Module 23

Iron Carbon System I

Lecture 23

Iron Carbon System I

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Keywords:Ferrite(),Austenite(),Ferrite(d):threedifferentformsofiron,solubilityofcarbonin
differentformsofiron,cementite,graphite,FeFe3Cmetastablephasediagram,pearlite,ledeburite,
hypoeutectoidsteel,hypereutectoidsteel,hypoeutecticwhitecastiron,hypereutecticwhitecast
iron

Introduction

The last five modules were devoted to the solidification behavior of binary alloys. This is best
representedbyitsphasediagram.Wearenowfamiliarwithawiderangeofsimpleandcomplexphase
diagrams.Howeverwhileintroducingthisweonlyconsideredhypotheticalcases.Nowletusconsidera
specificbinaryalloyofconsiderableimportance.Wearegoingtotalkaboutironcarbonsystem.Iron
canexistintwodifferentcrystallineforms.TheseareBCCandFCC.Thisisknownasallotropy.Carbon
toohasseveralallotropicforms.Howevertheformwhichisofrelevancetothissystemisgraphite.Ithas
ahexagonalstructure.Thisisconsideredtobethemoststablestateofcarbon.Anatomofcarbonatom
issignificantlysmallerthanthatofiron.Thereforeitcanbeaccommodatedwithintheinterstitialsitesof
ironlatticeresultinginaninterstitialsolidsolution.Solubilitycarbonislikelytobelimited.Apartfrom
thisironhasastrongaffinitytoformcarbide.Themostcommonformiscementite.Itschemicalformula
isFe3C.Thisistrulyametastable.HowevertherateofdecompositionofFe3CintoFeandCisextremely
slow.Inmostofthecommongradesironcarbonalloyexcesscarbonispresentascementite.Letus
firstlookattheFeFe3Cmetastablephasediagramandinalatermoduleweshalldiscussaboutiron
graphitephasediagramaswell.Thealloysbelongingtothissystemispopularlyknownassteelorcast
iron.Wewouldsoonlearnaboutthedifferencebetweenthetwo.

Solidificationofpureiron:

Fe : crystal structure
T
Liquid Solubility of carbon in Fe =
1539 f(structure, temperature)
BCC
1394
FCC
Where is the carbon Slide1
910 located in iron lattice?
Paramagnetic BCC
770
Ferromagnetic

2 time

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 The sketch in slide 1 is a typical cooling curve of pure iron. Solidification begins with nucleation and
growth of crystals ofironat1539C. ItisBCC (bodycenteredcubic).At1394C ittransformsintoFCC
(facecenteredcubic)structure.Thisisstabletill910CwhereitagaintransformsintoBCC.Eachofthese
transformationsappearsasstepsonthecoolingcurve.Apartfromthisthereisanothertransformation
which may not get detected by thermal analysis. This is the transformation from paramagnetic to
ferromagneticstate.Itoccursat 770C. This isknownasitsCurie temperature.Theproperty which is
most sensitive to detect it, is magnetic permeability. The three different forms of iron are known as
ferrite(),stableuntil910C,austenite(),stablefrom9101394Candferrite(),stablefrom1394
1539C.NotethattheBCCformofironisknownasferrite.Thereforeinordertodistinguishbetween
thetwo,thehightemperatureformistermedasdeltaferrite.Ifcarbonatomsareintroducedintoiron
thesearelikelytooccupytheinterstitialsitesbecausetheatomscarbonaremuchsmallerthanthoseof
ironatoms.TheinterstitialsitesinBCCandFCCareshowninslide2.Thesolubilityofcarboninironisa
functionoftemperatureandcrystalstructure.

SolubilityofcarbonishigherinBCCorFCC?

Interstitial sites in iron lattice

c c

Slide2

b b

a a FCC
BCC
Lattice site
Interstitial site

Slide2showsthelatticesitesoccupiedbyironatomsandpossibleinterstitialsitesforcarbonatomsin
bothBCC&FCCstructures.Theinterstitialsitesshownhereareknownasoctahedralsites.Thesketches
inslide2showonlythepositionsofironatomsandtheinterstitialsitesinoneunitcell.Thesiteslocated
withinthecellbelongexclusivelytoaunitcellsbutthoselyingonthefaces,theedgesorthecornersare
3
sharedbytheneighboringunitcellsaswell.BCChaseightcornersitesforironatoms.Eachoftheseis
sharedby8neighboringunitcells.Thecontributionofcornersiteisthus1/8.Theatomatthecentre
belongsexclusivelytothisunitcell.Thereforethenumberofironatoms/unitcell=8x(1/8)+1=2.Let

