Lecture35:AtmosphereinFurnaces

Contents:
Selectionofatmosphere:
Gasesandtheirbehavior:
Preparedatmospheres
Protectiveatmospheresapplications
Atmospherevolumerequirements
Atmospheresensors
Keywords:Heattreatment,furnaces,atmosphere,annealing,sintering,heating

Selectionofatmosphere:
Thesurroundinginthethermalenclosure(furnace)istermedatmosphere.Theatmosphereconsistsof
gasesandisusuallyair.However,insomeheattreatment,thermomechanicalprocessing,sinteringetc
specialtypeofatmosphereisrequiredto
Preventoxideformation,iftheheatingmaterialispronetooxidation.
Decarburizesteel.
Controlthesurfacechemistryofsteelwhichmeanstheelementsmustnotbeoxidizedor
reducedduringheating.

Produceblueingeffectinsteel.Theblueingeffectimpartsawearresistantandoxidation
resistantsurfacefinish.

reduceoxidesformedonthesurface.

Makethesurfacehardbyallowingcarburizingornitriding.

Gasesandtheirbehavior:
1. Nitrogenistheprimarycomponentofatmosphericair(78.1%).Oxygenis20.9%.Rest1%could
beothergases,whichisofverylittlesignificance.Nitrogenisconsideredtobechemicallyinert
andisusedasacarriergasforreactivefurnaceatmosphere,forpurgingetc.Athigh
temperatures,nitrogenmayshowreactionwithMo,Ti,CrandCo.

2. Hydrogenisareducinggasandisusedwherereducingatmosphereisrequired.Itmaybeused
topreventoxidationofiron

FeO+H
2
=Fe+H
2
O
Fe
3
O
4
+H
2
=H
2
O+3FeO

Hydrogencanalsobeusedtodecarburizethesteelforcertainapplications.Atthematerial
temperatureisgreaterthan973K,thefollowingreactionoccurs:

C+2H
2
=CH
4

Hydrogenmaybeabsorbedbythemetalatelevatedtemperaturesandcausehydrogen
embrittlement.

3. Carbonmonoxide:itisalsoareducinggasandisusedtocreateareducingatmosphere

4. Carbondioxide:itisamildoxidizinggas.Itformsoxideswithironatelevatedtemperatures.At
temperaturesgreaterthan540 ,thefollowingreactionmayoccur

Fe+CO
2
FeO+CO

andattemperatureslowerthan540 ,thefollowingreactionmayoccur
3FeO+CO
2
Fe
3
O
4
+3CO

Decarburizationmayalsoresultbythereactionlike
Fe
3
C+CO
2
3Fe+2COand
C+CO
2
2CO

5. ArgonandHelium:Bothareinertgasesandareusedtomaintaininertatmosphere.Insome
applicationsargonisusedforpurging.

6. Steam:itisusedtoprovideblueingeffectinsteelbetween573Kand923K.Blueingeffectisdue
totheformationofeitherFe
2
O
3
,Fe
3
O
4
,orFeO.Theformationofoxideofirondependson
temperature,andratiobypartialpressureofH
2
OtopartialpressureofH
2

intheatmosphere.
DewpointsquantifiestheconcentrationofH
2
Ovaporintheatmosphere.Dewpointisa
temperatureatwhichgasissaturatedwithwatervapour(100%relativehumidity).Inafurnace,
watergasreactioncontrolstheconcentrationofH
2
,H
2
O,COandCO
2
accordingtothefollowing
reaction:
CO+H
2
O=CO
2
+H
2
.

Preparedatmospheres
Forhealtreatmentandotherpurposesatmospherecomprisingofgasesispreparedaccordingtothe
requirement.AmericanGasAssociation(AGA)hasclassifiedatmospheresin6groups,onthebasisof
methodofpreparation
a) Exothermicbase(AGA100):Preparedeitherbypartialorbycompletecombustionofgaseous
fuelwithair.Watervapourmayberemovedtoproduceadesireddewpoint.Theatmosphereis
amixtureofCO+CO
2
+H
2
+H
2
O+N
2
.InaleanexothermicatmospheretheratioofCO
2
/COis
greaterthanarichexothermicone.
Thisatmosphereispreparedbyburningamixtureofhydrocarbonfuelandair.Thecombustion
productsarepassedtoacondensertoremovewater.Thecombustionproductsarefurther
driedbyusinganabsorbentsuchasactivatedaluminaoractivatedsilica.Thedriedatmosphere
isthentransferredtothefurnace.
Typicalapplicationsincludebrightannealingofsteel,copper,sinteringofnonferrousmetal
powders,andironpowders

