Sei sulla pagina 1di 108

TimeTemperatureTransformation

(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

The time taken to 1% transformation to, say pearlite or bainite


is considered as transformation start time and for 99%
transformation represents transformation finish. On quenching
in water austenite transforms to martensite.
But below 230C it appears that transformation is time
independent, only function of temperature. Therefore after
keeping in bath II for a few seconds it is heated to above
230C a few degrees so that initially transformed martensite
gets tempered and gives some dark appearance in an optical
microscope when etched with nital to distinguish from freshly
formed martensite (white appearance in optical microscope).
Followed by heating above 230C samples are water
quenched. So initially transformed martensite becomes dark in
microstructure and remaining austenite transform to fresh
martensite (white).
7

Quantity of both dark and bright etching martensites are


determined. Here again the temperature of bath II at which 1%
dark martensite is formed upon heating a few degrees above
that temperature (230C for plain carbon eutectoid steel) is
considered as the martensite start temperature (designated M S).
The temperature of bath II at which 99 % martensite is formed
is called martensite finish temperature ( MF).
Transformation of austenite is plotted against temperature vs
time on a logarithm scale to obtain the TTT diagram. The
shape of diagram looks like either S or like C.
Fig. 4 shows the schematic TTT diagram for eutectoid plain
carbon steel
8

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(b): A cabbage filled with water analogy of the


threedimensional structure of a single colony of pearlite,
aninterpenetratingbicrystalofferriteandcementite.
13

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

On cooling of metastable austenite 1% martensite forms at


about 230C. The transformation is athermal in nature. i.e.
amount of transformation is time independent (characteristic
amountoftransformationcompletesinaveryshorttime)but
functionoftemperaturealone.Thistemperatureiscalledthe
martensitestarttemperatureorMS.
BelowMswhilemetastableausteniteisquenchedatdifferent
temperature amount of martensite increases with decreasing
temperatureanddoesnotchangewithtime.
The temperature at which 99% martensite forms is called
martensite finish temperature or MF. Hardness values are
plotted on right Yaxis. Therefore a rough idea about
mechanicalpropertiescanbeguessedaboutthephasemix.

18

TTTdiagramgives
Natureoftransformationisothermalorathermal(time
independent)ormixed
Typeoftransformationreconstructive,ordisplacive
Rateoftransformation
Stabilityofphasesunderisothermaltransformationconditions
Temperatureortimerequiredtostartorfinishtransformation
Qualitativeinformationaboutsizescaleofproduct
Hardnessoftransformedproducts

19

FactorsaffectingTTTdiagram
Compositionofsteel
(a)carbonwt%,
(b)alloyingelementwt%
Grainsizeofaustenite
Heterogeneityofaustenite

Carbonwt%

As the carbon percentage increases A3 decreases, similar is the case


for Ar3, i.e. austenite stabilises. So the incubation period for the
austenite to pearlite increases i.e. the C curve moves to right.
However after 0.77 wt%C any increase in C, Acm line goes up, i.e.
austenite become less stable with respect to cementite precipitation.
So transformation to pearlite becomes faster. Therefore C curve
movestowardsleftafter0.77%C.Thecriticalcoolingraterequiredto
prevent diffusional transformation increases with increasing or
decreasingcarbonpercentagefrom0.77%Candeforeutectoidsteel
20
isminimum.Similaristhebehaviourfortransformationfinishtime.

Pearlite formation is preceeded by ferrite in case of


hypoeutectoid steel and by cementite in hypereutectoid steel.
Schematic TTT diagrams for eutectoid, hypoeutectoid and
hypereutectoidsteelareshowninFig.4,Figs.7(a)(b)andall
of them together along with schematic FeFe3C metastable
equilibriumareshowninFig.8.

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

Under isothermal conditions for various compositions


proeutectoid tranformation has been summarised below
(Fig. 9). In hypoeutectoid steel the observable ferrite
morphologiesaregrainboundaryallotriomorph()(Fig.11(a)
(d)),Widmanstttenplate(W)(Figs.1216),andmassive(M)
ferrite(Fig.11(f)).
Grain boundary allotriomorphs form at close to Ae3
temperature or extension of Aecm line at low undercooling.
Widmanstttenplatesformathigherundercoolingbutmainly
bellow Ae1. There are overlap regions where both
allotriomorphs and Widmansttten plates are observed.
Equiaxedferriteformsatlowercarboncompositionlessthan
0.29wt%C.
25

Ae1

CmW

0.77

Cm

Austenite

Ae3
0.0218

A ec

Temperature

Pearlite
Upperbainite
MF

Lowerbainite
MS
Mixmartensite

Lathmartensite

Platemartensite

Weight % carbon

Volume % of retained austenite

Fig9:Temperatureversuscompositioninwhichvariousmorphologies
aredominantatlatereactiontimeunderisothermalcondition

