(TTT)Diagrams
R. Manna
Assistant Professor
Centre of Advanced Study
Department of Metallurgical Engineering
Institute of Technology, Banaras Hindu University
Varanasi-221 005, India
rmanna.met@itbhu.ac.in
TataSteelTRAERFFacultyFellowshipVisitingScholar
DepartmentofMaterialsScienceandMetallurgy
UniversityofCambridge,PembrokeStreet,Cambridge,CB23QZ
rm659@cam.ac.uk
TTTdiagrams
TTTdiagramstandsfortimetemperaturetransformationdiagram.Itis
alsocalledisothermaltransformationdiagram
Definition:TTTdiagramsgivethekineticsofisothermal
transformations.
DeterminationofTTTdiagramforeutectoidsteel
DavenportandBainwerethefirsttodeveloptheTTTdiagram
of eutectoid steel. They determined pearlite and bainite
portions whereas Cohen later modified and included MS and
MFtemperaturesformartensite.Therearenumberofmethods
usedtodetermineTTTdiagrams.Thesearesaltbath(Figs.1
2) techniques combined with metallography and hardness
measurement,dilatometry (Fig. 3),
electricalresistivity
method, magnetic permeability, in situ diffraction techniques
(Xray, neutron), acoustic emission, thermal measurement
techniques, density measurement techniques and
thermodynamic predictions. Salt bath technique combined
with metallography and hardness measurements is the most
popularandaccuratemethodtodetermineTTTdiagram.
3
Fig.1:SaltbathIaustenitisation
heattreatment.
Fig.2:BathIIlowtemperature
saltbathforisothermaltreatment.
Fig.3(a):Sampleand
fixturesfordilatometric
measurements
Fig.3(b):Dilatometer
equipment
In molten salt bath technique two salt baths and one water
bath are used. Salt bath I (Fig. 1) is maintained at
austenetisingtemperature(780Cforeutectoidsteel).Saltbath
II (Fig. 2) is maintained at specified temperature at which
transformationistobedetermined(belowAe1),typically700
250Cforeutectoidsteel.BathIIIwhichisacoldwaterbath
ismaintainedatroomtemperature.
In bath I number of samples are austenitised at A C1+2040C
for eutectoid and hypereutectoid steel, AC3+2040C for
hypoeutectoid steels for about an hour. Then samples are
removedfrombathIandputinbathIIandeachoneiskeptfor
different specified period of time say t1, t2, t3, t4, tn etc. After
specified times, the samples are removed and quenched in
water. The microstructure of each sample is studied using
metallographic techniques. The type, as well as quantity of
phases,isdeterminedoneachsample.
6
100
AtT1,incubation
periodforpearlite=t2,
Pearlitefinishtime
=t4
Ae1
earlite
p
+
t
r
te
i
a
n
t
s
te
e
Aus
n
Pearlit
ati o
m
r
n i sh
sfo
rlitefi
n
a
e
a
P
r
T
50%
t3
t4
t
T2
T1
t0
t1 t2
Au
s
tas
Me
ten
te
eni
ust
le a
tab
Temperature
T2
T1
50%
ite
+u
p
CoarsePearlite
Pearlite
Finepearlite
50%veryfinepearlite+50%upperbainite
pe
rb
ain
i
Bai
te
n it e
Au
st
en
sta
rt
Ba
i ni
ite
Upperbainite
te
f
+lo
w
in i
sh
er
b
ai n
MS,Martensitestarttemperature
ite
Lowerbainite
Minimumincubation
periodt0atthenose
oftheTTTdiagram,
Hardness
%ofPhase
Fig.4:Timetemperaturetransformation(schematic)diagramforplaincarbon
eutectoidsteel
MS=Martensite
starttemperature
M50=temperature
for50%
martensite
formation
MF=martensite
finishtemperature
M50,50%Martensite
MF,Martensitefinishtemperature
Metastableaustenite+martensite
Martensite
Logtime
AtclosetoAe1temperature,coarsepearliteformsatcloseto
Ae1temperatureduetolowdrivingforceornucleationrate.
Athigherundercoolingsorlowertemperaturefinerpearlite
forms.
AtthenoseofTTTdiagramveryfinepearliteforms
Closetotheeutectoidtemperature,theundercoolingislowso
thatthedrivingforceforthetransformationissmall.However,
astheundercoolingincreasestransformationacceleratesuntil
the maximum rate is obtained at the nose of the curve.
Below this temperature the driving force for transformation
continuestoincreasebutthereactionisnowimpededbyslow
diffusion. This is why TTT curve takes on a C shape with
most rapid overall transformation at some intermediate
temperature.
10
Pearlitictransformationisreconstructive.Atagiventemperature(say
T1) the transformation starts after an incubation period (t 2, at T1).
