinthe Boussaâdadunecordon.ThisareaispartoftheZahrezGharbi basininthehighsouthofAlgeria[20].Thedunecordonisa recentgeologicalformationwhichappearsintheendofter- tiaryandthebeginningofthequaternary.Itiscomingfromthe softrocks(marlstoneandredclay)whichhavebeenextracted bytheerosionofthemountainaswellasthepresenceofthe saltLimestone,Gypsumandsolublesalts[20].

TreatmentofBoussaâdasand

Before the preparation of the samples (glass), SB sand is washed severaltimeswithdistilledwaterforremovingthe finefraction.Thenitisdriedinambientair,sievedtoaparticle sizegreaterthan100␮mandground.

boletín de la sociedad española de cerámica y vidrio57(2018)221–230

223

Table1–Proportionofrawmaterialsinthesamples(wt%).

Components Sand CaCO3 Na2CO3 Na2SO4 MgCa(CO3)2 TiO2

Proportion,wt% 61.29-x 14.36 19.85 0.5 4 x=0,0.1,0.2,0.4,0.6or1

GlassesElaboration

ThebasicglasscompositionsaresummarizedinTable1. A homogenizedmixtureof40gofrawmaterials:sand,dolomite and chemical reagents (Na₂CO₃, CaCO₃ and Na₂SO₄ from Cheminova International, Spain with a chemical purity of 99wt%)is placedina platinum cruciblein anelectric fur- naceforacalcinationstepat850^◦Cfor6h,followedbyafirst

meltingstepfor2hat1450^◦C.Theglassobtainedbyquench- ingisgroundtoincreasehomogeneity.Thisstageisfollowed byasecondmeltingstepat1450^◦Cfor4h,followedbyanneal- ingat560^◦Cforaperiodofonehour.Thesamplesarecutinto testtubes,polishing(P400,P600,P1200,P2500,P40000andwith diamondpaste)andgrindinguntilobtainingapowderwitha particle size≤0.63mm.Theexperimentalprocedureofthe obtainedmaterialsispresentedinFig.1.

S

, S

washed sands (fraction > or = to 100

m)

Crushing

(61.29-X) % crushing sand

14.36 % CaCO

, 19.85 % Na

CO

0.5 % Na

SO

4 % Mg Ca (CO

)

X%TiO, (x = 0 %, 0.1 %, 0.2 %, 0.4 %, 0.6 % and 1 %).

Mechanical

Homogenization Homogenous glass composition G

and G

Quenching Calcination and 1

melting

Crushing

Annealing 2n

melting

t= 15 min T = 850º C, t = 6h

T = 1450º C, t = 2h

t = 4h T = 1450º C

Melt

Glass

Glass power

Homogenous glass

Annealed glass

t= 1 h T = 560º C

Fig.1–Diagramoftheexperimentalprocedureoftheobtainedglasses.

Table2–Chemicalcompositionofrawmaterials.

Sand Oxides SiO2 Al2O3 CaO Fe2O3 MgO Na2O K2O TiO2 L.O.I

SB wt% 95.21±0.01 0.97±0.03 1.32±0.02 0.23±0.02 0.01±0.03 0.27±0.02 0.40±0.04 0.01±0.004 1.52±0.01 ST wt% 98.20±0.01 0.88±0.03 0.20±0.02 0.12±0.02 0.05±0.03 0.05±0.02 0.34±0.04 0.07±0.004 0.09±0.01 D wt% 0.48±0.01 0.36±0.02 30.77±0.01 0.06±0.02 21.00±0.03 n.d n.d n.d 47.42±0.01 L.O.I:LossOnIgnition,n.d:notdetermined.

Improvementoftheglassesproperties

Withtheaimtoimprovingthecolorandchemicaldurability ofSBglasses,severalglasseswereelaboratedbasedonTiO2

addition.Theyareelaboratedusingthesameprocedure:two meltingstepsandinthesameconditionsoftemperatureand time(Table1andFig.1).