W=Widmansttte
nplate
M=massive
P=pearlite
ub=upperbainite
lb=lowerbainite

Volume%ofretained
austeniteatroom
temperature
26

There are overlapping regions where both equiaxed ferrite


and Widmansttten plates were observed. However at very
low carbon percentage massive ferrite forms. The
reconstructive and displacive mechanisms of various phase
formationisshowninFig.10.
Inhypereutectoidsteelbothgrainboundaryallotriomorphand
Widmanstatten plates were observed. Massive morphology
was not observed in hypereutectoid steel. Grain boundary
allotriomorphswereobservedmainlyclosetoAecm orcloseto
extensionofAe3linebutWidmanstttenplateswereobserved
atwidertemperaturerangethanthatofhypoeutectoidsteel.In
hypereutectoid steel there are overlapping regions of grain
boundaryallotrioorphandWidmanstttencementite.

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(e): An idiomorph of ferrite in a sample which is


partially transformed into and then quenched so that the
remaining undergoes martensitic transformation. The
idiomorphiscrystallographicallyfacetted.
33

Fig.11(f):Massiveferrite(m)inFe0.002wt%Calloy
quenchedintoicebrinefrom1000C.CourtesyofT.B.
Massalski

34

Fig.12(a):SchematicillustrationofprimaryWidmansttten
ferritewhichoriginatesdirectlyfromtheaustenitegrain
surfaces,andsecondarywwhichgrowsfromallotriomorphs.
35

Fig. 12(b): Optical micrographs showing whiteetching (nital)


wedgeshapedWidmanstttenferriteplatesinamatrixquenchedto
martensite.Theplatesarecoarse(noticethescale)andetchcleanly
becausetheycontainverylittlesubstructure.
36

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

Fig. 16 (a) Surface relief of Widmansttten ferrite Fe0.41C


alloy, austenitised at 1200C for 6 hrs, isothermally
transformedat700Cfor30minandwaterquenced,(b)same
fieldafterlightpolishingandetchingwithnital.
40

For eutectoid steel banitic transformation occurs at 550 to


250C.Athighertemperatureitisupperbainiteandatlower
temperatureitislowerbainite.AsCincreasestheausteniteto
ferrite decomposition becomes increasingly difficult. As
bainitic transformation proceeds by the nucleation of ferrite,
thereforebanitictransformationrangemovestohighertiming
andlowertemperature.Withincreasingpercentageofcarbon
the amount of carbide in interlath region in upper bainite
increasesandcarbidesbecomecontinuousphase.Howeverat
lower percentage of carbon they are discrete particles and
amount of carbide will be less in both type of bainites. For
start and finish temperatures for both types of bainites go
downsignificantlywithincreasingamountofcarbon(Figs.8
9).Howeverincreasingcarbonmakesiteasiertoformlower
bainite.
41

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

For eutectoid steel martensite forms at around 230C. From


230Ctoroomtemperaturemartensiteandretainedausteniteare
seen.Atroomtemperatureabout6%retainedaustenitecanbe
there along with martensite in eutectoid steel. At lower carbon
percentageMStemperaturegoesupandathigherpercentageM S
temperature goes down (Fig. 4, Figs. 78, Fig. 28). Below 0.4
%Cthereisnoretainedausteniteatroombutretainedaustenite
cangouptomorethan30%ifcarbonpercentageismorethan
1.2%.Morphologyofmartensitealsochangesfromlatheatlow
percentage of carbon to plate at higher percentage of carbon.
Plateformationstartataround0.6%C.Thereforebelow0.6%
carbononlylathemartensitecanbeseen,mixedmorphologies
areobservedbetween0.6%Cto1%Candabove1%itis100%
platemartensite(Figs.2939).

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

Volume % of retained austenite

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)

(T. Maki K. Tsuzaki, I. Tamura: Trans. ISIJ, 20(1980), 207.)


57

Lenticularmartensite
(Opticalmicrograph)
Courtesyof
T.Maki
Fig.32: Fe-29%Ni-0.26%C
(Ms=203K)

Fig. 33: Fe-31%Ni-0.28%C


(Ms=192K)

Fig.34: schematic diagram for


lenticular martensite

58

Fig.35:Growthbehavioroflenticularmartensite
inFe30.4%Ni0.4%Calloy

cooling

surface relief

surface relief

g
lin
o
co

surface relief

after polished and etched

Courtesyof
T.Maki

(T. Kakeshita, K. Shimizu, T. Maki, I. Tamura, Scripta Metall., 14(1980)1067.)