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 ususethesameapproachtoestimatethenumberofinterstitialsites/unitcellforBCCstructure.The
sketchinslide2showsthelocationsofinterstitialsites.Thereare6sitesatthecentersof6faces.Each
faceissharedbytwounitcells.Thereare12sitesateachofthe12edges.Eachoftheseissharedby4
neighboringcells.Thereforethenumberofinterstitialsites/unitcellinBCCcrystal=12x(1/4)+6x
(1/2)=6.Notethatitis3timesthenumberofFeatomsinaunitcell.LookatthesketchforFCCunitcell
inslide2.Countthenumberoflatticesites.FollowthesameapproachtoshowthatthenumberofFe
atoms/unitcell=6x(1/2)+8x(1/8)=4.Inthesamewaythenumberofinterstitialsites/unitcellin
FCCstructure=1+12x(1/4)=4.NotethatinFCCstructuretheratioofthenumberofinterstitialsiteto
thenumberoflatticesites=1.Nowthatweknowaboutthepossiblesitescarbonatomscouldoccupy
isitpossibletoguesswhichoftheseislikelytohavehighersolubility?

D C
F
O
A B D
Fig1
A O C
E
B

E
(a) (b)

Fig. 1(a): Shows the lattice and the interstitial sites in a BCCunit cell. Circles are the lattice sites. The
black dots are the interstitial sites. In a lattice several of such cells are stacked one after the other. F
representsthebodycentersiteinaunitcelljustabovetheoneshowninthesketch.ThefigureABCDEF
formedbyjoiningthelatticesitesasillustratedisanoctahedron.Thereisaninterstitialsiteatitscenter
marked as O. All the interstitial sites are identical. Note that AB = BC = CD = DA = = the lattice
parameter.TheotheredgesoftheoctahedronAE=BE=CE=DE=AF=BF=CF=DF= 3/2.Itisnota
regularoctahedron.TheinterstitialsiteinBCCstructureisnotsymmetrical.ThegapalongEFisshorter
than that along AC or DB. It is 2 3 /2. The lattice parameter of BCC iron called ferrite is
0.286nm.Theshortestgapisequalto0.038nm.

Fig. 1(b): Shows the lattice and the interstitial sites in a FCC unit cell. Circles are the lattice sites. The
blackdotsaretheinterstitialsites.Inalatticeseveralofsuchcellsarestackedoneaftertheother.The
figureABCDEFformedbyjoiningthelatticesitesasillustratedisanoctahedron.Thereisaninterstitial
siteatitscentermarkedasO.Alltheinterstitialsitesareidentical.NotethatAB=BC=CD=DA=AE=

BE=CE=DE=AF=BF=CF=DF= ,where =thelatticeparameter.Itisaregularoctahedron.The
4 interstitial site in FCC structure is symmetrical. The gap along EF is equal to that along AC or DB. It
is 2 2 /2.ThelatticeparameterofFCCironcalledausteniteis0.362nm.Theinterstitialgapis
equalto0.106nm.Itismuchlargerthantheinterstitialgapinferrite.

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 FCChashigherpackingdensitythanBCC.YetthesolubilityofcarbonisFCCishigher.Thisisbecausethe
interstitial sites in FCC are bigger than that in BCC. There are two types of interstitial sites known as
octahedralandtetrahedral.InFCCthetetrahedralsitesaresurroundedbyfourclosepackedatoms.The
gapisextremelysmall,whereasinBCCthefouratomsaremorewidelyspaced.Thetetrahedronisnot
symmetric.Theshortestdimension(size)oftetrahedralsitesinBCClatticewasderivedinmodule5.This
isnearlysameormarginallylower(0.036nm)thanthatoftheoctahedralsite(0.038nm).Thenumberof
suchsitesismuchmorethanthatoftheoctahedralsites.AlthoughthepackingdensityinBCCislower
than that of FCC, the gaps are equally distributed between two types of interstices making these
significantlysmallerthanthatofFCC.Thisiswhythesolubilityofcarbonwhichisaninterstitialsoluteis
significantlylowerinferrite(BCC)thanthatinaustenite(FCC).ApartfromthistheinterstitialsiteinBCC
is asymmetric. When a carbon atom goes into the interstices the atoms along one of the axes are
pushed further apart. This results in a tetragonal distortion. We shall talk about it in one of the
subsequentmodules.

Phasesinironcarbonbinarysystem:

Ironcanexistinthreedifferentcrystallineformseachhavinglimitedsolubilityofcarbon.Thestabilityof
thesedependsontemperatureandcomposition.Thetwohightemperatureformsofironareferrite
which is BCC (stable above 1394C) and austenite (stable above 910C) which is FCC. The room
temperature form of iron is ferrite which is BCC. The solubility of carbon in ferrite is limited. The
maximum solubility is around 0.025wt% as against this the solubility of carbon in austenite is a little
more. It is about 2wt%. Apart from this iron carbon system may have iron carbide (Fe3C) called
cementite.It has6.67% carbon. Itisconsidered as anintermetalliccompoundhavingrelatively more
complexcrystalstructurethanthoseofferriteandaustenite.Itisametastablephase.Itmayexistfor
indefiniteperiodsoftimeatroomtemperature.Howeveronprolongedthermalexposureat600Cor
beyondittransformsintoferriteandgraphite.Thereforeironcarbonalloysofcommercialimportance
maybeconsideredasabinaryalloyofironandcementite.Letusfirstlookatitsphasediagram.Itis
also known as iron cementite metastable phase diagram. Although it is a binary system there are 5
differentphasesincludingtheliquid.Thisislikelytohavemorethanoneinvariantreactioninvolving3
phases.