Characterizationoftherawmaterialsandtheelaborated glasses

Themineralogicalcompositionsofthetwosandsweredeter- minedusedanX-rayPANalyticalX’PertPROdiffractometer (CuK␣,␭=1.540598 ˚A,2␪range0–80^◦,0.0252␪step).Thecol- lected data are processedby PANalytical X’Pert Highscore software.

TheThermo gravimetric and Differential Thermal sand analyses were carried out using a NETZSCH STA 409C/CD thermobalanceallowingthetwoanalyzestobecoupleddur- ingthesamethermalcycle.TheTGA/DTAcurvesareobtained usingarateof10^◦C/minfromroomtemperatureto1000^◦C.

Thesamples,about 300mg,are placedinaluminacrucible underargonatmosphere.

TheSBSandparticlesizedistributionwasrealizedusinga MASTERSIZER2000Lasergranulometer.

ThechemicalcompositionofSB, STSands anddolomite (Table2) were carried out by X-rayfluorescence (PANalyti- calPerl’X3).Thesampleswerepreparedinthepelletsfrom 8g of crushed sand with 4.5ml of a compacted Elvacite resin.

ThegrainmorphologiesofSTandSBsandsandtheelabo- ratedglassesaredeterminedbymeansofaScanningElectron MicroscopeME03,SEM:Merlin,Zeiss,Cist.Itallowsmaximum resolutionofthesecondaryelectron(SE)imagefrom0.8nm at15 KV,from 1.4nmat1kVand from 2.4nmat0.2kV.It alsoallowsbackscatteredelectron(BSE)imaging.Therangeof potentialaccelerationisbetween0.02Vand30kV.SEMiscou- pledtotheEnergyDispersiveX-raySpectroscopy(EDX)which providesinformationonthechemicalcompositionsofsands andelaborateglasses.

Thechemical composition of the glassesis determined by Electron Probe Micro-Analyzer (EPMA, CAMPARIS, Paris, France)withaCAMECASX-Fiveapparatusequippedwithfive Wavelength-DispersiveX-raySpectrometers(WDSs),driven by the Peak Sight software under Windows environment.

Analysesaremadewith15kVacceleratingvoltageanda10nA samplecurrent a4␮mspotsize.Thestandardsforcalibra- tionwerealbiteforNa,diopsideforMg,SiandCa,Orthoclase forAlandK,MnTiO3forTi,Cr2O3forCr,Fe2O3forFeandCu forCu.20pointsweretakenandobtainedcompositionswere averaged.GlassesCompositionofglasseswashomogeneous

accordingEPMA.ThesampleswereimmobilizedinanMECA PREXacrylicresin.Theshotscontainingtheglassesarethen polished,cleanedandmetalized.

Theopticalabsorptionspectraoftheobtainedglasseswere realizedwithadoublebeamPerkin-Elmer 1050spectrome- ter, intransmissionmode. Itscans arangeofwavelengths between300and4000nm.Thesampleswerepreviouslypol- ished with diamond paste. The optical absorption spectra werenormalizedbythesamplesthickness.

Thecolormeasurementsofthesampleswerecarriedoutby anX-Ritespectrometer,model962S/N000967(USA),X-Riteink formulationsoftwarePinterPro5.11operatingwithD65light source,cameraviewingangle10^◦.Themeasurementswere repeated three timesforeach composition and anaverage valuewastaken.Thesamplesthicknesswas2mm.

Knoophardnessmeasurementswerecarriedoutusinga Zwick/Roel(ZHV)microhardnesstester.Theloadusedinthe hardnesstestswas0.2KP(1.9613N)andthedwelltimeofthe indenterincontactwiththesamplewas20s.

Chemicalresistancetoacidsandalkalinesolutionsofthe samplesweredeterminedusingchemicaldurabilitytests[21].

