Lecture14:RefractoryMaterials

Contents:
Whatisarefractory?
Whatarethephases?
Propertiesrequiredinarefractory
Selectionofrefractory
Keywords:Refractory,steelmaking,furnaces,smelting,blastfurnace,soakingpits,annealingfurnaces

Whatisarefractoryandwhyisitrequired?
Refractoryisamaterialwhichcanwithstandhightemperatureanddoesnotfuse.Examplesare:fireclay,
alumina,magnesite,chromemagnesite,dolomiteetc.
RefractorymaterialsareproducedtomeetthediversifiedRequirementsofhightemperatureprocesses
carriedoutinmetalextraction,cement,glassmaking,manufacturing,ceramicetc.industries.The
refractoryisrequired

Toallowthermalenergydependentconversionsofreactantsintoproductsbecausemetallic
vesselsareneithersuitablenoreconomical
Sourceofenergyinhightemperatureprocessingismostlyfossilfuelseitherdirectlyorindirectly
i.e.electricityderivedfromfossilfuels.Thusrefractoryshouldminimizeheatlossestoconserve
energyresources.
Becausethereactionchamberisconstructedofrefractorymaterial,refractoryisrequiredto
sustainthephysicochemicalattackofdifferentphasesatdifferentintervalsoftimedoing
processing.
Whatarethephases?
Thefollowingphasesareimportantinhightemperatureprocessingtodesigntherefractoryfora
givenrequirement
a) Slag:Itisamixturemostlymoltenoxidesandsulphides,insomeprocessesphosphateisalsoa
constituentofslag.Oxidesareeitheracidicsuchassilica,fireclayorbasiclikeMgO,MgOC,
alumina,FeO.
AmongsulphidesCaS,MnS,FeS,PbSetc,areprominentphases.Theslagismoltenandits
temperatureindifferentprocessinglaywithintherange12001600C.

b) Liquidmetal
Inmetalextractionfromores,metalisextractedintheliquidstage.Compositionofmetal,andits
temperatureareimportant.Forexampleinironandsteelindustry,hotmetalisamixtureofiron,
carbon,silicon,manganeseandphosphorus.Thetemperaturevariesinbetween1300Cto1600C.
Incoppermakingthetemperaturesarewithintherange11001200C.Moltenaluminumis
producedat700750C,andlikewiseothernonferrousmetals.
c) Matte:itisahightemperaturesmoltenphaseandconsistsofamixtureofmoltensulphideslike
Cu
2
S,FeS,Ni
3
S
2
etc.Thetemperaturesvarywithintherange1100Cto1250C.

d) Gases:SeveraldifferenttypesofgaseslikeCO,CO
2
,N
2
H
2
O(vapor),argon,O
2
areusedathigh
temperaturesinseveralunitprocesseslikeroasting,calcination,smelting,refining,converting
etc.Thetemperaturesmayvaryinbetween600
O
Cto1500C.ThegaseslikeCO
2
,H
2
O,andO
2

areoxidizing,wherasthegaseslikeCO,andH
2
arereducing.N
2
andargonareinert.

e) Speissesaremoltensolutionsofarsenides,orarsenidesandantimonideswhenthematerials
beingtreatedcontainlargequantitiesofAsandSb.

f) Drosssesareheterogeneousproductsskimmedordrivenformthesurfaceofmoltenmetal
duringrefining.Theyaremixturesofprecipitatedsolidandliquidcompoundswithsubstantial
proportionofmechanicallytrappedmoltenmetal.
Propertiesrequiredinarefractory
The diversified applications of refractory materials in several different types of industries require
diversifiedpropertiestomeetthephysicochemicalandthermalrequirementsofdifferentphases.
In some industrial units more than one phase are present e.g. in steelmaking vessels slag /metal
/gasesaresimultaneouslypresentinthevesselathightemperatures.Intheheattreatingfurnaces
solid/reducing or oxidizing gases are simultaneously present. Below are briefly described the
propertiesoftherefractorymaterials:
Refractoriness
Refractorinessisapropertyatwhicharefractorywilldeformunderitownload.Therefractoriness
is indicated by PCE (Pyrometric cone equivalent). It should be higher than the application
temperatures.
Refractorinessdecreaseswhenrefractoryisunderload.Thereforemoreimportantisrefractoriness
underload(RUL)ratherthanrefractoriness.
PorosityandSlagpermeability
Porosity affects chemical attack by molten slag, metal and gases. Decrease in porosity increases
strengthandthermalConductivity.