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 Iron cementite phase diagram
1539 +L Peritectic
isotherm L
Eutectic
1394
+ isotherm
+L L + Cm
1148

910 Hypoeutectic Hyper-eutectic

Slide3
+ Cm

727
Eutectoid
Hypo Hyper isotherm
eutectoid eutectoid
0 0.8 2.0 %C 4.3 6.67

Slide3givesaschematicFeFe3Cphasediagram.Ithas3invariantreactions(transformation).Theseare
giveninslide4.Theoneoccurringat1495Cistheperitecticreaction.Thedeltaferritereactswithliquid
toformaustenite.Theoneat1148Cisknownastheeutecticreactionwheretheliquidtransformsinto
amixtureofausteniteandcementite.TheeutecticisknownasLedeburite.Theoneat727Cisknownas
eutectoidtransformationwhereaustenitedecomposesintoamixtureofferriteandcementite.Thisis
knownasPearlite. Onthe basis ofthis diagramiron carbon alloyshavinglessthan2.0%carbonare
knownassteel,whereasthosehavingmorethan2.0%carbonareknownascastiron.Thisclassification
isbasedontheirabilitytoundergolargeplasticdeformation.Steelisductilebutcastironisbrittle.

Slide4

Steel:

It is an iron carbon alloy where most of the carbon is present as metastable iron carbide called
cementite.Theupperlimitofcarboncontentis2%.Phasediagramhelpsusguessthestructureofalloys
6 and their properties. Let us look at what kinds of structure steel could have depending on its
composition.Wewouldonlyconsiderthestructurethatdevelopsunderequilibriumrateofcooling.The
steel on solidification is expected to have fully austenitic structure. It may be assumed to be

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 homogeneoussincetherateofcoolingisconsideredtobeslow.Dependingonitscompositionwemay
have3typesofstructures.(i)%carbon<0.02(ii)0.02<%carbon<0.8(iii)0.8<%Carbon<2.0.
L

1539
L
L+

+L L
1495
1394
+L
TC T Fig2

910
+Cm
727

+Cm
+Cm
0 0.02 0.8 2.0 Wt%C time

(i) Figure2explainsthesolidificationbehaviorofsteelhavinglessthan0.02%carbonwiththe
helpofasetofschematicdiagrams.Thesketchontheleftshowsapartoftheequilibrium
diagram (FeFe3C) with the location of the alloy by a vertical dotted line. It intersects the
liquidus, solidus, and a set of solvus curves. These are projected on to the cooling curve
shown on the right with the help of a set of horizontal lines. The cooling curve exhibits
inflectionpointsateachoftheseintersections.Solidificationbeginswithprecipitationofa
few grains of ferrite. The top most microstructure corresponds to this stage. The
solidificationtakesplacebynucleationandgrowth. Thecompositionofthe liquid andthe
solid keeps changing during this stage. When solidification is complete the entire liquid is
replacedbyferritehavingthesamecompositionasthatofthealloy.Thisisshownbythe
secondschematicstructurefromthetopinFig2.Thestructureremainsunchangeduntilthe
temperature crosses the boundary between / phase fields. Thereafter austenite
precipitatesfromferrite.Thegraincornersandboundariesarethepreferredsiteswhere
grains of austenite nucleate. The third microstructure from the top in Fig 2 represents its
mainfeatures.Itconsistsofgrainsof(white)andafewgrainsof(grey).Thereispartition
of carbon between these two phases. Bulk of the carbon goes into austenite. The
compositionofthetwokeepschangingasthetemperaturedrops.Thevolumefractionof
increasesatthecostof.Whenthe%carboninaustenitebecomesequaltothatofthesteel
ferritedisappears.Thestructurenowconsistsof100%austenite.Notethemainfeatures
ofthefourthmicrostructurefromthetopinFig2.Thegrainsizeisfinerthanthatof100%
7
ferrite.Thestructureremainsas100%austeniteuntilthetemperaturedropsbelowtheline
representing the boundary between and phase fields of the equilibrium diagram.
This is where ferrite starts precipitating from austenite. The grain boundaries and the