Thesamplesareimmersedinbeakersfilledwith1NHClor 1NNaOHsampleandthenboiledfor6hforHCland3hfor NaOH.Theglassesarethenwashedwithdistilledwaterand driedat105^◦Cfor24handtheirlossesinweightarecalcu- lated.TheglasseswerealsosubjectedtoHFattack.Adropof HF(10N)isdisposedonthe glassessurfacefor10min.The glasseswerewashed,withdistilledwaterandthendriedat 105^◦Cduring24h.Thelossesinweightofthesampleswere determined[22].

Results and discussion

Mineralogicalanalysis

Mineralogical analysis using X-ray diffraction of S_B sand shows presenceofquartz.Albiteisalsodetermined inthe X-raydiffractionpattern(Fig.2).

TGA/TDA

According tothe TGA/DTAthermogramofSB sand (Fig.3), threeendothermicpeaksareobserved.Thefirstpeakat105^◦C correspondstodehydrationorreleaseoffreewater.Thesec- ondpeakat573^◦Ccorrespondstothepolymorphicthermal transformationofquartz(quartz␣toquartz␤).Athirdpeak at803^◦Ccorrespondstothedecarbonationofcalcite.More- over,alargemassloss(1.5%)isnoticedontheTGAdiagram whichcorrespondstothedecarbonationandthelossofCO2.

boletín de la sociedad española de cerámica y vidrio57(2018)221–230

225

50000

40000

30000

20000

10000

0

10 20 30 40 50 60 70 80

2 theta(°)

Intensity (counts)

SB SBtreated

ST Q

Q

Q Q Q Q Q

Fig.2–DiagramofX-RaydiffractionofST,SBandSB

treatedsands(Q:quartz,A:albite).

100,8

100,4

100,0

99,6

99,2

98,8

98,4

100 200 300 400 500 600 700 800 900 1000 -0,04 0,00 0,04 0,08 0,12 0,16

Temperature (°C)

DTA (µv/mg)

573°C

105°C

803°C

1.5 DTA TGA

TGA (%)

Fig.3–TGA/DTAthermogramofSBsand.

Particlesizedistributionanalysis

Sandwithveryfinegrainsismorelikelytocontainironoxide and refractory minerals, while a largeparticle size causes fusedinclusionsinthefinalproducts,aphenomenonresult- ingfromtheslowermeltingofcoarsegrainsincomparison withthefinest[8].Hence,thegranulometriccontentofsands isamajorrequirementforglassmanufacturers.

Thelaser granulometric analysis carried out byCoulter (Fig. 4)revealsthat grainsare formedbypopulationscom- posedof40and1000␮msizes.Itisalsonoticedthat50%of thegrainsinthesandare243␮minsize.Theparticlesand sizeisfinebutSBsandmeetstherequirementsoftheglass industry(0.1–0.5mm)[23].Nevertheless,washingandsieving arenecessaryfortheremovaloftheclayfraction.

Chemicalcomposition

SBismainlycomposedof95wt%ofSiO2 (Table2),Fe2O3 is presentinasmallamount(0.23wt%),besidesAl2O3andTiO2

(Table2).Inanotherhand,SBcontainsclayfractionssinceits lossonignitionis1.59%.Theseresultsareinconcordancewith themineralogicalandTGA/DTAanalysis.Incomparisonwith

12

10

8

6

4

2

0

0,1 1 10 100 1000

Particle size (µm)

Volume (%)

d₁₀ = 138.32 µm d₅₀ = 243.229 µm

d₉₀ = 414.593 µm

B

Fig.4–ParticlesizedistributionofSBsand.

the chemicalcompositionofST,SB containsmoreofFe₂O₃ andlessofSiO₂andTiO₂oxides(Table2).Thefewamountof Fe2O3contentofthedolomiteisadditionallynoticed.