Strength
Itistheresistanceoftherefractorytocompressiveloads,tensionandshearstresses.
In taller furnaces, the refractory has to support a heavy load; hence strength under the combined
effectoftemperatureandload,i.e.refractorinessunderloadisimportant.
Specificgravity
Specific gravity of the refractory is important to consider the weight of a brick. Cost of bricks of
higherspecificgravityismorethatoflowerspecificgravity.Butstrengthofbricksofhigherspecific
gravityisgreaterthanonewithlowerspecificgravity.
Spalling
Spallingrelatestofractureofrefractorybrickwhichmayoccurduetothe
Temperaturegradientcausedbysuddenheatingorcooling
Compressioninastructureofrefractorinessduetoexpansion
Variationincoefficientofthermalexpansionbetweenthesurfacelayerandthebodyofthe
brickduetoslagpenetrationortoastructuralchange.

Onsuddenheating
Spalling tenuency
coeff. of theimal expansion
max
m
sheaiing stiain _theimal uiffusivity

Onsuddencooling
Spalling tenuency
coeff. of theimal expansion
max
m
tensile stiength _theimal uiffusivity

PermanentLinearchange(PLC)onreheating
Inmaterialscertainpermanentchangesoccurduringheatingandthesechangesmaybedueto
Changeintheallotropicform
Chemicalreaction
Liquidphaseformative
Sinteringreactions
PLC(%)lineai =
Incrcasc |dccrcasc In Icngth
orIgInaI Icngth
1uu
PLC%(volume) =
Incrcasc |dccrcasc In voIumc
orIgInaI volume

1uu
Thermalconductivity

Thesechangesdeterminethevolumestabilityandexpansionandshrinkageof
therefractoryathightemperatures.
Thermal conductivity of the bricks determine heat losses. Increase in porosity decreases
thermalconductivitybutatthesametimedecreasesstrengthalso.
Bulkdensity:
Decreaseinbulkdensityincreasesvolumestability,heatcapacity.
iscomplicated.Amongphysicchemicalthermalproperties,costisthe
mostimportant.Broadlyspeakingselectionmaydependon
to be heated; whether directly or indirectly. In indirect heating e.g coke
oven, Pidgeons process for Mg production, Krolls process (production of Ti by reduction of
operatecontinuouslyandothersbatchwise.Forexamplecokeovenis
keptcontinuouslyathightemperatureformonthsbutacupolaoperatesintermittently.
c)
unloadingrequired/unittime
:
presentatdifferentintervalsoftimeduringprocessing.The
combinationofdifferentphasesisshowninthefiguregivenbelow:
ephasesneedscarefulselection.

sareinvolvedinindustrialfurnace.Thereactionchambertemperaturesmayvary
.Abrasionduetomovement
Selectionofrefractory
Selectionofarefractory
1) FurnaceDesign
a) How the furnace is
TiCl
2
with Mg), walls of the furnace are heated and heat is transferred from the walls to the
charge. Among other properties, thermal conductivity of the refractory is important. Whereas
indirectheatingfuelandairmixtureissuppliedtothefurnaceandherewalloftherefractory
facingthereactionchambermusthavehighrefractorynessbesidesotherproperties.
b)Conditionofheating:
Therearefurnaceswhich
Loading
Loadingand
2)OperatingFactor
a.Chemistryofphases
Thedifferentphasesare

Figure..

Therefractoryfacingthes

b.Temperature:

Hightemperature
from 12001600C in liquid stale processing and 7001200C in various solid stale processing
operations.

Molten metal and slag are turbulent in nature. Gases are flowing at high speeds inside the
eactors.Therefractorychambershouldbeabletowithstandtheerosionandcorrosioncausedby
.timeforcompletereliningofthefurnaceisanimportantconsiderationanddepends
nseveralfactorslike,maintenanceandrepairtechnologies,conditionofthephases,temperature,
ementsoffuels.furnacesandrefractories.
s

r
themovementofthephases

d)Lininglife

Lininglife,i.e
o
qualityoftherefractoryetc.

References:
O.P.Gupta:el
P.MullingerandB.Jenkins:Industrialandprocessfurnace