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 graincornersarethepreferredsitesforprecipitation.ThefifthsketchfromthetopofFig2
is a typical representation of its microstructure at this stage. Ferrite grains are shown as
white and austenite grains are shown as grey. This continues through nucleation of new
grainsandgrowthoftheexistingonesuntilthetemperaturedropsbelowthelinebetween
andphasefieldsofthephasediagram.Atthisstagethestructureis100%ferrite().
The 6th sketch in Fig 2 is a typical representation of the microstructure. This remains
unchanged till the temperature drops below the solvus. At this stage excess carbon
precipitates as cementite. The last sketch in Fig 2 is a typical representation of its
microstructure.Theamountofcementitekeepsincreasingastheroomtemperaturedrops.
Itcanbeestimatedbyleverrule.Fromthephasediagramitisevidentthatthesteelatroom
temperaturewouldconsistofferritewithafewspecksofcementite.If%carboninthesteel
is 0.01 the amount of cementite is given by (0.01/6.67)x100 = 0.15%. The grains are
relativelyfinerthanthataftersolidification. L

1539
L
+L L L
1495

1394
+L
TC T
Fig3
910

+Cm
727

Pearlite
+Cm


0 0.02 0.8 2.0 Wt%C time

(ii) Figure3explainsthesolidificationbehaviorofsteelhavinggreaterthan0.02%carbonbut
lessthan0.8%carbonwiththehelpofasetofschematicdiagrams.Thesketchontheleft
showsapartoftheequilibriumdiagram(FeFe3C)withthelocationofthealloybyavertical
dottedline.Ithasaround0.18%carbon.Itintersectstheliquidusandasetoflinesdenoting
either phase field boundaries or isotherms representing 3 phase equilibrium. These are
projected on to the cooling curve shown on the right with the help of a set of horizontal
lines. The cooling curve exhibits inflection points or steps (discontinuity) at each of these
intersections.Solidificationbeginswiththeprecipitationofafewgrainsofferrite.Thefirst
microstructure from the top corresponds to this stage. Solidification takes place by the
nucleationofnewgrainsandthegrowthoftheexistingones.Thecompositionoftheliquid
and the solid keeps changing during this stage. When the temperature reaches 1495C
8
peritectic reaction sets in. This is an invariant reaction. The liquid having 0.55% carbon
reacts with ferrite having 0.08% carbon to form austenite () having 0.18% carbon. The
amount of is just enough to consume the remaining liquid. The alloy on solidification

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 consists of austenite () having 0.18% carbon. This is shown by the second schematic
structure from the top in Fig 3. The structure remains unchanged until the temperature
crossestheboundarybetween/phasefields.Thereafterferrite()precipitatesfrom
( austenite. The grain corners and boundaries are the preferred sites where grains of
ferrite nucleate. The ferriteprecipitating from austenite is known as proeutectoid ferrite.
The third microstructure from the top in Fig 3 represents its main features. It consists of
grainsofproeutectoid (white)andafew grains of(grey).There ispartitionof carbon
betweenthesetwophases.Bulkofthecarbongoesintoaustenite.Thecompositionofthe
two keeps changing as the temperature drops. The volume fraction of increases at the
cost of . When % carbon in austenite reaches 0.8% eutectoid reaction sets in. This is an
invariant reaction. As long as it continues the temperature remains constant. During this
stage both cementite and ferrite start precipitating from austenite at the same time. The
productisanintimatemixtureoftwophases.Itisknownaspearlite.Itconsistsofparallel
layers(plates)offerriteandcementite.Figure4givesaseriesofsketchesshowingvarious
stages involved in the formation of pearlite. When a cementite plate nucleates as in (Fig.
4(a)) at an austenite boundary it takes carbon from its neighboring area. This results in a
change in local carbon profile as shown in the sketch. Just beside cementite % C = 0.02
whereas at a distance far from this it approaches 0.8 % C (this is the composition of the
eutectoid).Whenthisbecomeslowenoughaferriteplatenucleates.Figure4(b)illustrates
this.Notethechangeincarbonconcentrationasafunctionofdistance.Figure4(c)shows
thearrangementofferritecementiteplatesinacolonyofpearlite.Thewidthofthetwois
approximately proportional to % ferrite and % cementite in eutectoid steel having 0.8%
carbon. Using lever rule % cementite in pearlite =100 x (0.80.025) / (6.670.025) = 12%
(approximately).Therefore%ferrite=88%.Theratioofthetwoisapproximatelyequalto
1:7. This means the width of the ferrite plate will be seven times the width of cementite
plate.Oncompletionoftheeutectoidreactionthestructureconsistsofproeutectoidferrite
and pearlite. Note the main features of the fourth microstructure from the top in Fig 3.
Whenthetemperaturedropsbelowtheeutectoidtemperature,excesscarbonfromferrite
()precipitatesascementite.Thisisknownastertiarycementite(Whythisiscalledtertiary
willbeclearfromsubsequentpartofthismodule).Howeverthechangeinstructurebelow
the eutectoid temperature is too little to detect. Steels having carbon within 0.02 0.8
consistofferriteandpaerlite.Theyareknownashypoeutectoidsteel.

