Steels crnd Heot Treolmenls

9.I

INTRODUCTION :

This group of ferrous Dlater.ials is ost inportart to ttre sociery because ol thir lvide
rarge ofproperties and varietv ofapplications. Theoreticallv steels are the allovs ofiron and

in {'hich the carbor content is between 0.008 and 2.0 per cent. Commercial steels
always contaiD sonre amounts of other elenlents. If these el.mcrts ire trccidentalty present
\1.ithout anv inteDtion, tLev are called inipurities. I{owever, ltthet, ar.e adde<i pur.posely, they
ale called alloying elenents. Sulphur and phosphorus.rre the corrrrrron nnpurities which
come frolr the coke and ore used in the manufacture of steel. To overcome the undsirable
eflects af s[\trur, manganese is always added in so re arnount to the stee]. Many other
elerDents are also present in certain amounts ajrd hence commrcial steels are rather
carbon

complex alioys. Presence ol these elements in small anounts do not appreciably chanee the
heat treatnent behaviour aDd microstructures of steels. Stels with other elements in small

rmounts are called plain carbon steels and thtu structures ard properties can be discussed
C (or Fe Fe3C) equilibrium diasram.

\!ith th he\r of}'e

Id cer.tailt cases, sone olthe elenents are intentionally added to steels to increase sonle
ofthe required properties. These steels are called alloy steels_ The plopertis ofalloy steels
car alsobe discussed witir the help ofFe C (or Fe Fe,C) equilibriun diagrarn bykeeprng in
rlnd the itlnuence ofthese elements on the above diagram or bv using a mocliliecl .liagraD.
Therefole, it is highly essential to study rtre fe-C (or Fe-FerC) equilibriuu or.phase
diagram nr detail.

9.2

IRON-IRON CARBIDE EAUILIBRIUM DIACRAM

The above equilibrium diigraxr is shown in Fig. 9.1.

(308)

309

Stsls and Heat Treaiments

L+6

1539

0.18

M
6
1400

910

Liquid (L)

768(}.,)

9
2g
E

2lo

3
Peicent carbon by

;ig. 9.1

4 4.3 5
weighi-"'

fe,C

di.sEm.
' lroFlrcn.otld..quillbrlm

The various phases existing in the diagram are as below

(i)

6.67

(Ferrite) : Ferrite is an inte$titial solid solution o{ carbon in low tempe}ature

B.C.C. cr ircn. It is almost a pule iron and the name ferdte comes from the Latin word
/errzn which ucans iron. The solubility of ca6on in d - iron at room temperature is
0.0087o and incieases with increasing tempemture to about 0.025% at 72?'C. It is a
relatively soft and ductile phase (hardness = 80 BHN). It can be extensively cold worted
without cracking. It is strongly ferromagnetic upto 768oC and becomes paramagnetic at
c.

768uC dudng heating. This temperature (?68oC) at which

fertite becomes palaroagrretic is

called Cutie tenlpetature. The parsmagnetic d which exists between 768oC and 9100 was
denoted as p in the old days.

310

Material Science and Metallurov

(ii)

y (Austenite)

Austenite is ar interstitial solid solution o{ carbon in F.C.C. 1called Austedite in honour of Sir Austin, who was one of the fiIst
metallographer to 6tudy its properties. It can dissolve upto 2.070 carbon at 1147oC. The
phase is stable only above ?2?"C. lt is a soft, ductile, malleable. ard non-magnetic
(paramagnetic) phase. It can be extensively worked at the temperatures ofits xistence.
(iii) d (6 - ferrite) : It is an inteNtitial solid solution ol carbon in high temperature
B.C.C. 5 iron. It is similar to o. - lerrite except its occuEence at high temperature.
(iv) Fe3C (Cementite) : lt is a]r intermetallic compound of iron and carbon with a fired
ca$or coltent of6.677, by weight. Cementite has a complex o*horhombic crystal structure
with 12 iron atoms and 4 carbon atoms in a unit cell. It is xhemely hard alrd bdttle pha6e
(hardness -900 VPN). It is Ierromagnetic upto 210oC and paramagnetic above this
temperature. It is also called lron C&rbide ot sin,ply Ca.fttd.e in the discussion of FFC

iron. The phase is

system.

