View metadata,citationandsimilarpapersatcore.ac.uk This article isprotected rights by All copyright. reserved. 10.1111/jace.16134doi: lead todifferences version between this andthe ofPleasec Version Record. been and throughtypesetting, proofreadingwhich may thecopyediting, process, pagination This article undergone has for and buthas accepted been not review publication fullpeer Articletype : PROFESSOR CRISTINA SILIGARDI (Orcid ID : 0000 SILVIADR BARBI (Orcid ID : 0000 MONIA MONTORSI (Orcid ID 0000: present, category a establishing new suitable fritfor The formulations thatpurpose. of exchange processan onlyof in the starting appropriateions is composition combination if elaborate model. the Vickersand SEM Hardness enhance to compositions the ionexchange process, starting a commercial from product. of technique. Experiments Design A Mixture been has carried outtofor glass glazed hardeningbased processceramicrational to following a onDesign tiles design resistance stresses. tomechanical Thisstudyapplicability investigates a the well of resistance efforts althoughshould tochemicals attacks, big Abstract:

Accepted Article3 Departmentand Methodsfor Modena ofSciencesand Engineering, UniversityReggio of 1 2 Interdepartmental forresearch Centre applied Department ofEngineering *[email protected]

Glazed ceramic tiles areGlazed tiles ceramic wall floor used coveringtheirs for and high thanksto Silvia BarbiSilvia motoring Article

Results suggestceramicResults thatfrits for ar tiles , University of Modena, University of and Reggio 1*

Chemical , Consuelo Mugoni, Consuelo - EDS techniques have beenEDS techniques the employedfrits have and toevaluate - 0001 “

, +390592056281, - Enzo Ferrari Enzo Emilia, Reggio Emilia, Italy; ReggioEmilia, Emilia, 0001 hardening - 5431 - 7217 Modena, Italy;Modena, - 6906) 2 -

, Monia Montorsi 7946) - of 0003 ”

, University of Modena and , UniversityReggio Emilia, ofModena glazed

- and servicesand and inadvanced mechanics 1642 via Vivarelli 10/1, 41125,Modenavia Vivarelli 10/1, porcelain tiles

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Emilia, Modena, Italy; Modena, Emilia, provided byArchivioistituzionaledellaricerca-UniversitàdiModenaeReggioEmilia be done toincrease their surface

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, Cristina Siligardi e affectedby positively ion

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CORE This article isprotected rights by All copyright. reserved. presence of movements promote Moreover, t alkaline relevant content (>10 be should on the Many 400 containingalkali suchas ions Na diffuse cations bathtothe glass from amolten salt network, [ problems ofother technologies with been electrodeswith high resistance tochemical attack applications, high includingglasses productionmechanicalwith of the strength and years,Over the Ionexchange 1 Keywords: 5 stoneware. results have employing confirmed been theoptim

Introduction -

Accepted6 Article

] °C and°C 500

. very developed to developed

Chemical tempering isa studies have been performed to investigate the roleperformed of the been studies have toinvestigate efficiency

in the opposite direction.in the opposite s

the diffusion due Alkaly tothe “Mixed small small

Hardness; Diffusion; Mechanical Hardness; Diffusion; properties; he presencemonovalenthe cation of

(Al [ 10

(IE)

3+ -

IE thicknesses °C 1

) of theprocess 2

that in tailored condition sincemodify aboutis used acentury of tothesurface properties glasses. work components for processes ]. ]. , for several (4 hours Furthermore ,

such as by Gorilla Glass™ Corning have been n , . The main result of these resultstudies of . The main

such as onthesurface opticalsuch premature distortion failure or IE + In configuration, common silicat themost ,

or Lior aluminosilicate glassesare promising most due the to the process

+ - developed and for industrialized multiple developed

120h) with mol ions are inabath immersed ofKNO

s for strengthening

%) is abletopromotediffusion thealkaline [1

s different shapes

[ (K 7 to to - E

+ 9 [ ) inthe startingglass ized fritized for theglazingofporcelain make effectiveexchange theion ffect” 1 ]. ]. - e 4

xchanging withsmaller cations ]. Others process].

Ion and

- E based on based divalent cation divalent , such as , such x change

®, glass suggests

thus avoiding the thus avoiding

chemical composition chemical composition

; Tile; the diffusion oflarger the diffusion curved es composition composition

improvements that e glasses s

3

limit the limit

or the glass in the range of wavy . which , ions

3 and - have 1 5

].

This article isprotected rights by All copyright. reserved. chemical tempering This studythe isfocused on temperatur generally typically thatsurely ahigher contains numberoxides, of interact formulation of a ceramic to 2009/607/CE wall coverings green needed for inthe European asDecisions building, stated Union efficiency route hardening toperform quenchingglass of water by immersion in mainlyglass, typesas composedofceramic known byfrit special hardening chemical attack In content increase of flexural strength is significative chemical composition andmineralogical growthsubcriticalcracks duringcooling of increase strength up to~74%the flexural ofunglazed Previous studie favoring Finally, other

hard Accepted Articleceramic production tile

coverings into theporcelaininto stoneware

the ,

the employment ofNathe of thin products, accordingof products, thin to e, generatinge,defects process fabrication [ the during

cations significant overcome the critical issues of such fragileIn criticalovercome the of materials. issues such s establishing

glass former s s

, covering porosity,interest allgrowi theopen is but have shown thathave standard ionexchange shown process

[ 20

process, diffusion ] .