6.67 6.67

%C %C
0.8 0.8 0.8 0.8
0.02 x 0.02 0.02 x 0.02
9 Fe3C Fe3C Ferrite

(a) Austenite (b) Austenite
boundary boundary Fig4

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Fe3C colony

(c) Austenite (d) Structure

boundary


Hyper-eutectoid steel (0.8-2.0% C)

1539 L L

1394 L+ L
(a)

910 Slide5

Cm
723

Cm
P

0 0.8 2.0 Time

Cm
%C

(iii) Slide5explainsthesolidificationbehaviorofsteelhavinggreaterthan0.8%carbonbutless
than 2.0% carbon with the help of a set of schematic diagrams. Such steels are known as
hypereutectoidsteel.Thesketchontheleftshowsapartoftheequilibriumdiagram(Fe
Fe3C)withthe location of thealloyas a verticaldottedline.Ithas around1.0% carbon.It
intersects the liquidus, solidus, solvus and the eutectoid reaction isotherm representing 3
phaseequilibrium.Theseareprojectedontothecoolingcurveshownontherightwiththe
help of a set of horizontal lines. The cooling curve exhibits inflection points or a step
(discontinuity) at each of these intersections. Solidification begins with precipitation of a
few grains of austenite. The top most microstructure corresponds to this stage. The
solidificationtakesplacebynucleationofnewgrainsandgrowthoftheexistingones.The
composition of the liquid and the solid keeps changing during this stage. When the
temperaturereachesthatofthesolidusthecompositionofthesolidbecomesequaltothat
of the steel. The alloy on solidification consists of 100% austenite () having 1.0% carbon
(say).Thisisshownbythesecondschematicstructurefromthetopinslide5.Thestructure
remainsunchangeduntilthetemperaturecrossesthesolvus,theboundarybetween/+
Cmphasefields.Atthisstagecementitestartsprecipitatingfromaustenite.Itgrowsatthe
costofaustenite.The%carboninaustenitekeepsdecreasingastheamountofcementite
increases.Thegrainboundaryisthemostfavoredsiteforprecipitation.Thefourthstructure
10
from the top in slide 5 gives a typical structure of steel at this stage. When % carbon in
austenitedecreasesto0.8%eutectoidreactionsetsin.Thisisaninvariantreaction.Aslong
as it continues the temperature remains constant. During this stage both cementite and

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 ferrite start precipitating from austenite at the same time. The product is an intimate
mixtureoftwophases.Itisknownaspearlite.Thedetailsaboutthepearliticstructureare
showninFig4.Cementiteisahardandbrittlephase.Thepresenceofacontinuousnetwork
of cementite makes steel extremely brittle. There are methods to avoid the formation of
suchanetworktomakeitsuitableforengineeringapplications.Weshalllearnaboutinone
ofthesubsequentmodules.

Estimationoftheamountofmicroconstituentsinsteelfromphasediagram:

Themicroconstituentsinsteelareferrite,austenite,cementiteandpearlite.Outoftheseaustenite
isnotstableatroomtemperature.Whenwelookatmicrostructuresofsteelwegetanideaabout
the distribution of various constituents. If the composition or % carbon in steel is known we can
estimatethevolumefraction(weightfraction)ofeachthelikelyconstituents.

L
T
(x) (y) 1145 Fig 5: Shows how to estimate the amounts of
910 microconstituents in steel at room temperature.
+Cm The phase diagram gives approximate % C for

727 variouspointsofinterest.Thesearedenotedasa,

+Cm b,c,d,&e.%Cinahypoeutectoidsteelisxand
thatinhypereutectoidsteelisy.
0
0.02 0.8 2.0 4.3 6.67
a b c d e

Figure5givestherelevantpartofFeFe3Cphasediagram.Forpracticalpurposewemayassumethatthe
solubility of carbon in ferrite is negligible. The general expressions for the amount of Pearlite (P),
Cementite(Cm),ProeutectoidFerrite&Totalferrite()inahypoeutectoidsteelhavingx%Careas
follows.

% 100 100
.

.
% 100 100
.

% 100 100
.

. .
% 100 100
.

This truly gives weight % of various constituents. When you look at the microstructure you get an
estimateofvolume%.Howeverifthedensityofthephasesareknownweight%canbeconvertedto
11 volume%.Inthecaseofsteelthedensityofferriteis7.87g/ccandthatofcementiteis7.662.Although
thedifferenceisnotmuchtheamountofCmseeninamicrostructure(volumefraction)willbealittle
morethanweightfractionobtainedfromtheleverrule.

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MicrostructureofFeFe3Ceutectic:

The slide 6explainsthe solidificationbehaviorofFeFe3Ceutectic. This isthebinaryironcarbonalloy

havingthelowestmeltingpoint.Itsolidifiesaseutecticat1148C.ItisknownasLedeburite.