Characterizationofthetreatedsand

Mineralogicalanalysis

AccordingtotheX-raydiffractionpatternsshowninFig.2, thesamplesofthetwosandstreatedSBandSThavethesame mineralogicalcomposition,whichconsistofquartz.Thedis- appearanceofalbitecharacteristicpeakisalsoobservedinthe S_Btreatedsand.

SEMandEDXanalysis

TheSEMmicrographsshowninFig.5revealthatthequartz grainsoftheSTSandareovoidinshapewithmarkedsurface asperities(i.e.,roughness)indicatingitsbelongingtofluvial origin.Ontheotherhand,thequartzgrainsofS_Bsandhave asphericalandrounderformwhichcharacterizesthedune aeoliangrainssand[24,25].TheEnergyDispersiveX-raySpec- troscopy(EDX)attachedtotheSEMsupportstheXRFresults concerningthesamechemicalelementscontainedinthetwo sands(Table2).

Characterizationandpropertiesoftheelaboratedglasses

Chemicalcomposition

Chemicalanalysisbyelectronmicroprobe(Fig.6)showsthat GBglasspresentsthehighestlevelofSiO2,Na2O,CaO,MgO, Al2O3andFeO,whileGTglasscontainsthehighestlevelofK2O andTiO2.ThehighSiO2contentintheGBsampleascompared toGTisanindicatoroftheimprovementinSTquality.This improvementresultsfromthetreatmentthatithasundergone (washesandgranulometricselection).

UV-Visible–IRSpectroscopy

AsisshowninFig.7,thesamplesexhibitordinaryabsorbance valuesforglasses.TheUVcut-offintheabsorptionspectra was shiftedtoahigher wavelengthfrom325nmto350nm for GT and GB samples, respectively. In the visible range

200µm

200µm

Bectron image 1

Bectron image 1

Ful scale 25743 cts oursor.0,000

Ful scale 25743 cts oursor.0,000

1 2 3 4 5 6 7 8 9

1 2 3 4 5 6 7 8 9

keV

keV Spectrum 4

Spectrum 4 Spectrum 4

Spectrum 4

Element

Element Weight % 16.63 56.88 0.26 1.63 23.85 0.52 0.22 100.00 C K

O K Mg K AI K SI K K K Fe K C K O K Na K Mg K Al K Si K Cl K K K Ca K Ti K Fe K Totals

Totals

100.00 0.84 0.18 0.53 0.51 0.57 19.33 2.91 0.36 0.28 54.03 20.95 Weight %

a b

c d

Fig.5–(a)SEM-SEIimageofTebessasandparticles,(b)EDXspectrumofTebessasandparticleindicatedin(a),(c)SEM-SEI imageofBoussaâdasandparticle,and(d)EDXspectrumofBoussaâdasandparticleindicatedin(c).

1,0 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0

AI203 K20 Ti02 Fe0 Cu0 Cr203

Oxides

GT GB

Amounts (wt %)

Amounts (wt %)

GT GB

70

60

50

40

30

20

10

0

SiO2Na2O CaO MgOAI203K2O TiO2 FeO CuOCr203

Fig.6–Chemicalcompositionsofglasses.

(400–800nm),GBhasbettertransmissionoflight,compared withGT.Thespectraoftwoglassespresentapeakat380nm characteristicof the Fe³⁺ ionscharge transfer[11]. Beyond 800nm,GThasthebest transmission.Theappearanceofa broadbandcenteredat1100nmcharacteristicofFe²⁺ionsin theGBspectrumisalsoobserved[11].

4,0

3,5

3,0

2,5

2,0

1,5

1,0

0,5

0,0

400 600 800 1000 1200 1400 1600 1800 2000 Wave length (nm)

1100 nm, Fe²⁺

380 nm, Fe³⁺

GT GB

Absorbance

Fig.7–UV-VisiblespectraofGTandGBglasses.