Locus of t2 for different for different temperature is called
transformationstartline.After50%transformationlocusofthattime
(t3 at T1)for different temperatures is called 50% transformation line.
While transformation completes that time (t4 at T1) is called
transformationfinish,locusofthatiscalledtransformationfinishline.
Therefore TTT diagram consists of different isopercentage lines of
which 1%, 50% and 99% transformation lines are shown in the
diagram. At high temperature while underlooling is low form coarse
pearlite.Atthenosetemperaturefinepearliteandupperbainiteform
simultaneouslythoughthemechanismsoftheirformationareentirely
different. The nose is the result of superimposition of two
transformation noses that can be shown schematically as below one
forpearliticreactionotherforbainiticreaction(Fig.6).
Upper bainite forms at high temperature close to the nose of TTT
diagramwhilethelowerbainiteformsatlowertemperaturebutabove
11
MStemperature.
Fig.5(a):Theappearanceofa(coarse)pearlitic
microstructureunderopticalmicroscope.
12
Fig.5(c):Opticalmicrographshowingcolonies
ofpearlite.CourtesyofS.S.Babu.
14
Fig.5(d):Transmissionelectronmicrograph
ofextremelyfinepearlite.
15
Fig.5(e):Opticalmicrographofextremely
finepearlitefromthesamesampleasusedto
createFig.5(d).Theindividuallamellae
cannotnowberesolved.
16
Ae1
Metastable
+P
CP
P
FP
50%veryFP+50%UB
UB
M
UB
eta
st a
bl
e
MS
M50
MF
LB
Hardness
Temperature
Fig.6:TimeTemperatureTransformation(schematic)diagramforplaincarbon
eutectoidsteel
=austenite
=ferrite
CP=coarsepearlite
P=pearlite
FP=finepearlite
UB=upperbainite
LB=lowerbainite
M=martensite
MS=Martensitestart
temperature
M50=temperaturefor
50%martensite
formation
MF=martensitefinish
temperature
LB
Metastable+M
Logtime
17
18
TTTdiagramgives
Natureoftransformationisothermalorathermal(time
independent)ormixed
Typeoftransformationreconstructive,ordisplacive
Rateoftransformation
Stabilityofphasesunderisothermaltransformationconditions
Temperatureortimerequiredtostartorfinishtransformation
Qualitativeinformationaboutsizescaleofproduct
Hardnessoftransformedproducts
19
FactorsaffectingTTTdiagram
Compositionofsteel
(a)carbonwt%,
(b)alloyingelementwt%
Grainsizeofaustenite
Heterogeneityofaustenite
Carbonwt%
21
Ae3
+
Ae1
t0
+P
FP+UB
+CP
+P
FP
UB
Metastable
MS
M50
MF
Hardness
Temperature
Fig.7(a):SchematicTTTdiagramforplaincarbonhypoeutectoidsteel
=austenite
=ferrite
CP=coarsepearlite
P=pearlite
FP=finepearlite
UB=upperBainite
LB=lowerBainite
M=martensite
MS=Martensitestart
temperature
M50=temperaturefor
50%martensite
formation
MF=martensitefinish
temperature
LB
Metastable+M
M
Logtime
22
Aecm
+Fe3C
Ae1
t0
+P
+
UB
veryFP+UB
Fe3C+CP
Fe3C+P
Fe3C+FP
UB
Metastable
+
LB
MS
M50
Metastable + M
Logtime
Hardness
Temperature
Fig.7(b):SchematicTTTdiagramforplaincarbonhypereutectoid
steel
=austenite
CP=coarsepearlite
P=pearlite
FP=finepearlite
UB=upperBainite
LB=lowerBainite
M=martensite
MS=Martensitestart
temperature
M50=temperaturefor
50%martensite
formation
LB
23
Fig.8:SchematicFeFe3Cmetastableequilibriumdiagram
andTTTdiagramsforplaincarbonhypoeutectoid,eutectoid
andhypereutectoidsteels
=austenite
=ferrite
CP=coarse
pearlite
(a)FeFe3C
metastablephase
diagram
MS
P=pearlite
FP=finepearlite
UB=upperbainite
LB=lowerbainite
(b)TTTdiagramfor
hypoeutectoidsteel
M=martensite
MS=Martensitestarttemperature
M50=temperaturefor50%martensite
formation
MF=martensitefinishtemperature
(c)TTTdiagram
foreutectoidsteel
(d)TTTdiagramfor
hypereutectoidsteel
24
Ae1
CmW
0.77
Cm
Austenite
Ae3
0.0218
A ec
Temperature
Pearlite
Upperbainite
MF
Lowerbainite
MS
Mixmartensite
Lathmartensite
Platemartensite
Weight % carbon
Fig9:Temperatureversuscompositioninwhichvariousmorphologies
aredominantatlatereactiontimeunderisothermalcondition
W=Widmansttte
nplate
M=massive
P=pearlite
ub=upperbainite
lb=lowerbainite
Volume%ofretained
austeniteatroom
temperature
26
27
Fig.10:Thereconstructiveanddisplacivemechanisms.