One ofthe main

variable glaze

the glazes toprotect stoneware themain have role from the porcelain

s of glazedof st porcelain

comparison among such as B such as to

of cations ecological

successfully

is even more complex thanthe formulationglass of ais even complex because more quantifycorrelations between s + , together is reduced strong toavoid glass decreases transition ofthe

[ 18 with 2 O

drawback ]

[1 s . criteria 3

of the porcelain

[

6 and P

with to 19] promoted promoted [ ]. ]. 17

the environmental requirements for floorthe environmentalrequirements and

. ]

. NowadaysIE

the process temperature different different 2 for oneware Related O s

5 of approach this

the could by porcelain

award

a restrained crystalline phasesa restrained crystalline

studies alsodemonstrate , glaze

stoneware promote local improving glaze may

of

19

formulations stoneware es

among them the , ].

obtained throughobtained fast very can be employedcan be to be considered as possible

composition and composition is that

n Community

are fact, the properties and the the g about gabout ,

the mo environments and thereforeand the

c t avoiding any he chemical eramicglazes are ,

. Moreover, undergoinga to the glaze st

Eco d

that the hardness - Label

This article isprotected rights by All copyright. reserved. micron) suitableIn forto investigate thethermalanalysis. order thebySEM bulk materials mol% ofthecomposition industrial frit is54SiO low thickness appli groups commercial of The industrial Industrial2.1.1 2.1 2 performances. hardening glass composition a attention onlyglaze onthe role. composition also been tested porcelain best the stoneware of interaction with othersperformance affect theof final Design Experiments method of concerns hardness tempering also applicationon after tested, been have main parts: of the glazed

glaze AcceptedMaterials andMethods Article Preparation of thesamples .

The frit composition

(HV) new

promoted

in porcelain stoneware

frits formulation frits the first glaze , scratch resistance, physical, scratch resistance, properties. andmicrostructural

was . glaze

The , in which

cation grinded , containing combination ofcomplex o a , was

leading to leading P , a commercial, a frits rocess parameters have been rocess parameters have been

prepared starting from an industrial frit,prepared industrial selectedan starting fromoverall themain

in the porcelain production stoneware

due high its Na content of

ground IE

by attitude is emphasized and thereforeattitude isemphasized the glaze that glazedstoneware porcelain .

using the To achieve this goalTo achieve this the study

in an agate mill for toobtainin anagate afine mill 20min powder(ca. 32 allows quantifyingeachcomponent howand potential its glaze deriving 2 -

has been considered and has its been 13B M The ixture from 2 O

innovative 3 -

8Al the frit optimized by the frit optimized maintained constant focus to our D + porcelain stonew . esign approach esign approach This glaze is generallyThis glaze is employed for 2 O

material [ 3 - with improved mechanical 12Na

xides results obtained results obtained

[2 has been 2

O with respect a to typical 2 21 ] - . 6CaO

The ] are as of atailoredtool .

behavior surface The application on

Mixture Design has ,

measured in in organized in - The 5MgO terms of lead topropose

second part chemical

to chemical - 2K

2 Vicker Vicker O two

the - This article isprotected rights by All copyright. reserved. data D Therefore, issues, savinginformation contentbothti oncomplex (OFAT) outlook,reducing testsneeded of the thenumber maximum experimental toprovide overcomes into intrinsic thesocalled thestrong simplifications One additional boundary the on constrains relative Mixture Design The investigated compositions in 2.1.2 Design new of (cold cold) to method and then account slurriesand thefraction were wetpassing througha sieved alumina balls havingwas Milling performed diameters. for different frit treatment from annealing temperature f 1cm Subsequently, the melt EDS characterizations, 25gfrit of urnace Acceptedesign Article was

3 . Finally, thesample arecheff thecanonical nas ials kno olyno the canon

was . proportion of the constituent proportion ofthe down toroom temperature poured into an industrial mill with 20wt% with poured mill anof into whiteclay industrial water and (kaolin) with

The slurry

to

used

manage this specific experimentalmanage region this the reaching the maximum temperature maximum reaching of1200 the 10

approach

the [

21 °C was

,2 frits each

over theover glass transitiontemperature toroomtemperature. 3 was was , 2 deposited on

t

4 was in which h specimen

]. Mixture modelforms].

rough curveselected DSC by the studying cast

annealed ed

the second part of study this the second part a

was

into a cubic graphitecubic a into

to two mainconstrains M (10x10cm) s

ixture ixture a remov

constituent proportion in the mixture melted in platinum cruciblesmelted inplatinum at1550

dry greendry at 750 e D

residual stressresidual esign approach

°C

was was

porcelain stoneware and let to cool naturally in theturnedand lettocoolnaturally in

(M , fired inanindustrialfor kiln 50minutes

and thesecond me and resources [ MF mold were

)

°C C 400 ost coonly ost used in fitting es . omputer

. This used: the first regardingused: thefirst having anof volume internal

were

from the formingfrom step the -

and mesh sieve was taken in mesh sieve ical givenby ical statistical based approach

designed designed performing theheatingperforming - 30

taking in accounttaking Factor A

tile

ided D ided min. Aftermin. milling the 21

support byairless support ]. ].

- °C at

[ by the using - 21 -

optimal optimal for 30min. A The ,2 - Time 5 ]

. The : ground

the

the - off

This article isprotected rights by All copyright. reserved. component The responsecontour plot w allowedpoints E work and their range. specific software the predicted estimable the R terms ofregression significantand thereforeneglected analyzed potentialdeviating out to point experiments samples obtained in samples statistical differencecan when among samples be thevariation defined power variance ( regression, and x here β ighteen Acceptedere Article

2 performed accordingrunperformed order tothe randomized

and Pred to describe i ,

and β was usuallyfactorchanges due toprocessor by the p by the experiments

ANOVA from the independent variables s

on the final propertyon thefinal considered

values used to ij estimating

- are regression coefficientsare from data theexperimental regression by calculated multiple R i

-

and x 2 value approach:value between the relationships ) .

analysis and thepredictionanalysis of power themodels

R was the of the dependent variablesof the the data the , 2

including one is

j

same experimental conditions

are oftheindependent thelevels variables[ employed to

the

the odel’s lack of fit as ellthe odel’sasreliability of lack its was

proportion ofthe inthe variance dependent variable analys

used

p for - is as functional tools in explaining in as tools functional

values higher than 0.05 higher values center

evaluate modelsignificanceand predictive the its

[

the model formulation [2 the model formulation 2

8

and ]. ].

, points replicatedpoints 4times,

Table

compositions compositions . as well asas theregression well coefficients

Pred

[ 21

,

1 is largervariation enough within thanthe -

].