L*a*b*Colormeasures

AccordingtoTable3,itisnoticedthatG_Tisbrighterandclearer thanGBwithL*values91.96and87.67,respectively.GBisalso themostchromaticglasswithC=2.21.Thisisduetoitshigher contentsofFeOandTiO2thanGT(0.09,0.07wt%ofFeOand 0.07,0.04wt%ofTiO2forGBandGT,respectively).

Thenegativevalueofa*parameterindicatesaslightgreen color, whichismainlyduetothe presenceofamixtureof

boletín de la sociedad española de cerámica y vidrio57(2018)221–230

227

Table3–L*a*b*andCcolorparametersofGTandGB

glasses.

Glass L* a* b* C

GT 91.96 −1.41 −0.02 1.41

GB 87.67 −1.32 −1.77 2.21

GB1 88.62 −1.56 −1.29 2.02

GB2 90.10 −1.47 −1.08 1.82

GB4 90.50 −1.49 −1.05 1.82

GB6 90.80 −1.37 −1.02 1.71

GB10 91.05 −1.78 −0.48 1.84

Fe²⁺andFe³⁺ionsintheglassmatrix.Thisvalueisnegative asthismixtureishigh (caseofGBcomparatively withGT).

However,theb*parameterisinfluencedbyTiO2andFe²⁺/Fe³⁺

glassesamounts.Theb*parameterofG_Tpresentavalueclose tothecharacteristicofslightyellowishcolor.Thisresultis duetothehighproportionofFe³⁺inGTglassthaninGBglass, thisisinagreementwithUV-Visiblespectroscopyanalysis.On theotherhand,GTcontainsmoreTiO2thanGB;thisinduces yellowishhue[26].

Knoopmicrohardness

Asshown inFig.8,theKnoopmicrohardnessvaluesofthe samplesGTandGBare465and451HKrespectively.Theinden- tationhardnessdependsonthechemicalcompositionofthe glass,accordingtoScholze[27],additionofalkalisdecreases hardnessinsilicateglasses.Infact,thecontentofNa2OofGB

andG_Tglassesare13.24and13.03wt%respectivelywhereas K2Oamountsare0.24and0.75wt%respectively.Thehighest microhardnessvalueofGT canbeattributedtothehighest amountofTiO2presentinthisglasscomparativelywithGB

glass(0.08wt%and0.04wt%respectively)[10].

Improvementoftheglassesproperties

SEMandEDXanalysis

TheSEMobservationsillustratedinFig.9,revealsthatGB0and GB2presentavitreousmatrixfreeofbubblesandinclusions.

WithoutTiO2addition,theglassexhibitsahomogeneousmor- phologywith amoreor less compactvitreous network.In

600

500

400

300

200

100

0

GT GB GB1 GB2 GB4 GB6 GB10

Glasses

Knoop hardness (HK)

Fig.8–Knoophardnessvaluesfortheelaboratedofglass.

contrast,theglassresultedfrom0.2wt%ofTiO₂additionis morecompact.TheEDX Spectroscopy attachedtothe SEM reportthepresenceofTiandFeinGB2sample.

UV-Visible-IRSpectroscopy

In general,thedevelopedglassesabsorption spectrainthe UV-VisiblenearIRregion(Fig.10)havesimilarprofiles.With theTiO2additions,theUVcutoffintheabsorptionspectra, showinganinfiniteultravioletabsorptionandazeroemission, wasshiftedtoahigherwavelengthfrom 350nmto370nm.

SimilarresultswereobtainedbyKumar[28].Adecreaseinlight transmissionbythedopedglasses,inthevisiblerange,was additionallynoticed.TiO2additionsalsoinfluencethebroad bandaround1100nmcharacteristicofFe²⁺ions(Fig.10)[11].