28
Fig.11(a):schematicdiagramofgrainboundaryallotriomoph
ferrite,andintragranularidiomorphferrite.
29
Fig.11(b):Anallotriomorphofferriteinasamplewhichispartially
transformedintoandthenquenchedsothattheremaining
undergoesmartensitictransformation.Theallotriomorphgrows
rapidlyalongtheaustenitegrainboundary(whichisaneasydiffusion
30
path)butthickensmoreslowly.
Fig.11(c):AllotriomorphicferriteinaFe0.4Csteelwhichisslowlycooled;
theremainingdarketchingmicrostructureisfinepearlite.Notethatalthough
some particles might be identified as idiomorphs, they could represent
sectionsofallotriomorphs.MicrographcourtesyoftheDoITPOMSproject.
31
Fig.11(d):Theallotriomorphshaveinthisslowlycooledlowcarbonsteelhave
consumed most of the austenite before the remainder transforms into a small
amountofpearlite.MicrographcourtesyoftheDoItPomsproject.Theshapeof
theferriteisnowdeterminedbytheimpingementofparticleswhichgrowfrom
differentnucleationsites.
32
Fig.11(f):Massiveferrite(m)inFe0.002wt%Calloy
quenchedintoicebrinefrom1000C.CourtesyofT.B.
Massalski
34
Fig.12(a):SchematicillustrationofprimaryWidmansttten
ferritewhichoriginatesdirectlyfromtheaustenitegrain
surfaces,andsecondarywwhichgrowsfromallotriomorphs.
35
Fig.13:Thesimultaneousgrowthoftwoself
accommodatingplatesandtheconsequentialtentlike
surfacerelief.
37
Fig.14:Transmissionelectronmicrographofwhatopticallyappears
tobesingleplate,butisinfacttwomutuallyaccommodatingplates
withalowanglegrainboundaryseparatingthem.Fe0.41Calloy,
austenitisedat1200Cfor6hrs,isothermallytransformedat700C
for2minandwaterquenched.
38
Fig.15:Mixtureofallotriomorphicferrite,Widmanstttenferrite
andpearlite.MicrographcourtesyofDOITPOMSproject.
39
Fig17:Summaryofthemechanismofthebainitereaction.
42
Fig.18:Upperbainite;the
phasebetweentheplatelets
ofbainiticferriteisusually
cementite.
43
Fig.19:Transmissionelectronmicrographofasheafofupperbainitein
a partially transformed Fe0.43C2Si3Mn wt% alloy (a) optical
micrograph, (b, c) bright field and corresponding dark field image of
retained austenite between the sub units, (d) montage showing the
44
structureofthesheaf.
Fig.20:Correspondingoutlineofthesubunitsnearthesheaftip
regionofFig.19
45
Fig.21:AFMimageshowingsurfacereliefduetoindividualbainite
subunit which all belong to tip of sheaf. The surface relief is
associatedwithupperbainite(withoutanycarbide)formedat350C
for 2000 s in an Fe0.24C2.18Si2.32Mn1.05Ni (wt% ) alloy
austenitised at 1200C for 120 s alloy. Both austenitisation and
isothermal transformation were performed in vacuum. The
microstructure contains only bainitic ferrite and retained austenite.
46
Themeasuredshearstrainis0.260.02.
Fig.22:Opticalmicrographillustratingthesheavesoflowerbainitein
a partially transformed (395C), Fe0.3C4Cr wt% ally. The light
etching matrix phase is martensite. (b) Corresponding transmission
electronmicrographillustratingsubunitsoflowerbainite.
47
Fig.23:(a)Opticalmicrographshowingthinandspinylower
bainiteformedat190Cfor5hoursinanFe1.1wt%Csteel.(b)
Transmissionelectronmicrographshowinglowerbainitemidribin
samesteel.CourtesyofM.Oka
48
Fig.24:Schematicillustrationof
variousothermorphologies:(a)
Nodularbainite,(b)columnarbainite
alongapriorausteniteboundary,(c)
grainboundaryallotriomorphic
bainite,(d)inversebainite
49
Withinthebainitictransformationtemperaturerange,austeniteof
large grain size with high inclusion density promotes acicular
ferrite formation under isothermal transformation condition. The
morphologyisshownschematically(Figs.2527)
Fig.25:showsthemorphologyandnucleationsiteof
acicularferrite.