R

reports considered thecomponents inthis

D

2

is

[2 esign

to avoid environmental conditioning to avoidenvironmental

5 similar toR

]

and .

E The residual analysis

w

xpert (version (version xpert properties

ere 6

,2

not 7

2 ]. ]. were 2 the role of 5

were but calculated through considered as statically The quality fit in ofthe ]. among all the . The experiments .

. The

evaluated by using In particulara planned. Replicate 8 analysis of , Stat the main s

were

was that is that is - Ease

used used

) . This article isprotected rights by All copyright. reserved. °C scanningcalorimetryanalysis performed Netzschair (DSC, 404) at rate10 inaheating of evaluatederror (XRF oARL and analysisADVANT’ Ther las a(ICP) XP+) inductively cou led glazes The characterizations 2 was cleaned waterremovewith hot and residue any dried to at salt 120 °C The specimens I 2.2 therefore same applied methodology withthe resulted Design from Mixture Therefore, wereemployed as to were K experimental plan(Table Technicalgraderaw materials 2.1.3 .3 2

1550 CO

/min using/min 30mg of Accepted Article

for Experimental Experimental

chosen fromchosen literature as commonly employed themost forglass[ float E

mixed inbatch of50g,mixed mel New

3 . process 4

, Li The chemical composition of the chemicalcomposition The

h °C

employing (LEMA, kiln an industrial TC20A) 2

frit the same procedure applied for industrial frit for procedure appliedthe same industrial CO with afinal dwellof time 40min s

3

were

preparation ±0.1 wt%. ±0.1 and P Characterization

pure

completely immersed in a bath ofmeltedcompletely inabath KNO immersed 2 were O powdered sample

oxide 5

3 with purity(the >97%industrial puritymaterials) isthesame of

T

). In). particular performed using a multiple techniques forperformed approach usingafrits and multiple he thermal s

was were or carbonate ted in platinum cruciblested inplatinum

taken as inconsideration base

employed in orderemployed to in behavior s industrial frit , .

SiO The glass transitiontemperatureThe (Tg) s

), to enhance the composition to enhance the

mentioned 2 and thenquenchedand inwater. , H

of of 3 BO each

3 was , Al

. was

frits frits

in paragraph 2.1.1.

Subsequently, specimens the obtain ( heating of rate 10

obtained by X 2 O

employed. was 3 , Na frits according tothe

to produce a glazeto producea and measured usingmeasured differential

2 °C CO 3 at atemperature450 of

for 24h. for 24h. 3

The The , CaCO

careful - Rayfluorescence

All raw materials

7

optimized

- °C/min from 25 °C/min 9 This process ] 3

. , MgO, control was

, with

were frit as .

This article isprotected rights by All copyright. reserved. crack border theformation tothe footprint. of near preliminary test constant load of0.5 kgf processVickers aMicro using Vickers micro hardness (Wolpert, 402 tester the conclusions canreasonably befritsfor alsothe drawn successfully used respectamount ofNa the to distance from thesurface evaluate deviation standard procedure kV, toavoid the mobility of employed avoiding the bordercore the tothe ionexchanged of surfaces the cross concentration along cross the the ionexchange isanear an w The cross process Tg temperature below the sensitivity ( the instrument of theslope.shifting and on thetangent calculatedas the cross

Accepted Articleere energy X dispersive

frits and

observed using scanning electron microscopyobserved scanning using ( - any interference betweenany interference measurem twonear section section - . section was The voltage of the voltage beam electron The of glazes stoneware porcelain

performed onat leastareas for fivedifferent theperformed same of sample s

was performed toderive s in

of previous previous

conducted conducted and glazedfrits stoneware porcelain - - point between on point thetangent

ray device spectroscopy and

of exchange - surface process, the results should display should surfaceresults process,difference the ainions s +

. light dwell of time 15

- was Ion Depth Exchange studies section. ,

to retain the vitreous structure thevitreous to retain through ± alkali ions under theelectronalkali under ions beam. detected 10

on E °C). the highest load of penetration avoiding possible, the highest load the

Therefore, to the core, valuated errorvaluated on

w ion exchange process punctual

as . This evaluation This evaluation It

measured before and after the ion exchangemeasured beforeafterthe and was

is worth noting that is worth s.

This load (EDS, Oxford INCA Oxford (EDS,

reduced as much as possible, workingas atreduced muchas 5 possible, the the

EDS throughout ( Twenty were performed on indentations IED ,

ESEM the initial straightthe initial before line baseline to semi analyzed ents

identify changesconcentration inion ) measurement

this measurementassociatedthis with is parameter

was - , polished , polished withdiamond papers, was quantit , due to

FEI

a higher amount ofK amount a higher of the glass.of the selectedas

in necessary to

in t

Q glass this this ati the magnification uanta 200 uanta his

was ve , -

method This measurementThis 350). es made

work [ work chemical

, evaluated as the

therefore useful a

- result ofseveral

Considering that ensure MVD) with a every 5 ) equipped with 2

was 9 - ten 31 analysis of

already

the ] + times times .

 with HV of m from

IE

t o

,

This article isprotected rights by All copyright. reserved. tests werereplicate forcoating, run ineach the wear. and therefore and a total sliding of500 distance Test include conditions G99 on glaze mechanisms. optical microscopy defining allowed thecritical loadsspecific for damage theonset of respective scratch fro test”) 0. 200 CH) Peseux, scratch On these specimens microstructure after and before the immersion in performed Philips) G glazed layer indentations were oncubic performed specimens each lazed porcelain stoneware

Accepted- Article disk geometry

µm

[3 specimen

(L 4

and wear resistance test -

c ] with Cu radius spherical 2 . Specifically, Al ) following ISO) following 20502procedure [ ly. Three tracks Threely. tracks

following the standardISO ENfollowing 10545 the

l

for

was the weights werethe weights with analyticalwith sensibility measured balance of In studycritical this the inaccount load taken was the difference

and the results wereresults and the

porcelain stonewareporcelain - Ka radiation andconventional

carried out usingcarried aC Rockwell (High

a 0

further mechanical characterization 1 d glazed - N to30

Temperature AntonPaar TriTec) Tribometer, according toASTM tip andtip a constant 5 normal load of were s w

in weightafter before and the test as samples

s

performed on each sample. Visual oneach inspection ofperformed thetrack by

. Scratch test N. Scratch and speed length were 6 o erating ithlinearly increasing load(“rogressive characterized through

m. indicated

tiles

Three

were .

at 25

33 repetitions tested against atested 6

as average deviation ±standard (Micro ]. 