Structure of eutectic (Ledeburite)

T L
T
cm Slide6

cm

a b c d e time
% in eutectic at TE = (de/ce) x100
% P in eutectic at RT = (de/be) x100

% carbon in the eutectic is 4.3. Solidification occurs at a constant temperature. Immediately after
solidificationthealloyconsistsofamixtureofausteniteandcementite.%austenite=100x(ed)/(ec)=
100 x (6.67 4.3)/(6.672.0) =52% (approx). The solubility of carbon in austenite decreases with
decreasingtemperature.Attheeutectoidtemperaturethesolubilityofcarboninausteniteisonly0.8%.
Thereforeasthealloycoolscementiteprecipitatesfromtheausteniteintheeutectic.%austentiteat
theeutectoidtemperature(justbeforethedecompositionofaustenitestarts)=100x(ed)/(eb)=
100x(6.674.3)/(6.670.8)=41%(approx).Whentheeutectoidreactionsetsintheaustenitehaving
0.8% carbon transform into pearlite. The eutectic after this transformation is known as transformed
Ledeburite.Itapproximatelyconsistsof41%Pearliteinamatrixofcementite.Figure6showsthemain
features of the eutectic that forms at 1148C. It is initially a mixture of cementite and austenite. On
coolingthe%cementiteincreasesandthecarboncontentofaustenitedecreasestillitreaches727C.
This is where the austenite having 0.8% carbon transforms into pearlite. Thereafter as per the phase
12
diagram%ferritewithinthepearliticregionwoulddecreaseassomecementitewouldprecipitateoutof
it.Thisisduetothedecreaseinthesolubilityofcarboninferritewithdecreasingtemperature.However
thechangeistoolittletobedetectedfromthemicrostructure.

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Cm Cm



Pearlite



Fig.6:Showsaschematicrepresentationofthe Fig.7: Shows thestructure oftheeutecticFeFe3C

eutecticconsistingofcementiteaswhitematrix atroomtemperature.Notethatvolumefractionof
andausteniteasgreyparticlesat1145C.Itis austenite has decreased and it has transformed

calledledeburite. intopearlite.Itiscalledtransformedledeburite.

Whitecastiron:

If%carbonisgreaterthan2.0butlessthan6.67theFeFe3Calloyisknownaswhitecastiron.Suchan
alloy can be easily cast into various shapes but it has poor ductility. The fracture surface has silvery
whiteluster.Thisiswhyitisknownaswhitecastiron.Onthebasisofitsmicrostructuretherearetwo
typesofwhitecastiron.Theseare(i)hypoeutecticwhitecastiron(2.0<%C<4.3)and(ii)hypereutectic
whitecastiron(4.3<%C<6.67).Cementite(Fe3C)isthehardestconstituentintheFeFe3Csystem.Its
hardness is of the order of 1000HV (Vickers Hardness Number). This is why it has excellent wear
resistance.Recallthatthe%carbideineutecticisaround60%.Hardmaterialsareknowntobebrittle.
Thereisnowonderthatwhitecastironhaspoorductility.Letuslookattheevolutionofmicrostructure
inhypo&hypereutecticwhitecastiron.Thishasbeenexplainedwiththehelpofasetofsketchesgiven
inFig89.

x
1539
+L L L
1495
1394 L+Cm L
+L
TC T +L Ledeburite Fig8

910
+Cm
Cm Transformed
727 Pearlite
Ledeburite
+Cm

+Cm

13
0 0.02 0.8 2.0 3.0 4.3 6.67 time

Wt%C

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 Figure 8describestheevolutionofthemicrostructureina hypoeutecticcast iron.Theverticaldotted
linemarkedxisthelocationofthealloywithrespecttotheFeFe3Cphasediagram.Thesketchonthe
right gives itscoolingcurve. Solidificationbegins withnucleation andgrowthofaustenitegrains.Asit
coolstheamountofausteniteincreasesatthecosttheliquid.Thecompositionoftheausteniteandthe
liquidkeepchanging.Attheeutectictemperaturethecompositionofliquidis4.3whereasthatofthe
austeniteis2.0.If%Cinthecastironis3.0,%austeniteatthistemperature=100x(4.33.0)/(4.32.0)=
57%.Thebalance43%isliquid.Oncoolingthisitsolidifiesasamixtureofausteniteandcementite.The
eutecticisknownasledeburite.Theaustenitethatformsbeforeeutectictransformationiscalledpro
eutectic austenite or primary austenite. On subsequent cooling, the volume fraction of cementite
increasesatthecostofaustenite.Attheeutectoidtemperaturetheprimaryausteniteandtheaustenite
in the eutectic transform into pearlite. The final structure would consist of relatively large nodule of
pearlite(originatingfromprimayaustenite)andafinedispersionoftinynodulesofpearlite(originating
fromtheausteniteintheeutectic)inamatrixofcementite.

x
1539
+L L L
1495 Cm
1394 L+Cm L
+L
TC T +L Ledeburite Fig9
Cm
910
+Cm
Cm
727 Cm Transformed
+Cm Ledeburite
+Cm