Ihe

(i)

above diagram contains thrce differcnt transformatrons which are described below

Peritectic transforBation

S,+L+
!"b[*ml:lF

Constet

In general, peritectic transformation is denoted as

S,r

'

{heie

Sr and Sz are two different solids and L is liquid.

peritectic
The
region in tlle upper lelt hand colner ol Fig. 9.1 is shown on an enlarged
scale in Fig. 9.2. In Fe-C system, this transformation occurs at point P and is as below :

o'
E

Weigb( % Cdbon --.---)

Fig.9.2

(ofo.l%c)

! P.;t

.ri. r.gt6l| cl F+< phor

L
+ (of0.55%c)+

dtqgrem.

t19xc

{of0.i8%c)

"(9'1)

6 o10.17, C combines with liquid of 0.55% C at 1492oC and foims y of 0.182oC. The
amounts of 6 and L can be found out by applyhg lever rule :
0.55 - 0-18
q.
Amount of ti =

ffi

xloo =

42.2

Sieels and Heet Treatments

Amoun-ofriquid

31',I

- 018-01
;.;;_ ;i''nn
=

17

.8%

For hypopeFitctic steels (i.e. steels ol carbon content less than 0 187,), the
transformation can be written as

6.L t"'"c ,6.1

$2)

and for hlTerperitectic steels (i.e. steels of carbon content more than 0-187r, the
transformation can be written as :
...(9.3)
y+L
6+ LEquations 9.2 and 9.3 are similar to peritectic translormation as shown by equation
9.1. Equation 9-2 indicates that for hypoperitectic steels, there is an excess of 6 and
equation 9.3 indicats t}Iat t}lerc is an excess of liquid for hyperperitectic steels befor the
start of translormation and hence some amount ofthese phases remain after the completion
of trans{ormation. This indicates that the peritectic hansformation range is from 0.1% C to
0.55% C. All the steels containing carbon between 0 1 and 0 55% exhibit peritectic
transformation when cooled from the liquid state. Other steels (i.e. steels containing carbon
from 0-008 to 0-1% and 0.55 to 2.0%) do not undergo pedtectic hansformationThe above translormation occurs at a very high temperature where the steels, ifheated,
show buming and hence is of no use for the modification olpmpedies ofsteels.
(ii) Dutectoid transfor"mation : In general e tectoid transformation is denoted as :

to""*t

s,r

s2

* sl

tDprahr
where Sr, 52 and 53 are diffeftnt solid phases.

121

9
i
z
e
E

0.008

Weight % Cdbon

Fis, 9.3 : Eot .loid rogion

-----r

ol;+< ph.i.

dlcgrom.

Marerial Science and lMetallur

312

the eutectoid region in the lower left hand side of Fig. 9 1 is showrr on an enlarged
in ! rs. 9.3.
liutectoid transformation in Fig. 9.3 occuN at point E and is
127'C

YJO
lolr).8% C)
t.c.(i.

as below

scale

...(9.4)

Fe,C

(0f0025tc)
8.0.c.

Ar sterrite of 0.8% C decomposes at constaDt temperature of ?27' C and lorms a nixture

of 1errite lof 0.0257. C) and cementite. This eutectoid mixture of fenite ard cementite is
called pearlite, due to its pearly appearance under the optical nicroscope lt consists of
alternar;e lamellae of fer:rite and cementite. The amount offerrite and cementite iD pearlite
at room temperature are as below ;
6.67 - 0.8
,\Dount offerrite =
6.67 - 0.008
88.17,
0 8 0.008
,\.uollllr. of cenFrtite =
6.67 0.008
11.9

This clearly Ieveals that the fenite iamella is 7.4 tiDes (i e. about 7 times) thicker than
.ementite lamella. (Please renenber that tlrcse calculations haoe been. done assumirE tlre
densi.ties of fen ite a d ccnrcntite to be equaL, and also the sutfa.e at eas of fert ite and cenrcntite
LameLLae i.n peat lite ate equtLl). T]Ire propedies of pearlite depend upon its i terlarrellar
spacing. Slraller the spaci g, higher are the nrechanical properties The interlane]lar
spaci g depends on the cooljng rate and within liDit, the spacirg becomes less And less with
increasing cooliDg rates. The hardDess ofpearlite with the usual cooling rates is between
230 and 270 BHN. Ilo!1'el,er, lor a1l practical purposes, lhe value of bardness ay be taken
as 250 BHN.
The intellaDrellar spacing ofa parlite is defiDed as tire distance fro the centre ofa
ferriLe (or ce enlite) lalnella to the centre olthe next adjacert ferrit (or cenentite) lamela.