-

the the Wear resistance test °C °C  of molded material , typeconical having diamond indenter a

 in order toevaluate difference

with 60 - molten molten N, a relative of0.20 speed sliding  Combi Tester,PaarCombi TriTec, Anton geometry

X were -

s ray diffraction (XRD, PW3710, PW3710, ray (XRD, diffraction

was % relative humidity. salt bath

performed for each forperformed

mm

. were

were

due to the flakedue tothe W - ater diameter

mm and 1 and mm

consider performed through performed andonthe frits for [3 was absor 2 ]

. performed

a ption (AA)ption . ed

lumina

The mm/min, mm/min, -

to evaluate off s specimen

in the 10 of the

- on ball on ball. mode - 5

m/s m/s

g. was was

All - This article isprotected rights by All copyright. reserved. observedabsencecracks relevant of the goodIE defects surface a or before very suggesting calculatedHV byIE which about In speaks glass ahardened Figurecan 3it also process. be but significant, indentati ofthe decreasing measured increasingIEHV process. after of measurement SEM that the Considering error thecalculated associatedHV measurements is totheit IEas the showninTabletheHV and 3where before after process The effectiveof theindustrial measurements frit has hardening confirmed by been hardness according stated inparagraph isabout10 tothe definition 2.3, whereas theopposite isobserved Na for particular,K the highlighted of the by antheconcentrationIn close twoions inversion tothe of reaction zone. Considering anear process is thatthis The2) EDSresults highlight (Figure that industrialfrit cantreatedIE be successfullywith expected due tothermal treatment overFinally the Tg. specimen °C show that structure °C industrial The aim ofthe analysis thermal Industrial3.1 fri 3 Results andResults Discussion

Accepted Article ) mustbe because

comparison average asubstantial the of isstatically and reliable out values point

and the softening of the frit during the IEfrit duringprocess.and ofthe the thesoftening

selected frit the industrial frit the

below .

The meltingbathIE employed ofthe temperature during saltthe process (450 Tg i t +

concentrationhigher is at theand surface

equal to equal the s equal to 590 to equal s ,

no crystalline inFigure isvisible no peak 1therefore nocrystallization is Tg

of the fritof the

750 canIEfor be tested process

°C was

s °C , ,

as previously (2.1.1), tostands isconfirmed discussed , in order to avoid anyavoid , inorder change touncontrolled inthe network therefore, the frit cantherefore,classified theglossy. be as to investigate theglass temperatureto investigate transition . Moreover, theannealing also temperature ofthe bulk - surface activity, the occurrence of IE activity,samplesurface is theoccurrenceinthis of +

confirming the IEconfirmingIED process. parameter, theThe on s

afterIE reportedFigureshow in 3 employinga

lower near thelower core ofthe sample, DSC results (FigureDSC 1)clearly 

and this is consistentthe and with is this m. have

temperature eqtemperature

has possible toconcludepossible

been measured. s

(Tg) a slight, ual 450 to

of the of .

This article isprotected rights by All copyright. reserved. andproportion scratch between resistance property. load effect scratchand the onthe surfaces most property isreasonable This load hasas during beenthehighestconsequently, achieved chosen thetest, theexpected obs Hertzian circular thewith spallationinside cracks trace,opticalas microscopy shownthrough increased.of thescratch Allthe traces testsreported are characterized by tensile value obtained necessarythat is glaze theouter from of part thesupport the (L toremove mechanical the characterizations, scratchresistance has critical evaluated been as the load of naturallyaffected state a stress by betweenglaze includes frit and clay differentin factchemical compositions, asstated inparagraph glaze composition 2.1.1the glazed are porcelain si stoneware with the general industrialfritresults characterization. from IEsignificantlytreatment, after thestrong reaching value thefinal of0.68 GPa,in similarity scratchobtained. Consideringcan resistance be glazedindustrial stoneware;In porcelain fact, asignificant increase and wear ofhardness, As showninTableresults obtained 2thefor frit can achieved theindustrial bealso for the Industrial3.2 glazed for frit,istreated. formulation nevertheless acomplex of oxides more content of Na performance the annealing of

Acceptedfrits) Article ervation ,

and this is consistentthelowerand with is values this obtained s

(Figurewhere 4)effect the +

and porcelain stoneware support >10% and theabsenceIE and >10% ofcrystalline phases ensurea successful treatment after the IE treatment,after theasreported . Moreover, porcelain stoneware porcelain

treatment. According

gnificantly thanthe lower ones obtained frits for dueto due to due

after cooling

s the difference in

of the test finalload(30N)of thetest , with respect (as , with a to bulkmaterial

(data notreported)(data Table 3the HV increases parameter Table

in Table 3 in to

results from literature about glass, literature aboutresults a from

coefficient of thermal expansion of expansion coefficient thermal In Figureglaze surface 4a the before

,

The HVobtained values for suggests that .