0 0.02 0.8 2.0 4.35.0 6.67 time

Wt%C

Figure9describestheevolutionofthemicrostructureinahypereutecticwhitecastiron.Thevertical
dottedlinemarkedxisthelocationofthealloywithrespecttotheFeFe3Cphasediagram.Thesketch
on the right gives its cooling curve. Solidification begins with nucleation and growth of primary (pro
eutectic)grainsofcementite.Asitcoolstheamountofcementiteincreasesatthecosttheliquid.Note
thatcementitehasafixedcomposition.Howeverthecompositionoftheliquidkeepschanging.Atthe
eutectic temperature the composition of liquid is 4.3. If %C in the cast iron is 5.0, %liquid at this
temperature=100x(6.675.0)/(6.674.3)=70%.Onfurthercoolingitsolidifiesasamixtureofaustenite
and cementite. The eutectic is known as ledeburite. The cementite that forms before eutectic
transformation is called proeutectic cementite or primary cementite. On subsequent cooling, the
14 volumefractionofcementiteincreasesatthecostofaustenitewithintheeutectic.Thecementitethat
formsduringthisstageiscalledsecondarycementite.Attheeutectoidtemperaturetheausteniteinthe
eutectictransformsintopearlite.Thefinalstructureconsistsofrelativelylargeprimarycementiteanda
finedispersionoftinynodulesofpearlite(originatingfromtheausteniteintheeutectic)inamatrixof
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 cementite. The eutectic in cast iron at room temperature is known as transformed ledeburite. The
cementitepresentinironcarbonsystemhasseveraldistinctmorphologies.Inhypereutecticwhitecast
iron has all of theses. Cementite precipitating from the liquid is called primary cementite, that
precipitating from austenite is called secondary cementite, and those precipitating from ferrite below
eutectoidtemperatureiscalled tertiary cementite. Apart fromthesecementite isalsopresent as thin
plateswithinnodulesofpearlite.

Summary:

InthislecturewehavelearnedFeFe3Cmetastablephasediagram.Itgivesagraphicalrepresentationof
thestabilityofdifferentphasesonemaycomeacrossinsuchasystemoverarangeoftemperature(0
1550C) and compositions (06.67%C). It has 3 invariant reactions. These are peritectic, eutectic and
eutectoid.Barringpureiron,cementiteandtheeutecticallalloysbelongingtothissystemdonothavea
definite melting point. We have learnt how to draw or guess the cooling curve of an alloy if its
compositionwereknown.Ithelpsinpredictingthetypeofstructurethatevolvesduringsolidification.
Iron carbonalloys having less than 2% carbon are known as steel whereas those having carbon more
than 2% but less than 6.67% are known as cast iron. At room temperature all iron carbon alloys are
madeofferriteandcementite.Howeverthedistributionandtheamountofthesemayvarywidely.On
thebasisofthedistributionofthetwophaseswecanhave3typesofsteelandtwotypesofcastiron.
Theseare(i)terminalsolid solution havingonlyferriteorat bestextremely small amounts of tertiary
carbides (ii) hypoeutectoid steel (iii) hypereutectoid steel (iv) hypo eutectic white cast iron and (v)
hyper eutectic white cast iron. How the structure evolves in these during solidification has been
explained with illustrations. The iron cementite phase diagram at the end of this lecture gives an
overviewofthestructuralfeaturesofeachofthe5typesofalloysbelongingtothissystem.However
whiletalkingabouttheevolutionofstructurewedoassumethatcoolingrateisslow.Thisindeedisa
major limitation of phase diagram. We have already seen the effect of nonequilibrium cooling on
segregation during liquid to solid transformation. In FeFe3C system we do have a eutectoid
transformationwheretheeffectofcoolingrateislikelytobemuchmoresevere.Weshalltalkaboutit
inasubsequentlecture.

Exercise:

1. FCCisamoreclosepackedstructureyetsolubilityofcarboninaustenitewhichisFCCishigher
thanthatinferritewhichisBCC.Whyitisso?
2. Sketch the microstructure of 0.2% C steel. Calculate %Pearlite % cementite, % proeutectoid
ferriteand%totalferrite.
3. Estimatetheratioofthewidthsofferriteandcementiteplatesinlamellarpearlite.
4. Sketchthetemperarturetimediagramduringtheheatingcycleofa0.8%Csteel.Usestandard
FeFe3Cphasediagram.
15 5. Estimate%CminLedeburitejustbeloweutecticandjustaboveeutectoidtemeratures.Whatis
itsstructureatroomtemperature?

Answer:
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 1. Thereare2typesofinterstitialsitesoctahedral&tetrahedral.InFCCtheformerissignificantly
largerthanthelatter.WhereasinBCCthesearenearlysame.Thetotalopenspaceissharedby
morenumberofsites.TherforeinterstitialgapinBCCismuchsmallerthanthatofFCC.Thisis
whycarbonwhichoccupiesinterstitialsitehashighersolubilityinaustenite(FCC).

2. Thestucturewouldconsistofproeutectoidferriteandpearlite.Assumesolubilityofcarbonin
.
ferrite is negligible. Refer to phase diagram to get % Pearlite in 0.2% carbon steel =
.
.
100 25 Balance 75% is proeutectoid ferrite. % Cementite = 100 3% and total
.
ferrite=97%.