b) Preparednitrogenbase(AGA200)
Theyareexothermicatmospheresandproducedbycombustionofamixtureofairandfuelgas.
CarbondioxideandH
2
Oareremovedfromproductsofcombustion.
Theyareusedtoheattreatlowcarbon,mediumcarbonandhighcarbonsteels.N
2
atmosphere
cannotbeusedfordecarburization.
c) Endothermicbaseatmospheres(AGA300).
Endothermicbaseatmospheresarepreparedbyusingaleanmixtureofhydrocarbonfuelwith
air,i.e.massofairislessthanstoichiometric(theoretical)amountrequiredforcomplete
combustion.TheobjectiveistoproduceCOandH
2
.
Asamountofairislessthanstoichiometeric,acatalystandextraamountheatarerequiredtofacilitate
combustion.Theendogasiscooledimmediatelytopreventthefollowingreaction:
2C0 = C0
2
+C
Ic o] u
o] CH
4
Typicalapplicationsincludebrightannealingofsteelofanycarboncontentwithoutdecarburizationor
carburization,heattreatmentofsteelofanycarboncontent,brightcopperbrazing,andcarriergasfor
gascarburizingorcarbonitriding.
Considercompletecombustionofmethane
CH
4
+2(O
2
+3.76N
2
)=CO
2
+7.52N
2
+2H
2
O
Fortheratioof
mo
moIc
= 9.S2,theatmosphereconsistsofCO
2
,N
2
andH
2
.Howeverifthesaidratio
islessthan9.52e.g.1.88,thenaccordingtofollowing,reaction,
2CH
4
+(O
2
+3.76N
2
)=2CO+4H
2
+3.76N
2

theatmospherecomprisesofCO,H
2
andN
2
.Thevolumeofatmospherewouldincreaseby3mole
volumes.Theatmospherewouldcompriseof20.4%CO,40.8%H
2
and38.8%N
2
.
d)Charcoalbaseatmospheres(AGA400)
Itisproducedbyfollowingreaction
2C+O
2
+3.76N
2
=2CO+3.76N
2
.
Theoreticallyatmospherewouldconsistof34%COand66%N
2
.Duetomoistureandvolatilesin
charcoalandincompletecombustionofcarbon,thereactionwouldproduceCO
2
,CO,H
2
,CH
4
andN
2
.
Normallytheatmosphereisneutraltohighercarbonsteelsbutthecarbonpotentialmaybeincreased
byaddingnaturalgas.
Thecharcoalbasedatmosphereisusedforhardening,annealingandnormalizinghighcarbonsteels
withoutscaleformationordecarburization.
e)ExothermicEndothermicbaseatmospheres(AGA500)
Theyarepreparedbycombustingamixtureofairandfuel.POCisdehydrated,andapredetermined
quantityofhydrocarbonfuelisadded.Themixtureismadetoreactinpresenceofacatalyst.
Typicalapplicationincludescarburizingandcarbonitriding.Duetothecostofproduction,these
atmospheresarenotveryoftenused.

f)Ammoniabaseatmospheres(AGA600)
Ammoniadissociationisusedtopreparehighestpuritynitrogenwhichisfreefromoxygen.
Liquidammoniaisvaporizedintoaheatexchangerandisfedtodissociateinareactorcalledas
dissociater.Thedecompositionofammoniatonitrogenandhydrogenbeginsataround300320
0
C.Rate
ofdecompositionincreasesastemperatureincreases..
Itsprimaryuseisforbrightannealingmetalssuchassilicontoobtainelectricalproperties.Ferrousand
nonferrousmetalsarebrightannealedinammoniaatmosphere.
Brightsilverbrazingandcopperbrazingofsteelareotherapplications.
Protectiveatmospheresapplications
Composition(vol%)
Atmosphere

Lean
exothermic
N
2

86.8

CO
2

10.5
CO

1.5
H
2

1.2
CH
4

Dewpoint

4.5
Applications.

Bright
annealingof
Cu,sintering
offerrites
Rich
exothermic
71.5 5.0 10.5 12.5 5 10 Bright
annealing
lowCsteel,
silicon
steels/Cu
brazing,
sintering
Dissociated
NH
3

25 75 50to+60 Brazing
sintering
bright
annealing
Endothermic 4045 00.5 20 3440 0.51 10to+10 Hardening,
carburizing
withCH
4
,
sintering
brazing
Nitrogen

H
2

99.9 99.9 60

68
Naturalfor
annealing

Reducing,
sintering
ArorHe:Thesearepureandinertgasesandareusedtopreventoxidationduringweldingof
stainlesssteel,aluminumetc.andheattreatmentofspecialsteels.

Atmospherevolumerequirements
Itdependson
i) Typeandsizeoffurnace
ft.
es.
ed.
xit.
ii) Environmentandpresenceofdra
iii) Thenatureandsizeofworkpiec
iv) Metallurgicalprocessinvolv
v) Presenceorabsenceofcurtainsatentranceande
Atmosphericsensors
Itisimportanttomeasuretheconcentrationofvariouscomponentsoftheatmosphereduringthe
treatmentinthefurnace.TheconstituentsofatmosphereareCO,CO
2
,H
2
,H
2
O,N
2
andhydrocarbon
gasessuchasCH
4
.Themainobjectiveoffurnaceatmosphereistopreventdecarburization,hydrogen
embrittlement,oxidation,surfaceblueingandsootformation.
ORSATanalysiscanbeusedtodeterminethecompositionofO
2
,COandCO
2
.ORSATanalysisis
describedinlecture10.
Amongothertechniquesgaschromatography,thermalconductivity,oxygensensors,dewpointarealso
used.Detailsaboutthesensorscanbeobtainedinreferencesgivenattheendofthelecture.

References:
Y.V.Deshmukh:industrialheating.2004.
Furnaceatmospheresandcarboncontrol:ASMCommitteeonfurnaceatmospheres