Taking inacco critical, theinverse due

the applied glazethe applied

has

ha c2 this load must be loadmust this ve ) and therefore the

been show. been unt the further - type

in the case is

This article isprotected rights by All copyright. reserved. 3 Tab The range 3. deriveglaze formulation. a potentialnew strengtheningIE and therefore by using Mixturefocused onit Design the be can concluded toanswer frit issuitable that chemical the industrial tothe requirements of andIE afterthewith very of thepeaks(Figure process 5) intensities similar porcelain phases where stoneware same have support before crystalline the identified been s parameterthis change not significantly, does confirmingof theporcelain thatopen porosity salt bath.molten thewater Forabsor first, beenany evaluated toensure glazedFinally,aboutalso porcelain stoneware, microstructure and water absor significantly higher. is weigh glaze the only to related percentage the therefore specimen, stoneware porcelain the account in taking estimated is quantity this that considered seem could 0.04% of difference a Nevertheless, glaze. industrial the for registered is 0.05% to 0.09% from loss material of reduction a fact, In treatment. IE the ball the during removed material of (%) amount of other the with similarity strong In damage ispresent. surface stoneware; inFigureglaz onthe opposite, 4bthe IE a damaged,relevant and glaze part ishardly isdetachedporcelainfrom ofthe the toneware isconfirmed same The result isunvaried. byperformed XRDanalysis the onthe

Acceptedare reported themeasured 3 Article

New frits from le

1

from which the experimental planof from experimental whichthe s

of selected compositions the for

m

ixture design analysis

parameters undesired modification of thesupport modification undesired duetothetreatment the in analyzed

( Tg,

ption

properties, the wear resistance, indicated in terms terms in indicated resistance, wear the properties, M HV, Table ixture

has beenshowninTable 3, has as considered and, ed surfaceIEed and after a less isshown,

 HV 3 - D

on has been esign are investigation detailed in ,

- IED) foreach surface test, strongly decreases afte decreases strongly test, surface

derived. On the rightOn derived. egt f l te glazed the all of weight s

frit insignificant it must be must it insignificant

obtained. . It. can be ption ,

as base to

The of Table of Table have r This article isprotected rights by All copyright. reserved. (eq.2) between andthecompositions final measured responses explore theregion ofinterest. residuals reliable out the excellencemodel validity ofthe > one (equalwith ap 191.6) to he ANOVA for each calculated differentfrits uncertain been reported hereafter. the ANOVA beforeIEbetweenHV the HVand process final IEthe process andal strongwith industrialfrit. HV similarity parameterhas been exchange process temperature of450 included inthe range 530 results statically reliable. estimatedglass errortransitiontemperature onthe is

Accepted0.05 Article . ,

allowingconclude thatthemodel significant is to correlation between correlation between experiment

has been since

average values of average values

results , and lead

according ,

e ven Tg ifbelow

analyzed

in

a so the HV variation so the llowing a statically reliable acomparisonllowing statically amongdata. s Table Table

to very to The to the distance glass from their transition -

As shownfrom Table 610

(data confirming notreported) thatthemodel be can used to glass 4 - IED, 

value < lackvalue 0.05,and offit the significant a isnot with p

The resulting model allowedThe resulting model

HV parameter has beenHV hasthe parameter possible considered toovercome show °C similar resultssimilar ,

and boththe annealing of750 point composition and composition HV the same IEcan same temperature effectsthe produce different in s

that thetwoF testsaresatisfied: F °C

and

with values

( becan employed 

 HV HV ,

therefore only the data analysis for therefore analysis thedata only )

. 3 the estimated errorsthe has been inaccounthas asthe taken difference

HV

all theglass temperaturesare transition  very close to

HV ± and 10

. as showninthe

.

°C The normal distribution of the The normal distribution 

Moreover, for thisgroup specimensfor of

HV to

measured for each and experiment

describ data data 1.00,

temp have been have

fall e R

°C

afterthe application of the relationships the relationships 2 which explain erature -

value ishigher than value and Pred calculated

in the range and theion and

. analyzed About the  R

HV regression 2

point point of of

it , in a - has value

5% by

This article isprotected rights by All copyright. reserved. order toretain observed for theconcentration thatlimit Concerning the At thesame time, high the P depolymerization present work on typeand amount of withthe is consistent further ofP increase P Considering themain others three more (data notreported). surface. Liconsidering amount of thattheselected due tothe restrained numbe Figure 6 thecorrelationinteractions explain and composition contribute to between The analysiscoefficient of the  2 HV

AcceptedO Article 5

glass interconnectivity 2

content from theminimum themiddle value to producesanof increase the

= O 1144.66549 *B + 1858.88634*P 1813.51071 *B Li - 5

7.16978 * B 7.16978 *

In

(a) 2 content O + 289.68752 *B O + 289.68752 fact, .

InFigure and(b)figure(a) 6 6 B the increasingthe a 2

O

B a furthera high high further 3

2 significant which results inahigh ofcations move tendency to an increaseNa of

O and suggest that Therefore, 3 2 2

, O O

 already singular its networkits 2 2 3 5 other oxide other HV O O

- content upto increase 2

increasingLi of content O 3 3 1798.9514 *P

. Moving higher toward * P * Na 5

IE r of comparable components graph ina and response surface of starts to * Na

2 factors known , in similarity with P , insimilarity with O 2

s

effects, the P O th

2 3 of the models O * LiO *

5 s e following * P 2

+ 39.27082*B former O + 1081.00785*P the network formerthe network role s

2 Na 2 in formulation .

O or B O or 2

reduce O role ofP

O

3 5 + the most the most 2 5 wt%

O + 2155.14629*P

actingmodifier as 2 content not have * Na

O role results inamoreresults role 2 5 O generatesO the largestarea ofthe 2 s

- O

the Lithe leads a to

part of theanalysis has focused on the part been the ions mobility and then the IE mobility the ions and thenthe 2 8.60007 *Na 2 3 suggests thatsingle alsotheir factorssuggests but O + 172.12578*B O

content leadsof a to decrease significant 5 2 2 as glass both former O 2 O

2 [1 values in O content equal has been to fixed O

3 over 2wt% 5 6 * Na . ] 2 restrained : Na O for theseriesfrits inthe studied of 5 to

2

2

* Li promotes the start to O 2 O + 481.3966*B one

O be

2 Na

O effect is

- 2 5 increase

is P packed structure O + 419.15942*Na +

172.5346 * Li 172.5346 *

* Na

lead

decrease of decrease of concentration results in a concentration 2

take place andtake therefore the O 2 O 3 s

2

, * P 5

O *Li stronger thanstronger theone

to a decreasingto a of or favoring in fact d

network network

2 over over modifier O  5

HV 2

* Li 2  O  response

a 2 O the ef HV. Thistrend O + HV. n increase

3

the

fectiveness at high  as shownin * Li 2 10wt% , O HV, buta

according IE 2 - O * 2

2 ; when

wt% 

in of HV HV .