AdecreaseinintensityofthisbroadbandintheGB1spectrum wasnoticed.Indicatingadecreaseinthelevelofferrousions intheGB1compositioncomparedwiththeotherglasses.Char- acteristicabsorptionbandsoftheTi³⁺ionsat480–510nm,570 and680nmarenotdetected.Theseresultsareexpectedas underordinarymeltingconditions,anditisdifficulttoobtain reducedTi³⁺ionsinsoda-limesilicateglasses[29].TiO₂addi- tionalsocontributestotheincreaseinintensityofthepeak at380nm,characteristicoftheFe³⁺ ionschargetransfer[11]

andthepeaksat430and480nm,characteristicoftheFe³⁺ions.

Accordingtothestudiesoftheiron-dopedglassesbyRusetal.

[30]andKukkadapuetal.[31],Fe³⁺ ionspresentabsorption bandsintherange325–450nmand350–500nm,respectively.

L*a*b*Colorproperties

AccordingtoTable3,theglassGBwithnoadditionofTiO2is themostchromaticglass(C*=2.21),byaddingasmallamount ofTiO₂(0.1,0.2,0.4and0.6wt%),thechromaticitydecreasesto 1.71.IncreasingtheTiO2contentto1wt%,theglassbecomes morechromaticbutstilllessthantheGBglass.Theaddition ofTiO2increasestheparameterb*,approachingthepositive valuescharacteristicofyellowishcolor.However,thevalues oftheparametera* arestronglyinfluencedbytheinterfer- encebetweenFe²⁺/Fe³⁺andTi³⁺/Ti⁴⁺[26].Itsnegativevalues indicateaslightgreencolorattributedtothemixtureofFe²

+andFe³⁺ions.TheTiO2additionbringsanimprovementin theglassesclarityrepresentedbytheL*parameterfrom87.67 to91.05forGBandGB10,respectively.

Knoopmicrohardness

AsshowninFig.10,TiO2additionimprovesKnoopmicrohard- nessofSBbasedglasses.Anincreaseof∼8.65wt%ofKnoop microhardnessisnoticedforGB10(with1wt%ofTiO2)com- parativelywithGB.TheseresultsconfirmtheTiO₂effectasan oxideinfluencingthismechanicalpropertyfoundinthecase ofGBandGTglasses.TiO2additionreinforcestheglassnet- workandproducesanincreaseintheobtainedglassesdensity [10],thusresultinginanincreaseinmicrohardnessforglasses containingTiO₂.

Chemicaldurabilityoftheelaboratedglasses

HClandNaOH

ThechemicaldurabilitytestsinHCl(1N)andNaOH(1N)solu- tionsshowed(Fig.11)thattheglasssamplesaremoredurable inacidicsolutionthanalkaliones.Thus,inacidicsolution,GB

50µm Bectron image 1

50µm Bectron image 1

Ful scale 25743 cts oursor.0,000

Ful scale 25743 cts oursor.0,000

1 2 3 4 5 6 7 8 9

keV

1 2 3 4 5 6 7 8 9

keV Element

C K O K Na K Mg K Al K SI K S K K K Ca K

C K 29.41 39.17

47.58 3.49 0.22 0.12 8.22 0.65 1.07 0.00 0.02 14.58

5.02 0.33 0.20 14.42 0.13 2.69 0.15 0.07 100.00 O K

Na K Mg K Al K Si K K K Ca K Ti K Fe K Totals

Totals 100.00 5.39 0.16 0.11 22.14 0.18 0.40 5.26 40.50 25.27 36.00

43.32 4.36 0.28 0.11 13.49 0.06 0.07 3.30 Weight %

Atomic %

Element Weight% Atomic %

Spectrum 4

Spectrum 4

Spectrum 4 Spectrum 4

a b

c d

Fig.9–(a)SEM-SEIimageG_B0glass,(b)EDXspectrumofG_B0glassindicatedin(a),(c)SEM-SEIimageofG_B2glassand(d) EDXspectrumofGB2glassindicatedin(c).

1,0 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2

400 600 800 1000 1200 1400 1600 1800 2000 Wave lenght (nm)

Absorbance

GB GB1 GB2 GB4 GB6 GB10

Fig.10–UV-VisiblespectraofGBwithTiO₂addition glasses.

resistsbetter,whileitismorevulnerableinthepresenceof alkalinesolutioncomparativelywithGT.