50
Fig.26:Acicularferrite
51
Fig.27:Replicatransmissionelectronmicrographof
acicularferrireplatesinsteelweld.CourtesyofBarritte.
52
53
Fig.28:EffectofcarbononMS,MFtemperaturesandretainedausteniteinplaincarbon
steel
Austenite
m
A ec
Ae3
Ae1
0.77
Ferrite+pearlite
Pearlite+cementite
Volume%ofretained
austeniteatroom
temperature
MS
MF
Lathmartensite
Mixmartensite
Weight % carbon
Platemartensite
0.0218
Austenite+cementite
Pearlite
Temperature
Ferrite
Ferrite+austenite
54
Fig.29:Morphologyandcrystallographyof(bccorbct)martensitein
ferrousalloys
Courtesyof
T.Maki
Lath
(Fe-9%Ni-0.15%C)
Lenticular
Thin plate
(Fe-29%Ni-0.26%C) (Fe-31%Ni-0.23%C)
Substructure
Dislocation
Dislocation
Twin (midrib)
Twin
Habit plane
{111}A
{557}A
{259}A
{3 10 15}A
{3 10 15}A
O.R.
K-S
N-W
G-T
G-T
Ms
high
low
55
Fig.30:Lathmartensite
Courtesyof
T.Maki
56
Fig.31:effectofcarbon
onmartensitelathsize
Packet: a group of laths
with the same habit plane
( ~{111} )
Block : a group of laths
with the same orientation
(the same K-S variant)
Lenticularmartensite
(Opticalmicrograph)
Courtesyof
T.Maki
Fig.32: Fe-29%Ni-0.26%C
(Ms=203K)
58
Fig.35:Growthbehavioroflenticularmartensite
inFe30.4%Ni0.4%Calloy
cooling
surface relief
surface relief
g
lin
o
co
surface relief
Courtesyof
T.Maki
Fig.36:LenticularmartensiteinFe33%Nialloy
(Ms=171K)
Courtesyof
T.Maki
schematic illustration
Optical micrograph
midrib
twinned region
60
0.0026%C
0.18%C
0.38%C
0.61%C
Courtesyof
T.Maki
61
Courtesyof
T.Maki
Fig.39 : Orientation
image map
Alloying elements:
HoweverAl,Co,andSiincreaserateofnucleationandgrowth
of both ferrite or pearlite and therefore shift TTT diagram to
left. In addition under the complex diffusional effect of
variousalloyingelementthesimpleCshapebehaviourofTTT
diagram get modified and various regions of transformation
get clearly separated. There are separate pearlitic C curves,
ferritic and bainitic C curves and shape of each of them are
distinctanddifferent.
64
Theeffectofalloyingelementsislesspronouncedinbainitic
region as the diffusion of only carbon takes place (either to
neighbouringausteniteorwithinferrite)inaveryshorttime
(withinafewsecond)aftersupersaturatedferriteformationby
shearduringbainitictransformationandthereisnoneedfor
redistribution of mostly substitutional alloying elements.
Therefore bainitic region moves less to higher timing in
comparison to proeutectoid/pearlitic region. Addition of
alloyingelementsleadtoagreaterseparationofthereactions
and result separate Ccurves forpearlitic and bainitic regions
(Fig. 40). Mo encourage bainitic reaction but addition of
boron retard the ferrite reaction. By addition of B in low
carbon Mo steel the bainitic region (almost unaffected by
additionofB)canbeseparatedfromtheferriticregion.
65
Temperature
Fig.40:EffectofborononTTTdiagramoflowcarbonMosteel
Ae3
Ae1
FerriteCcurveinlow
carbonMosteel
Additionofboron
FerriteCcurveinlow
carbonMoBsteel
PearliticCcurveinlow
carbonMosteel
Additionofboron
PearliticCcurveinlow
carbonMoBsteel
Metastableaustenite
Bainitestart
Bainite
MS
Metastableaustenite+martensite
Logtime
66
AdditionofsignificantamountofNiandMncanchangethenatureof
martensitictransformationfromathermaltoisothermal(Fig.41).
Temperature
1%
%
30
Logtime
Fig.41:kineticsofisothermalmartensiteinanFeNiMnalloy
68
T= MS.a,barefittingempirialconstants,
m=averageaspectratioofmartensite=0.05assumed,V
=averagevolumeofaustenite.f=detectablefractionof
martensite=0.01(taken).
It is expected similar effect of grain size on M F as
on MS.