This article isprotected rights by All copyright. reserved. frit. Consideringfrits characterization the but alsobeforethe and after glaze).frit and characterized samefor procedureperformed followingthe thestarting materials (industrial f Optimized 3.4 ion exchange process is confirmed that pure error. IEDThe statistical analysissignificant themodel for not isnotreported since is duetohigh of in practice tothe structuraltransition due D results fritindustrial component enhanced hardening be selected toenhance inorder detail Also, increasing over behavior strong esignallowed

Acceptedcomponents take Article Optimized frit andOptimized glazed porcelain stonewar

the interaction effectshave been in

interference eq

F can ual to igure Taking therange inconsideration due to the strong interaction among oxides in a complex formulation inacomplex due tothesuch strong interactionamongas oxides rit

s be supposed for Li forbe supposed .

(13.5B

Therefore, The composition ofthe optimized frit,The considering composition variated the only

13.5B 6 2 to

wt% should beavoided wt% should t (b) he point out how small changes in composition can yield can changescomposition outhowsmall point considerable results in in the diffusive in the s

by . place. place. EDS

2 2 It be can highlighted that applicability ornot O O IE canreached be 3 3 - -

1P 1 a comparison be notonly can made andIE beforeafter the process method P

M 2 2 O O ixture ixture 5 5  2 - - O 10.5 Na HV. 1 0.5 allows only toderive

path that D

From this compositional analysis, compositional this From can it be stated that Na examined esign of the optimization ,

of the high in fact

2 2 . , (data notreported) ,

O O

considering

occurring interactionamong when as shown inTable 2 as shown - - 2Li 2Li s

of formulation ,

an intermediateaneach content of 2 2 follows follows

O) O e and and

.

percentageexchanging of ions A rational approach applied on the main a restrained a

the same trendNa of semi

. s

-

quantitative reported inthe , result porcelain stoneware

the IEDthe parameterresults

chemical formulation of the range of range of s

have beenhave

such as such

information information w

2 a t% of each M O large oxide ixture ixture M and any reported . ixture ixture , A

factors, ha number

s should should D imilar s on the

esign been

in

This article isprotected rights by All copyright. reserved. residues are notable to nature,very a a porosity, salt materialwith lowamount ofopen therefore thepossible pattern are same. inpracticedue Thisis tothe fact the that theis,for porcelain stoneware its microstructure part of porous fact thematerial, in ofthe characterization, ranges are around close for tothe one theindustrial observed frit for glaze a theoptimized d shows (Figure spallation produces showninFigure lessdamage, as damage isneeded onthesurface it + equal to about + resistance results drawn the for frits av IE is4.5GPa differenceevaluatedfor andIE afterthe process frit consideringoptimized between before difference frit thattheHV theoptimized GPa) average value unchangedafter mixture design the optimization, even ifaof increment significant

Accepted Articleerage values. instead of the industrial one instead ofthe industrial 1 4 4.8 5 b) and to the optimized glazeIE and before tothe optimized b) (Figure

0% for theoptim tests

N and after the IEN and afterthe process ).

after the IE processafter the after the IEafter theprocess

. The scratch resistance of the optimized glazed scratch resistance. The surface ofthe optimized res This trend is also in agreement isalsoin theThis trend restrainederrors onthe with measured The mechanicalglazed ofThe suggest properties the thatthe investigated surface

it must beIE does must notedthat haveit not the impact treatment a onthe negative lower values of materialloss. lower ized glaze (

penetrate (6.3 GPa) isequal(6.3 to the industrial frit industrial the are

confirmed

: the microstructure. the

ifference

(4.5GPa) is detected is detected the scratchIE resistance the measured before process is Figure 4d) 1 50% ofthe 50% is , taking in considerationand, takingthescratchwear in

12.3 and

4 of . : Again,

a

2.5 GPa 2.5 up to + up to

0.04 with respectIEglazewith theindustrial to afterthe equal to to equal , nevertheless N load load

. About glazed porcelain stoneware load This means produce that to thesame % from before to after the IE% from before the toafter

of the IEthe by process results promoted the

4

, orinother same terms the 0% and therefore 30N produces a very restrained30N produces avery 1.1GPa

water absor water 4

employing the c) . is evidentthat

The wear resistanceThe

( before ption larger than the samelarger IE is optimized frit optimized

(AA%)XRD and ults improvedults of

for theformer 3.4 GPaand after process, very s load

obtained

HV (3.8GPa)

(6.3 the

This article isprotected rights by All copyright. reserved. ceramicindustrial products. tiles confirm the of thewear resistance (+ formulation anoptimized increase (+ ofthe HV This result isconfirmed higherHV. 1 which in P compositions fundamentalfrits design role innew Li suitable best candidatefor the formulation oxide improving thefrit hardness process porcelain stoneware determined using stoneware Inf work this 4 Conclusions 0.5

Accepted 2 Article O have vari been wt %, established to find a tailored fritto finda formulation tailored

the B production and production effective potential

unctional relationship betweenunctional relationship

2 O

M

3 than aglass generalfloat

at most within 13.5wt% at within most for

ed ixture ha

M

pointing outthat the pointing s chemical

ixture ixture after application of the frits asglazeafter applicationof thefrits for onporcelain stoneware: the 130 been characterized 2 O

their hardness, obtained throughtheir hardness, obtained D , 5

%) can by highlighted be IE applyingprocess the esign approach. although is present within atmost

D application ofchemical this method also strengtheningfor esign study hardening

for technological applications. frit s for porcelain stonewares for .