(iii)

Eutectic tunsfornratior

Ll gereral, eulectic transformation is denoted as:

C,,""!"'.!,
1.mt)drture

S *S.,

rvhere Sr alld 52 ar' t\i'o diflerent so]ids alrd L is liquid.

In Fe C syste , this reaction oceurs at 114?"C and 4.39; C and is as belorv

r1?

L
(,,14.:.,7

Cl

ll

F..,(.

{ul2.on.C)

(,,i{i.6?% C)

...(9.5)

Liquid of 4.3% carbon transforms at constant tenperature of 1147''C and gives

an

eutectic mixture of austenite (of 2.07. C) and cemeAtite. This eutectic mixture of austenite

and cenentite is called ledeburite. AusteAite from the ledeburite is not stable at low

Steels and Heal Treatmnts

313

temperatlrrl's and gets transformed to pearlite with slow lates of cooling at 727oC; and
hence at loom tempcraturc. structurc consists of pearlite aDd cementite. This mixture is
called trarslormcd icdeburitc. Thc amounts of pcarlitc aDd ccmcntite in transformed
ledeburitc :rt roon tcmperaturc according to levcr rule are as foilows :

667

43

Anr,'trnt ,'t I( .if lrte =

6lj ? j-,

Arnlont ut crnrcnhtL-

40.4%

,.

59 6'/'

:1

08

,.-_

Cemcntitc is hard and pcarlitc is also fairly hard and therefore, transfomred ledebudte
is also hard rnd subsequently britUe.

9.3

CRITICAITEMPERATURES

The tenperatures at which the phase changes occur dudng heating and cooling arc
called criticftl tcmperaturcs. Thcsc tcmpcraturcs and tcmpcratures at which magnetic
changes occur are denoted by symbols. These symbols with thei meaning dudns heating
under equilibrjum conditions are siven biow :
Tlris denotes the temperature at which cementite changes ftom ferromagnetic to
Iranmagnetic character. This is indicated by a dotted line AB at 210oC in
Fig.9.1.
'l'his denotes the temperaturc at which pcarlite transforms to austenite. This
transformation occurs at a constant temperature of ?27oC called eutectoid
tonperalure and does not depend on the carbon content in the alloy. lt is
dcroted by the line DEF nr Fig. 9.1. This temperaturc is known as lowcr critical

This indicates the temperature at $'hich ferronagnetic ferrite becomes

prrrmagretic. This is shown by a dotted llnc cH in Fig. 9.1 at 768"C (Cu e
tenperatulc). Tlre loss offeuomagnetism continues rvith the line HEF.

It is the temperaturc at which the last trace of frce turito gets dissolved to fron
100.1 austcnite It reprcscnts the tcmperature al \cr +.t)/.t phasa boundary
rn{l is a lunction ofcarbon cortent. It decrcascs fron 9100(: at 0.1 Cto727oC

^t
0.8', C, \\'hich is shorvn by a line CIIE in Fie. 9.1. Ihis tenrperatur is kiown as
uppcr

-itical ienrpcratnre

for ferrite.

l.r)r steels containing about 0.5./, C to 0.87,C disappearance of f.r!.orraenetisrr

(,\2r coincides with disappearance of ferrite (A3), and hence tirc upr).r critical
tilnperaiure in ihis region is frequontly identified as At2. ln hlrrcr.utectoid
srcels, :il1 At, A2 ard Aa coincidc with the eutectoid temperatLrre rnd nence to the
risht of0.8'l. C, the lower c tical temperature is often designated as A1, I.

Material Sqience and M.xallrrrsv

314

at which last trace offree cementite gets dissolved to forr

1007, austenite. It represents the temperature of ('I+ FeBC)/y phase b rndar-v
and like A", is a function of carbon content. This temperature is shown b]' the
line nl in Fig.9.1 and increases fiom ?2?oC to 1147oC witb increase in
'arbon
fron 0.8 to 2.07o. It is also known as upper criticat te perature for ceme-ltite'
The A"- line is considerably steeper than the Aj line