59

Fig.36:LenticularmartensiteinFe33%Nialloy
(Ms=171K)
Courtesyof
T.Maki
schematic illustration

Optical micrograph

midrib

twinned region
60

Fig. 37: Optical microstructure of lath martensite (Fe-C alloys)

0.0026%C

0.18%C

0.38%C

0.61%C

Courtesyof
T.Maki

61

Block structure in a single packet (Fe-0.18%C)

Courtesyof
T.Maki

Fig. 38: SEM image

Fig.39 : Orientation
image map

Alloying elements:

Almost all alloying


elements (except, Al, Co, Si) increases the stability of
supercooled austenite and retard both proeutectoid and the
pearliticreactionandthenshiftTTTcurvesofstarttofinish
torightorhighertiming.Thisisduetoi)lowrateofdiffusion
of alloying elements in austenite as they are substitutional
elements, ii) reduced rate of diffusion of carbon as carbide
forming elements strongly hold them. iii) Alloyed solute
reducetherateofallotropicchange,i.e. ,bysolutedrag
effect on interface boundary. Additionally those
elements (Ni, Mn, Ru, Rh, Pd, Os, Ir, Pt, Cu, Zn, Au) that
expand or stabilise austenite, depress the position of TTT
curves to lower temperature. In contrast elements (Be, P, Ti,
V, Mo, Cr, B, Ta, Nb, Zr) that favour the ferrite phase can
raisetheeutectoidtemperatureandTTTcurvesmoveupward
tohighertemperature.
63

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

However bainitic reaction is suppressed by the addition of some


alloying elements. BS temperature (empirical) has been given by
Steven&Haynes
BS(C)=830270(%C)90(%Mn)37(%Ni)70(%Cr)83(%Mo)
(elementsbywt%)
AccordingtoLeslie,
B50(C)=BS60
BF(C)=BS120
MostalloyingelementswhicharesolubleinaustenitelowerM S,MF
temperatureexceptAl,Co.
AndrewsgavebestfitequationforMS:
MS(C)=539423(%C)30.4Mn17.7Ni12.1Cr7.5Mo+10Co7.5Si
(concentrationofelementsareinwt%).
EffectofalloyingelementsonMFissimilartothatofMS.Therefore,
subzero treatment is must for highly alloyed steels to transform
67
retainedaustenitetomartensite.

AdditionofsignificantamountofNiandMncanchangethenatureof
martensitictransformationfromathermaltoisothermal(Fig.41).

Temperature

1%
%
30

Logtime
Fig.41:kineticsofisothermalmartensiteinanFeNiMnalloy

68

Effect of grain size of austenite: Fine grain size shifts


S curve towards left side because it helps for
nucleation of ferrite, cementite and bainite (Fig.
43). However Yang and Bhadeshia et al. have shown that
martensite start temperature (MS) is lowered by reduction in
austenitegrainsize(Fig.42).
Fig. 42: Suppression of Martensite
start temperature as a function
austenite grain size L. MOS is the
highest temperature at which
martensite can form in large
austenite grain. MS is the observed
martensitestarttemperature(at0.01
detectable fraction of martensite).
Circlesrepresentfromlowalloydata
andcrossesfromhighalloydata.
69

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

For finer austenite

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

Where Xi=mole fraction of component i, i=activity coefficient of component i,


R=universal gas constant, assuming 0 for Fe, 1for C, i=2 to n for Si, Mn, Ni,
Cr, Mo, Cu,V, Nb, Co, W respectively.
84

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

Where To is the phase boundary


temperature for pure Fe-C system and To
is given by .

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

In the above equation, T refers to MS temperature in absolute


scale,Risuniversalgasconstant,x=molefractionofcarbon,Yiis
theatomfractionoftheithsubstitutionalalloyingelement,Tmagi
andTNMi arethedisplacementintemperatureatwhichthefree
energy change accompanying the transformation in pure
iron (i.e. FFe) is evaluated in order to allow for the changes
(per at%) due to alloying effects on the magnetic and non
magneticcomponentsofFFe , respectively.Thesevalueswere
takenfromAaronson,Zenner.FFevaluewasfromKaufmann.
92

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

f*=Zener ordering term was evaluated by Fisher.


Theremainingterm, FFe=freeenergychangefromaustenite
to martensite as only function of carbon content. and is
identical for FeCand FeCYsteels as structureforbothcases
are identical (Calculated by Bhadeshia )=900 to 1400 J mol 1
(for C 0.01 to 0.06 mole fraction, changes are not monotonic).
However LacherFowlerGuggenheim extrapolation givesbetter
resultof1100to1400Jmol 1(Carbonmolefraction0.010.06).
Theequationwassolvediteratativelyuntilthebothsidesofthe
equation balanced with a residual error of <0.01%. The results
underestimatethetemperatureof1020K.Theerrormaybedue
to critical driving force for transformation calculation consider
onlyafunctionofcarboncontent.

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

The optimum values of p and corresponding values of C, Q for


differenttypesofsteels(TableI)whereconcentrationsareinwt%are
summarisedbelow[Bhadeshiaet.al.](TableII).
TableII:Theoptimumvaluesoffittingconstants
FS=ferritestart,FF=ferritefinish,BS=bainitestartand
BF=bainitefinish

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

Potrebbero piacerti anche