In particular ofB thecontent

.

of glass of interactions between and

and Liand

in order to in order A In thefirst part study ofthis the s a

4

treated composition offrits suitablecomposition for 0%), ofresistance0%), thescratch (+ consequence, 2 . This treatment has positive effect. Thistreatment haspositive on O 1 2

wt wt explore a range compositional through a

% % an , theNa

promoted frits characterized by

ion exchange

this industrial frit industrial this oxide well has

2 In study this O at most within O at within most

- have s known 2

O concentration

a 3 , P commercial for frit

a more complex process, 2 ,

O ion exchange allow 5 porcelain , Na 1

resulted 50%) and and 50%)

ing has beenhas 2 O play a

3 to

and the

This article isprotected rights by All copyright. reserved. 21. Montgomery 20. 2009/607/EC: 19. Eitel 18. 17. 16. Zeng 15. Du 14. 13. 12. 11. 10. 9. 8. 7. 6. 5. 4. Doremus 3. Hale 2. 1. References

Jacoby Fisher 1115 GyIonexchange glass R. for Sci Mater EngB strengthening. Solid LessonsVarshneya AK.StrengtheningLearned ofGlass: Chemical Yet and ToBe Accepted ArticleBartholomew Bartholomew Mater.Glasses, Sci. J. Donald 2001. C(2009) 5613. the award the Community of eco yEsp Ceram Vidr. 2018;6 DOI: TemperingTiles. Cer ofPorcelain Del 2013;36(9):397History, Rivista NuovoCim. applications. evolution and 8. KNO 2003;90(15):155507. Press,1980, engineered materials 25 strengthened Technol. 2008;149(2):159 IntLearned. ApplGlas J Phys. A Battaglin Uhlmann Dal Chemical BóF. Bol temperingporcelaintiles. M,Medina toSpanish applied la Soc Dal Bó introducing pentoxide phosphorus Structural of investigation chemicalglass through aluminosilicate strengthening AluminosilicateSilica Yttrium Glasses G CarturanMazzoldi P, Quaranta S, SglavoIon A,C, exchange Sada VM. process: XiangchenZ,Ouli H,Cengzuo salt Z. Themolten X,Yinghuanin effect ions ofimpurity Adams Alkali Effect S.Swenson Mixed J, Glasses. in PhysLett Rev [Internet]. Gonella Linati Leonelli

: lass 34

J. - DK. 10.1016/j.ceramint.2016.06.138. 11 3

-

W.

. WK.

36. H Molecular Dynamicsofthe StructureLow Simulations of and Properties

on ion

M. L. IW. J. Phys. B.J. Chem. 20

.2005;

, M

F RH.

Wang

Strengthening of silicate glasses exchange Strengthening ofsilicate byion C Industrialglass: glazes enamels and G DR Influence of small additions of AlInfluence additions of small of

New applications for glass forapplications New emerge , ,

, pp , Moore Quaranta Improving for Oxide theMechanical Properties ofMethod Dominguini

Lusvardi

Cattaruzza

- glass laminates

, RF RF.

exchange and strengthening of glass. J NonCrystexchange strengtheningglass. J and 1986;80(1 Solids. of 217 Glass Sci 81 D.C. Design

Kreidl

Commission Decision of 9July2009establishing theecological

L , :

1065 , – Garfinkel Ion

Ye 267. MJ.

h -

1989; A DOI: NJ

G Exchange F - andbook

1071. ence , Rosenblum

, ,

E

, L P Yang Montorsi Sci. 2010;1(2):131 2011; . editors adovani – , –

10.1103/PhysRevLett.90.155507 Copper diffusion inion 24 65. and and Zimmer 11.

. HM. .

New York WO 2012051038A1, 2012. WO :

4177

105 B . In press a

. Metals Park, . - nalysis of ,

I

Chemical Strengthening Glass of label to hard coveringslabel(Notified hard to under Glass Science and Technology Chen

n: .

S

: . M Int.

– SS. 919

, A Front. Mater.2016 ASM International ASM

4208. , Sada

, Menziani

Grando -

2016; Shi :

. J 927. DOI:

, Wiley andWiley Sons J. Am.Cer J.

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O .

42 42. 10.1016/j.bsecv.2018.03.002 . New York.

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D’A Thomas Chemical News & Engineering 3

S

:15

on thepropertiesNa of G

M.C ,

, Kaspari P capito -

199 Sun exchanged soda am. Soc. ,

Menabue

;3: - JC. JC.

. New York 15202

L. editor

; F 1 :

1994. , - Mechanical Academic Press,Academic . i

7. – Maurizio nventor ,

Nature

Hotza D Hotza 2009; 483

. .

Ceramics and glasses,

L

. .

, New York:New

. - .1968; 92 Mustarelli ; - s;

State Mater AdvState I lime glasslime John Wiley& Sons n:

C . : Chemically

– 87 .

Chemical , 2

O

– document document 217 - 95.

3SiO 1976 – :

Academic .2012;

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. criteriafor .

–

3):313

: – This article isprotected rights by All copyright. reserved. 34 33 32. 31. Cornell 30. 29. 28. Stat 27. Eriksson 26. Colbourn 25. Akalin 24. Cornell 23. 22.

Accepted. . Article ASTM B. Vol. Stand. 03.02,2017. Determination ofceramic of adhesion scratch coatings by testing relativedensity density and bulk Cryst 2017;473:170 Solids. exchangeimprovement process for ofand thesurface Non bulkmechanical strength. J DOI: andsalt impurities treatment NonCryst temperature. J Solids Hall Society

DataMixture IonTalimian A,Sglavo VM. and IntelligentLaboratoryand Systems performancefor mixture experiments, concrete testsusing Chemometrics onmortar Simul. Scheffe DOI: andtechnologicalcomposition properties ceramicEffectsfrits stoneware for bodies: porcelain sintering, onphase Zanelli İ AydinErdeeringD . Cheical sodaglasses Guldiren esilicate by te ion li of experiments principleand applications ISO 20502 ISO 10545 A TM G99 − 17: tandardA TMG99−Wear Testing 17:Method Test for ithaPin : - 2006. 10.1016/j.jnoncrysol.2016.10.032 Ease, Design 10.1016/j.ceramint.2006.11.008 2000; .1958;

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C J.A. J.A. H.