Grainsizeofausteniteaffectsthemaximumplateorlathsize.
i.e.largertheaustenitesizethegreaterthemaximumplatesize
orlathsize
70
Ae3
Ae1
+P
50%FP+50%
UB
+CP
+P
FP
UB
Metastable
MS
M50
MF
Hardness
Temperature,T
Fig.43:EffectofaustenitegrainsizeonTTTdiagramofplaincarbon
hypoeutectoidsteel
=austenite
=ferrite
CP=coarsepearlite
P=pearlite
FP=finepearlite
UB=upperBainite
LB=lowerBainite
M=martensite
MS=Martensitestart
temperature
M50=temperatureat
which50%martensite
isobtained
MF=martensitefinish
temperature
LB
Metastable+M
M
Log(time,t)
71
Heterogeinityofaustenite:Heterogenousausteniteincreases
transformation time range, start to finish of ferritic, pearlitic
and bainitic range as well as increases the transformation
temperature range in case of martensitic transformation and
bainitic transformation. Undissolved cementite, carbides act
as powerful inocculant for pearlite transformation.
Therefeore heterogeneity in austenite increases the
transformation time range in diffussional transformation and
temperature range of shear transformation products in TTT
diagram.
72
ApplicationsofTTTdiagrams
Martempering
Austempering
IsothermalAnnealing
Patenting
Martempering:Thisheattreatmentisgiventooilhardenable
andairhardenablesteelsandthinsectionofwaterhardenable
steel sample to produce martensite with minimal differential
thermal and transformation stress to avoid distortion and
cracking. The steel should have reasonable incubation period
at the nose of its TTT diagram and long bainitic bay. The
sample is quenched above MS temperature in a salt bath to
reduce thermal stress (instead of cooling below MF directly)
(Fig.44)
73
Surfacecoolingrateisgreaterthanatthecentre.Thecooling
schedule is such that the cooling curves pass behind without
touching the nose of the TTT diagram. The sample is
isothermallyholdatbainiticbaysuchthatdifferentialcooling
rate at centre and surface become equalise after some time.
ThesampleisallowedtocoolbyairthroughMSMFsuchthat
martensite forms both at the surface and centre at the same
time due to not much temperature difference and thereby
avoid transformation stress because of volume expansion.
The sample is given tempering treatment at suitable
temperature.
74
Ae3
Austenite+ferrite
Ae1
Centre
Surface
Temperature
Fig.44:MartemperingheatreatmentsuperimposedonTTTdiagram
forplaincarbonhypoeutectoidsteel
t0
+CP
+P
te
arli
e
P
te+
i
n
e
t
Aus
FP
50%FP+50%UB
UB
Metastable
Tempering
LB
MS
M50
MF
Metastable+martensite
Martensite
Logtime
=austenite
=ferrite
CP=coarsepearlite
P=pearlite
FP=finepearlite
t0=minimumincubation
period
UB=upperbainite
LB=lowerbainite
M=martensite
MS=Martensitestart
temperature
M50=temperatureatwhich
50%martensiteisobtained
MF=martensitefinish
temperature
Temperedmartensite
75
Austempering
Austempering heat treatment is given to steel to produce lower
bainiteinhighcarbonsteelwithoutanydistortionorcrackingto
thesample.Theheattreatmentiscoolingofausteniterapidlyina
bath maintained at lower bainitic temperature (above M s)
temperature(avoidingthenoseoftheTTTdiagram)andholding
itheretoequalisesurfaceandcentretemperature(Fig.45)and.
tillbainiticfinishtime.Attheendofbainiticreactionsampleis
aircooled.Themicrostructurecontainsfullylowerbainite.This
heattreatmentisgivento0.51.2wt%Csteelandlowalloysteel.
Theproducthardnessandstrengtharecomparabletohardened
and tempered martensite with improved ductility and toughness
and uniform mechanical properties. Products donot required to
betempered.
76
Ae3
Austenite+ferrite
Ae1
Centre
Surface
Temperature
Fig.45:AustemperingheatreatmentsuperimposedonTTTdiagram
forplaincarbonhypoeutectoidsteel
t0
+CP
+P
te
arli
e
P
te+
i
n
e
t
Aus
FP
50%FP+50%UB
UB
Metastable
Tempering
LB
MS
M50
MF
Metastable+martensite
Martensite
Logtime
=austenite
=ferrite
CP=coarsepearlite
P=pearlite
FP=finepearlite
t0=minimumincubation
period
UB=upperbainite
LB=lowerbainite
M=martensite
MS=Martensitestart
temperature
M50=temperatureatwhich
50%martensiteisobtained
MF=martensitefinish
temperature
Lowerbainite
77
Isothermalannealing
Isothermalannealingisgiventoplaincarbonandalloysteels
to produce uniform ferritic and pearlitic structures. The
product after austenising taken directly to the annealing
furnacemaintainedbelowlowercriticaltemperatureandhold
isothermallytillthepearliticreactioncompletes(Fig.46).The
initialcoolingoftheproductssuchthatthetemperatureatthe
centre and surface of the material reach the annealing
temperature before incubation period of ferrite. As the
products are hold at constant temperature i.e. constant
undercooling) the grain size of ferrite and interlamellar
spacing of pearlite are uniform. Control on cooling after the
endofpearlitereactionisnotessential.Theoverallcycletime
islowerthanthatrequiredbyfullannealing.