TheadditionofTiO₂inG_Bglassimprovesitschemicaldura- bilitywithrespecttotheHClacidbyreinforcingthevitreous network.However,inNaOHsolution,theimprovementisalso observedexcept inthe case ofGB10 composition (1wt% of TiO2).SimilarobservationshavebeenreportedbyEl-Bataletal.

[32]fortheG_B1sample.TheexceptionrelatedtoG_B10com- positionisduetothefactthatSi–O–Sibondsareinfluenced

1,5 1,4 1,3 1,2 1,1 1,0 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0,0

GT GB GB1 GB2 GB4 GB6 GB10

Glass samples

Weight loss (wt %)

HCI NaOH HF

Fig.11– Weightloss(wt%)ofthestudiedglassesbyvarious solutions.

bytheadditionof1wt%ofTiO₂.Itmakestheirbreakdown bythe hydroxyl ions(OH⁻)containedin thealkaline solu- tion easier. The incorporation of this TiO2 amount in the glass networkmay increase the substitutionofSi⁴⁺ bythe Ti⁴⁺ ionwithits largerionicradiusthan thatofSi⁴⁺ (0.061 and 0.040nm,respectively)and thusincreasetheexchange engagedbetweenthetwoions[33].

boletín de la sociedad española de cerámica y vidrio57(2018)221–230

229

DurabilityoftheglassesinHF

ThestudyofchemicaldurabilityinHF(10N)forthedeveloped glasses(Fig.11)revealedthatthevitreousnetworkoftheGT

sampleismoreresistanttoattackthanthatoftheGBsample.

ThisisrelatedtothehighersilicacontentofGBcomparedto GT.

TheSBsandglasscompositionspreparedwithTiO₂addi- tion are more attacked by HF than the basic composition without TiO2 addition. The variation of glass composition modifiestheglassstructure,leadingtochangesinthecon- centrationoffragilebonds.Anexceptionisnoticedinthecase ofGB1(withadditionof0.1wt%ofTiO₂)whereanimprove- mentinitsdurabilityisobserved(withamasslossof0.602 comparedto0.807and0.472wt%forGBandGT,respectively).

Conclusions

Thephysico-chemicalcharacterizationoftheBoussaâdasand revealedthepresenceofafractionwithaparticlesize<100␮m carryingtheferrousimpurity,thusrequiringpriortreatment beforeitsuse intheglasseselaboration.Afterthe physical treatmentsbyseveralwashesandagranulometricselection, thecharacterization ofS_BbyX-raydiffractionrevealed the disappearanceoftheclayfraction(albiteandcalcite).

Thesoda-limeglassproducedfromtheBoussaâdasandis colorless,hasaninterestinglighttransmissionthatisbetter thantheTebessasandglassandhasabetterchemicaldura- bilityinacidsolution(HCLsolution(1N)).

TiO₂additionstoS_B-basedglasseshaveenhancedtheclar- ityandtransparencyfromL*=87.67toL*=91.05andimproved theKnoopmicrohardnessfrom451HKto490HKforGBand GB10,respectively.Thisimprovementisduetothefactthat TiO2affectontheFe³⁺/Fe²⁺ionsequilibriuminthevitreous matrix.

Theglasschemicaldurabilitytoattackbyacid(HCl)and alkaline(NaOH)solutionsisenhancedbytheadditionofTiO2

amounts.However,thechemicalresistancetoattackbyHFis enhancedonlyinthecaseofGB1composition(with0.1wt%

TiO₂).

Thedune sandofBoussaâda ispromisingforits use as arawmaterialfortheelaborationofglasses.Moreover,the addition ofTiO2 improves its colorimetric and mechanical propertiesbesidesits chemicaldurabilityinacids(HCl, HF) andalkaline(NaOH)solutions.

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