, , L

C.C Akay Baldi :2016. , Experiments with mixtures, with Experiments ofthe Journal Royal Statistical – Johansson

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. New York Ex Developing St models,areweJ. mixture done? 20 3: ,

: Dinitz 2018. : 127 periments Mixtures: Designs, with Analysis of Models,and the

344 K.U G - Fine ceramics advancedceramics) (advancedceramics, technical , Expert VersionExpert 7,Stat

- Dondi - 144. , 360.

Determination ofapparent water absorption, apparent porosity, Sennaroglu J.H. J.H.

E

: ,

John John Wiley& Sons Kettaneh

M – Handbook of Combinatorial Designs 8. - , exchange strengthening of borosilicate glass: Influenceexchangeglass: strengtheningborosilicate of of

Ercolani

B

- .2010; Wold ,

Tez

.Stockholm; .Stockholm; G

- ,

. M. 104

Ease Inc., Minneapolis,Ease 2010. N

Guarini Ceram. Int.2008Ceram. ,

; Optimization ofchemical admixture Wikström : 2002. 233 –

G

Umetrics Acade 242. ,

Raimondo

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Wold ;34: at. Comput. . 2017;456:12 455 .London; .London;

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Design of 465.

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This article isprotected rights by All copyright. reserved. quantities are wt% expressed in P Figure 6 079 IdentifiedICCD:01 (Q) phases:Quartz crystalline Figure 5 IEIEand glaze for(c)the optimized after and before (d) Figure 4 Figure 3 the industrial frit Figure 2.K Figure frit industrial curve ofthe 1.DSC List offigures 2

AcceptedO Article - 5 1454 ( - Na . . . . 2 indentations (a)Comparison of O (a)Variation of (a)Variation of theXRD patternComparison of (red) beforeIEand the after(blue) process. scratch glazeComparisonfor of testsand atbefore industrial (a) (b) 30N after the Al +

(

Li and Na and 5

SiO 2 O

=2 wt%) (b)focus onaincorrespondence 2Dslice to 9 ); +

AlbiteICCD: (A) 00 concentrations vs. distance from theconcentrations surfacefrom vs.distance samplecore towards the of  H V through 3D response surfaceV through 3Dresponse ofthe

before and (b) afterand before - 001 - 0739 (NaAlSi 0739 - 083 - 0539 (

3 the IEthe SiO O 8 )

2 ); MulliteICCD: (M) 01 system (A system for industrial fri for industrial  HV=2.4. All - B - C) C) B t

2 O 3 -

- This article isprotected rights by All copyright. reserved. Accepted Table for 4.ANOVA themodel results Article TableIED, 3. Experimental planand (Tg,HV, measured properties glazes Tablethe industrialmechanical 2. Summary andoptimized ofthe frits properties and of Table components and 1. Mixture theirofreal range interms List ofTables

 HV

values (wt%)values  HV ) foreachrun

This article isprotected rights by All copyright. reserved. Accepted ARE STONEW AIN PORCEL GLAZED FRITS ArticleTable 2. Table 1

Before IE OPTIMIZED After IE Before IE INDUSTRIAL After IE Before IE OPTIMIZED After IE Before IE INDUSTRIAL After IE

Name Na B P Li

( IED ~10 ~10 ~10 ~10 2 2  2 0 0 0 0 O O 2

m) O

O 5 3

0.81±0.01 0.69±0.01 0.68±0.01 0.52±0.01 6.3±0.2 3.8±0.3 4.5±0.2 3.4±0.3 (GPa) Low ( level HV

10 10

1 0

resistance - 12.3±0.2 4.8±0.2 7.9±0.2 Scratch 1) 3.4±0.2 (N)

/ / / /

High (+1) level

15 15 5 3 - - - - 0.05±0.01 0.09±0.01 0.03±0.01 0.07±0.01

Wear (%) / / / /

0.18±0.05 0.40±0.10 0.16±0.04 0.37±0.12 AA % / / / /

This article isprotected rights by All copyright. reserved. Accepted Article Table 3. 18 17 16 15 14 13 12 11 10 9 8 7 6 5 4 3 2 1 RUN

12.3 11.0 10.0 13.0 10.0 13.0 10.0 12.3 10.0 15.0 11.0 11.0 11.3 10.0 15.0 13.3 12.3 11.7 wt(%) B 2 O

3

0.0 wt(%) P 1.5 1.0 0.0 3.0 3.0 0.0 1.5 1.0 1.0 0.0 3.0 3.0 1.5 0.0 1.0 0.0 1.5 2 O

5

10.5 10.0 12.0 10.0 13.0 10.0 10.5 11.0 13.0 10.0 10.0 12.0 11.5 15.0 10.0 12.7 10.5 13.0 wt(%) Na 2 O

3.0 2.0 3.0 1.0 2.7 2.0 1.0 1.0 2.7 2.3 wt(%) Li 2.7 5.0 5.0 2.0 1.0 4.0 5.0 2.7 2

O

540 600 610 630 575 520 610 530 570 550 (°C) Tg 575 570 530 600 605 595 560 580

7 3 4 0 0 5 20 0 2 2 ( IED 15 10 0 10 4 0 7 10 

m)

6.33 5.52 5.47 5.72 6.25 4.57 6.10 4.92 6.20 4.41 (GPa) HV 6.26 6.13 4.23 5.49 5.74 5.44 5.20 6.30

+2.76 +1.99 +1.97 +2.11 +2.74 +0.98 +2.55 +1.40 +2.64 +0.84 (GPa)  +2.65 +2.57 +0.67 +1.93 +2.16 +1.91 +1.61 +2.64 HV

This article isprotected rights by All copyright. reserved. Accepted Article Table 4.

F 191.6 - test

<0.0001 p - value

Lack offit test 3.91

p - 0.15 value

0.98 R 2

Pred R 0.92

2

This article isprotected rights by All copyright. reserved. Accepted Article

This article isprotected rights by All copyright. reserved. Accepted Article

This article isprotected rights by All copyright. reserved. Accepted Article