78
Ae3
Austenite+ferrite
Ae1
Centre
Surface
Temperature
Fig.46:IsothermalannealingheattreatmentsuperimposedonTTT
diagramofplaincarbonhypoeutectoidsteel
t0
+CP
+P
te
arli
e
P
te+
i
n
e
t
Aus
FP
50%FP+50%UB
UB
Metastable
LB
MS
M50
MF
Metastable+martensite
Martensite
Logtime
=austenite
=ferrite
CP=coarsepearlite
P=pearlite
FP=finepearlite
t0=minimumincubation
period
UB=upperbainite
LB=lowerbainite
M=martensite
MS=Martensitestart
temperature
M50=temperatureatwhich
50%martensiteisobtained
MF=martensitefinish
temperature
Ferriteandpearlite
79
Patenting
Patenting heat treatment is the isothermal annealing at the
nosetemperatureofTTTdiagram(Fig.47).Followedbythis
the products are air cooled. This treatment is to produce fine
pearlitic and upper bainitic structure for strong rope, spring
products containing carbon percentage 0.45 %C to 1.0%C.
The coiled ropes move through an austenitising furnace and
entersthesaltbathmaintainedat550C(nosetemperature)at
end of salt bath it get recoiled again. The speed of wire and
lengthoffurnaceandsaltbathsuchthattheaustenitisationget
overwhenthewirereachestotheendofthefurnaceandthe
residencyperiodinthebathisthetimespanatthenoseofthe
TTTdiagram.Attheendofsaltbathwireiscleanedbywater
jetandcoiled.
80
Temperature
Fig.47:PatentingheattreatmentsuperimposedonTTTdiagramof
plaincarbonhypoeutectoidsteel
Ae3
Austenite+ferrite
Ae1
t0
+CP
+P
te
arli
e
P
te+
i
n
e
t
Aus
FP
50%FP+50%UB
UB
Metastable
LB
MS
M50
MF
Metastable+martensite
Martensite
=austenite
=ferrite
CP=coarsepearlite
P=pearlite
FP=finepearlite
t0=minimumincubation
period
UB=upperbainite
LB=lowerbainite
M=martensite
MS=Martensitestart
temperature
M50=temperatureatwhich
50%martensiteisobtained
MF=martensitefinish
temperature
finepearliteandupperbainite
Logtime
81
Predictionmethods
TTTdiagramscanbepredictedbasedonthermodynamic
calculations.
MAP_STEEL_MUCG83program[transformationstart
curvesforreconstructiveanddisplacivetransformationsfor
lowalloysteels,Bhadeshiaetal.],wasusedforthefollowing
TTTcurveofFe0.4wt%C2wt%Mnalloy(Fig.48)
Fig.48:Calculated
transformationstartcurve
underisothermal
transformationcondition
82
ThebasisofcalculatingTTTdiagramforferroussytem
1.CalculationofAe3Temperaturebelowwhichferrite
formationbecomethermodynamicallypossible.
2.BainitestarttemperatureBSbelowwhichbainite
transformationoccurs.
3.MartensitestarttemperatureMSbelowwhichmartensite
transformationoccurs
4.AsetofCcurvesforreconstructive
transformation(allotriomorphicferriteandpearlite).
AsetofCcurvesfordisplacive
transformations(Widmanstttenferrite,bainite)
AsetofCcurvesforfractionaltransformation
5.Fractionofmartensiteasafunctionoftemperature
83
1.CalculationofAe3temperatureformulticomponent
system.[MethodadoptedbyBhadeshiaetal.]
(ThisanalysisisbasedonKirkaldyandBarganisandisapplicablefortotalalloying
elementsoflessthan6wt%andSiislessthan1wt%)
General procedure of determination of phase boundary
Assume T is the phase boundary temperature at which high
temperature phase L is in equilibrium with low temperature phase .
In case of pure iron then T is given by
forAe3temperature,low
temperaturephasetobe
substitutedbyandhigh
temperaturephaseLtobe
substitutedby)
Where Xo is the mole fraction of iron then
and0GL=standardGibbsfreeenergyofpurehightemperature
phaseand0G=StandardGibbsfreeenergyofpurelow
temperaturephase
Similarlyforcarbon(n=1)orcomponenti
TheWagnerTaylorexpansionfortheactivitycoefficients
aresubstitutedintheaboveequations.