Ach: It is the tempemture

Critical phase transformation temperahlres Al, A3 and Atn are influenced by he'ting or
cooling lates. Dudng rapid heating, these tempelatures are raised and during rapid cr ')irg,
they are lowered. For extremly slow cooling or heating rates i.e unde" equilibrium
conditions, the critical temperatures are the same as shown by the equilibrium dt'r3;am'
Under non- equilibrium conditions, the departule ir critical temperatures fl"m their
equilibrium values will be more arrd more with increasing rates ofheating or cooli: g This
change in temperature is due to thermal hysteresis and during heating, it is den' ted by a
suffix letter'c' (c flom the French word chaufag, means heating) and during cooling, by a
letter'r' (r from the French word, refoidissmerrr, means cooling). Thus, lor exarple, At
observed duing heating becomes A.1 and during cooling becor'.res Arr' For eqrilibrium
cooling, letter 'e' is used. This method of notation is commonly used to explain the
Az
depariures from equilibrium condition. However, such a change is not observed in A.
'nd
temperatures because of no h,'steEsis in nagntic transition. Various criticai terrrperatures
ofiron carbon alloys aie summaised in Table 9.1

9.4 AI.I.OIROPY, COOITNG CURVE AND VOLUME CHANGES OT PURE IRON

(i) Allotropy of pure iron : Iron changes its crystal structure ftom B C.C. to F.C.C at
910"C, then again changes to B.C.C. at 1400"C and with fu her heating, it melts at
1539oC.

This change ol crystal structure is called allotropy. These allohopic han.:ormations

are shown below

Cune

(?68"C)

el0t :r400'c
<-r"^.ae'*i"'-".-rf --r",-"e*t
<--

BCC

"

t519"c

6BCC ----------r

Stels ahd Heat Tratmnts

315

Table 9.1 : Critical Temperatures of Iron-Carbon Alloys

Sr.

Critical points (Symbols)

Tedperature

210

Siglrificance during heating

No.

t.

Cementite becomes

paramagnetic

(Cnrie temperature of cementite)

A1

Pearlite starts hransforming to

austenite

(Lower critical temperature)

Ferrite becomes paramagnetic

768

(Curie temperature of ferdte)

A3

727

Completion

-910

olferit

to austenite

transformation

(Upper critical temperature for

hypoeutectoid steels)

.\-

5.

721-1141

Completion ol cementite to

austenite

(Upper critical temperatuie for

hypereutectoid steels)

A,

6.

(ii)

1400-1492

Cooling curve of pure

ifon:

Completion olaustenite to
ferrite hansformation.

The cooling curve ofpure

Liquid

&ircn, body centred cubic

t
I

lnon,

face

cerred cubic

e
8.
E

910

76a

FiE, 9.4 ! coolins

.urv. of pur6 lr.h.

ironis shoFn in Fig.9.4.

Material Science and Metallurqv

316

(iii)

Volurne changes of pure iron

Due to the atrove structural changes, sharp

volume changes occur during heating and cooling. Ihese voluine changes are Bhowu in Fig.

s.5

1
E

910
TemPerarure. C

ib.

9.5 !

-"""')

1400

1539 {Meltsl

volum..hong.. of Pur. ils.

Due to the sharp volume change at Aa, iron (or stel) may crack during fast cooling or

heating.

Usually the FFC equilibrium diagram is terminated at about 57. carbon or drawn
dotted beyond 57o carbon because of the following limitatioN :

(i)

Carbon sublimes at atmospheric pressure instead of melting

alloyB are very

diftcult

a-Dd

representative

to prepare and

(ii)

Cementite decomposes as soon as it forms. For alloys above - 5% carbon, graphite

flakes which form due to decomposition ofFe3C are long and thick. These flakes float to the
surface of a solidifying casting and the casting appesB blacki8h like a burnt .asting. Snch
long and thick flakes are not desirable becuase they reduce the properties. This type of
gaphite a called &ts[ grapnite.

part of Fe-C phase diagram (i.e. above 57. carbon) is not useful. A1l the
commercial alloys contain carbon well blow the composition of Fe3C (i.e. 6.6?'/o C) and at
T'his particular

this composition the diagram is usually terminated. I'he Fe-C diagram which is teminated
at 6.67qo C b called as Fe-Fe3C equilibrium diagram because for 6.677. C, the amount of
FesC

is 1007,.

Iron-carbon phase diagram shows various types of trans:ormations due to allotropic

changes in iron and non-metallic character of carbon. Fu.themore, maghetic-non magtretic
chadges in ferrite and cementite lead to the apparcnt complexity of the diagram.

lxompl. 9.1 z Iron

undergoes a polymorphic phase transfotmation

structure. Calxulate thz percent

ch.ange in density d.ue to

[ron a B.C.C. to F.C.C.

this volunv change.