3. Assumedensityofferriteandcementitetobesame(Notethatinrealitydensityofcementiteis
. .
alittlehigher thanthatof ferrite).%ferrite inpearlite= 100 88. Balance12% is
.
cementite.Thereforetheratioofthewidthsofthetwo=12/88.Thisisapproximatelyequalto
1:7.

4. 0.8%carboncorrespondstoaneutectoidsteel.Itwouldfirsttransformintoausteniteandthen
itstartsmeltingwhenthetemperaturereachesitssolidustemperature.Itbecomestotallyliquid
whentemperaturegoesbeyonditsliquidus.Shematicheatingcurveisasfollows:

liquid
L+

T

+cm:Pearlite

Time

. .
5. Assume%Cineutectic=4.3.%Cmjustbeloweutectictemperature= 100 49%and
. .
. .
just above eutectoid = 100 60%Between eutectic to eutectoid temperatures
. .
proeutectoid cementite precipitates from austenite in eutectic. On subsequent cooling the
austenitetransformsintopearlite.Atroomtemperatutrewhatwehaveistransformedeutectic.

16

NPTELPhaseII:IITKharagpur:Prof.R.N.Ghosh,DeptofMetallurgicalandMaterialsEngineering|||
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 IronCementiteMetastableBinaryPhasediagram

0.08 1550
1539 +L=
L
+L 0.55

1495
1394 0.18 L=+Cm
L+Cm
+L
TC

1146
910
=+Cm

+Cm +Cm+LD Cm+LD
727 727

+Cm+P Cm+P P+TLD+Cm Cm+TLD

+Cm Hypoeutectoid Hypereutectoid Hypoeutectic Hypereutectic
steel steel whitecastiron whitecastiron

0 0.02 0.8 2.0 4.3 6.67

Fe Cm
Wt%C

Theabovesketchisalittleenlargedversionofthephasediagram.Fe&Fe3C(alsoknownascementite)
are the two components. Nomenclature: P denotes Pearlite the product of eutectoid reaction in iron
carbonsystem.Itisamixtureofferriteandcementite.Ferrite=,=austenite,=hightemperature
ferrite, LD = Ledebutite: the product of the eutectic reaction. Note that austenite can form either by
peritecticreactionbetween &L andalsobydirectprecipitationfromliquidwhen%C>0.55.TLD=
transformed Ledeburite. Ledeburite is a eutectic mixture of austenite and cementite. At room
temperatureausteniteisnotstable.IttransformsintoPearlite.TLDthereforeconsistsoftinynodulesof
pearliteincementitematrix.Italsodescribesthemainstructuralfeaturesoffivetypesofironcarbon
alloys.Lowcarbonsteelconsistsofferriteandtertiarycementite.Hypoeutectoidsteelhasferrite,pro
eutectoid cememtite andpearlite. Hypereutectoid steelhasproeutectoidcementite(secondary) and
pearlite. Hypoeutectic cast iron has pearlite, transformed ledeburite and proeutectoid (secondary)
cementite.Hypereutecticcastironhasprimarycementiteandtransformedledeburite.Sofarevolution
ofmicrostructurethattakesplaceduringsolidificationofironcarbonalloyshasbeenexplainedwith
thehelpofschematicmicrostructure.Thefollowingpagegivesafewtypicalmicrostructuresofsteeland
17 castiron.ThesewerepreparedbysomeofmystudentsandcolleaguesatIITKharagpurandCSIRNML
Jamshedpur.

NPTELPhaseII:IITKharagpur:Prof.R.N.Ghosh,DeptofMetallurgicalandMaterialsEngineering|||
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 Typicalmicrostructuresofsteelandcastiron

Fig A1: Microstructure of 0.15% carbon steel Fig A2: Microstructure of medium carbon steel
consisting of ferrite (bright) and pearlite (dark). consisting of ferrite (bright) and pearlite (dark).
Lamellar feature pearlite is not visible. (Curtsey G Amount of pearlite increases with % carbon.
DasCSIRNMLJamshedpur) (CurtseyGDasCSIRNMLJamshedpur).

Fig A3: Microstructure of a near eutectoid steel FigA4:SEMimageof0.84%Csteelhavingnearly

havingalittleproeutectoidcementiteinamatrix 100% pearlite. Lamellar feature is clearly visible.
of pearlite. In some of regions finer details of The dark region is proeutectoid cementite.
pearlitic(lamellar)structureisvisible. (CurtseyGDasCSIRNMLJamshedpur)

18
FigA5:Microstructureofhypereutecticwhitecast Fig A6: Microstructure of grey cast iron having
ironshowingprimarycarbides(cm).Therestofthe graphite flakes in a matrix consisting of mostly
region consists of a mixture of pearlite and ferrite and some amount of pearlite. (Curtsey G
cementiteortransformedeutectic(ledeburite). DasCSIRNMLJamshedpur)
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