85
TheWagnerTaylorexpansionsforactivitycoefficientsare
k=1to11inthiscase
Where=0(assumed)
aretheWagnerinteractionparametersi.e.interactionbetween
solutesarenegligible.ThesubstitutionofWagnerTaylor
expansionsforactivitycoefficientsgivestemperaturedeviation
Tforthephaseboundarytemperature(duetotheadditionof
substitutionalalloyingelements
86
Inmulticomponentsystem,thetemperaturedeviationsdueto
individualalloyingadditionsareadditiveaslongassolute
soluteinteractionsarenegligible.Kirkaldyandcoworkers
foundthatthisinteractionarenegiligibleaslongastotal
alloyingadditionsarelessthan6wt%andSiislessthan1wt
%].
EventuallyTtakesthefollowingform
87
Andwhere
forwhich
and
wheren=1oriandHoandH1arestandardmolar
enthalpychangescorrespondingtoGoandG1.
88
IftherelevantfreeenergychangesoGandtheinteraction
parametersareknownthenTcanbecalculatedforany
alloy.
Sinceallthethermodynamicfunctionsusedaredependenton
temperature, T cannotbeobtained fromsingleapplication
ofallvalues(usedfromvarioussources)butmustbededuced
iteratively.InitiallyTcanbesetasTo,Tiscalculated.Then
T=T+ T is used for T and T is found. Iteration can be
repeated for a few times (typically five times) about till T
changesbylessthan0.1K.
ThismethodobtainsAe3temperaturewithaccuracyof10K.
89
2. BainitestarttemperatureBSfromStevenandHaynesformula
BS(C)=830270(%C)90(%Mn)37(%Ni)70(%Cr)83(%Mo)
(%elementbywt)
Both bainite and Widmansttten ferritenucleateby same mechanism. The
nucleus develops into Widmansttten ferrite if at the transformation
temperature the driving force available cannot sustain diffusionless
transformation. By contrast bainite form from the same nucleus if the
transformationcanoccurwithoutdiffusion.ThereforeinprincipleB S=WS.
Bainitetransformationdoesnotreachcompletionifausteniteenriches
withcarbon.Butinmanysteelscarbideprecipitationfromaustenite
eliminatestheenrichmentandallowtheaustenitetotransformcompletely.
Inthosecasesbainitefinishtemperatureisgiven(accordingtoLeslie)by
90
3.MSTemperature:
AttheMStemperature
91
Theotherparametersareasfollows
(i)thepartialmolarheatofsolutionofcarboninferrite,
H=111918Jmol1(fromLobo)and
H=35129+169105xJmol1(fromLobo)
ii)theexcesspartialmolarnonconfigurationalentropyof
solutionofcarboninferriteS=51.44Jmol1K1(fromLobo)
S=7.639+120.4xJmol1K1(fromLobo)
=theCCinteractionenergyinferrite=48570Jmol1(average
value)(fromBhadeshia)
=thecorrespondingCCinteractionenergyinaustenitevalues
werederived,asafunctionoftheconcentrationsofvarious
alloyingelements,usingtheprocedureofShifletandKingman
andoptimisedactivitydataofUhrenius.Theseresultswere
plottedasafunctionofmolefractionofalloyingelementsand
averageinteractionparameterwascalculatedfollowing
KinsmanandAaronson.
93
94
4.TransformationstartandfinishCcurves
Theincubationperiod()canbecalculatedfromthefollowing
equation[Bhadeshiaetal.]
WhereTistheisothermaltransformationtemperatureinabsolute
scale,Risuniversalgasconstant,Gmaxisthemaximumfreeenergy
changeavailablefornucleation,Qisactivationenthalpyfor
diffusion,C,p,z=20areempiricalconstantobtainedbyfitting
experimentaldataofT,Gmax,foreachtypeoftransformation
(ferritestart,ferritefinish,bainitestartandbainitefinish).By
systematicallyvaryingpandplottingln(Gpmax/Tz=20)against1/RT
foreachtypeoftransformation(reconstructiveanddisplacive)tillthe
linearregressioncoefficientR1attainsanoptimumvalue.Oncephas
beendeterminedQandCfollowfromrespectivelytheslopeand
interceptoftheofplot.Thesameequationcanbeusedtopredict
95
transformationtime.
TableI:Chemicalcompositions,inwt%ofthesteel
chosentotestthemodel
96
97
ThebainitefinishCcurveoftheexperimentalTTTdiagram
not only shifts to longer time but also but is also shifts to
lower temperature by about 120C. Therefore this is taken
carebyplottingagainst
inordertodeterminep,QandCforthebainiticfinishcurve.
Based on Q, C and Gmax value it can be predicted that Mo
strongly retard the formation of ferrite through its large
influenceonQ.howeveritcanpromotebainiteviathesmall
negative coefficient that it has for the Q of the bainitic C
curve.Crretardbothbothbainiteandferritebutneteffectis
topromotetheformationofbainitesincetheinfluenceonthe
bainitic Ccurve is relatively small. Ni has a slight retarding
effect on tranformation rate. Mn has also retarding effect on
ferriteasaswellasbainitictransformation
98
Fractionaltransformationcurves
Fractionaltransformationtimecanbeestimatedfromthefollowing
JohnsonMehlAvramiequation.
X=transformationvolumefraction,K 1israteconstantwhichisa
functionoftemperatureandaustenitegrainsized,nandmareempirical
constants.Byselectingsteelsofsimilargrainsize,theaustenitegrain
sizecanbeneglectedthentheaboveequationsimplifiesto
99
Assumingx=0.01fortransformationstartandx=0.99for
transformationfinish.Foragiventemperaturetransformation
starttimeandfinishtimecanbecalculatedthenK1andncan
besolvedforeachtransformationproductanafunctionof
temperature.
Thenfractionaltransformationcurvesforarbitaryvaluesofx
canthereforebedeterminedusing
100
Representationofintermediatestateoftransformation
between0%and100%canbederivedbyfittingtothe
experimentalTTTdiagramasfollows:
Wherexreferstothefractionoftransformation.
InmostofTTTdiagramsofRussellhasaplateauatits
highesttemperature.Thereforeahorizontallinecanbedrawn
atBSandjoiningittoaCcurvecalculatedfortemperatures
belowBS.
101
Relationbetweenobservedandpredictedvaluesforferritestart(FS),
ferritefinish(FF),bainitestart(BS)andbainitefinish(BF)areshown
in Fig. 49. Predicted value closely matches the observed values for
selected low alloy steels. Predicted TTT diagrams are projected on
experimental diagrams (Figs. 5052). The model correctly predicts
bainitebayregioninlowalloyaswellasinselectedhighalloysteels.
ThemodelreasonablypredictsthefractionalCcurves (Fig.52).Mo
stronglyretardtheformationofferritethroughitslargeinfluenceon
Q.howeveritcanpromotebainiteviathesmallnegativecoefficient
thatithasfortheQofthebainiticCcurve.Crretardbothbothbainite
andferritebutneteffectistopromotetheformationofbainitesince
the influence on the bainitic Ccurve is relatively small. Ni has a
slight retarding effect on transformation rate. Mn has also retarding
effect on ferrite as as well as bainitic transformation The model is
impiricalinnaturebutitcanneverthelessbeusefulinprocedurefor
thecalculationofmicrostructureinsteel.
102
Fig.49:RelationbetweenobservedandpredictedQ(Jmol1)
valuefor:(a)FSferritestart,(b)FFferritefinish,(c)BSbainite
startand(d)BFbainitefinishcurves.
103
Fig.50:ComparisonofexperimentalandpredictedTTTdiagram
forBSsteel:(a)En14,(b)En16,(c)En18and(d)En110.
104
Fig.51:ComparisonofexperimentalandpredictedTTTdiagramfor
USsteel:(a)US4140,(b)US4150,(c)US4340and(d)US5150
105
Fig.52:ComparisonoftheexperimentalandpredictedTTT
diagramsincludingfractionaltransformationcurvesat0.1,0.5
and0.9transformfractions:(a)En19and(b)En24.
106
Limitationsofmodel
The model tends to overestimate the transformation time at
temperaturejustbelowAe3.Thisisbecausethedrivingforce
term Gmaxiscalculatedonthebasisofparaequilibriumand
becomeszeroatsometemperaturelessthanAe3temperature.
The coefficients utilized in the calculations were derived by
fitting to experimental data, so that the model may not be
suitable for extrapolation outside of that data set. Thus the
calculation should be limited to the following concentration
ranges (in wt%):C 0.150.6, Si 0.150.35, Mn 0.52.0, Ni 0
2.0,Mo00.8Cr01.7.
107
5.Fractionofmartensiteasafunctionoftemperature
Volume fraction of martensite formed at temperature T =f and
f=1-exp[BVpdGv)/dT(MS-T)]
Where, B=constant, Vp=volume of nucleus, Gv=driving force
for nucleation, MS =martensite start temperature. Putting the
measured values
the above equation becomes
f=1-exp[-0.011(MS-T)]
[Koistinen and Marburger equation].
The above equation can be used to calculate the fraction of
martensite at various temperature.
108