Fe_C Diagram

● Pure iron exist in more than one crystal structure in solid state.
● Soft iron is the best known example for allotropy of iron, which can be
strengthened/hardened by adding small amount of other metals.
● Addition of carbon to soft iron can increase the hardness of soft iron by 1000
times, the alloy is called as steel.
● There are three allotropic forms of carbon α (BCC),  (FCC), and  (BCC)
● When liquid iron is cooled down, it crystallizes at 1538 C to
•  (BCC) iron.
● Upon further cooling, the crystal structure gets converted to  (FCC) at 1394
C.
● The crystal structure changes into α-phase (BCC) at 912C .
● These allotropes are treated as different phases.
Allotropic forms
● Family of iron carbon alloys having carbon content upto 2.14% is
called as steel.
● Steels are solid solutions of iron and carbon
● If the carbon content is more than 2.14% then it is called as cast iron.
● In cast irons most of the carbon exists as inter metallic
compound, iron carbide.
● In phase diagram, the allotropic forms of iron forms different solid
solutions which also can be considered as phases.
● The intermetallic compound, iron carbide, is also a phase present in
the system.
 ferrite
● BCC  ferrite is also an interstitial solid solution of carbon in BCC iron.
● In the BCC  ferrite, only small concentrations of carbon are soluble; the m a xi m u m
solubility is 0.022 wt% at 727C and at room temperature it is reduced to 0.008%.
● The limited solubility is explained by the shape and size of the BCC interstitial
positions, which make it difficult to accommodate the carbon atoms.
● Even though present in relatively low concentrations, carbon significantly
influences the mechanical properties of ferrite.
● This particular iron–carbon phase is relatively soft, may be made magnetic at
temperatures below 768C.
A u s te n ite FCC
● The austenite, or  phase of iron (FCC), when alloyed with carbon alone, is not
stable below 727C.
● The maximum solubility of carbon in austenite, 2.14 wt%, occurs at 1147C. This
solubility is approximately 100 times greater than the maximum for BCC ferrite.
● Stable between 912-1394C
● The FCC interstitial positions are larger, and, therefore, the strains imposed on the
surrounding iron atoms are much lower.
● The phase transformations involving austenite are very important in the heat
treating of steels.
● Austenite is non-magnetic.
● The  and  ferrite is virtually the same as ferrite, except for the range of
temperatures over which each exists.
Ce ment ite or Fe 3 C or iron carbide _ORTHORHOMBBIC

● Cementite(Fe3C) forms when the solubility limit of carbon in ferrite is

exceeded 0.002% below 727C (for compositions within the +Fe3C phase
region).
● Fe3C will also coexist with the phase between 727 and 1147C).
● Mechanically, cementite is very hard and brittle; the strength of some steels is
greatly enhanced by its presence.
● Strictly speaking, cementite is only metastable; that is, it will remain as a
compound indefinitely at room temperature.
● However, if heated to between 650 and 700C for several years, it will
gradually change or transform into a iron and carbon, in the form of
graphite, which will remain upon subsequent cooling to room temperature.
● It m a y be noted that one eutectic exists for the iron–iron carbide system,
at 4.30 w t% C and 1147C;
Pearlite structure
• A laminated structure formed of alternate layers of ferrite and
cementite with average composition 0.83% carbon
• Pearly lustre in the microscope
• Interference of light in its regular layers
• Most common constituent of steel
• It combines the hardness and strength of cementite with the
ductility of ferrite and is the key to the wide range of the
properties of steel
• The laminar structure also act as barrier
to crack movement as in composites.
This gives it toughness.
ledeburite
●ledeburite is a mixture of 4.3% carbon in iron and is a
eutectic mixture of austenite and cementite.
• Peritectic reaction at 1495˚C and 0.18%C,
-ferrite + L -iron (austenite)

Eutectic reaction at 1147˚C and 4.3 %C,

➢ L -iron + Fe 3 C (cem ent it e)
[ledeburite]
Eutectoid reaction at 727˚C and 0.77%C,
 -iron α– f errit e+ Fe 3 C (cem ent it e)
[pearlite]
● The microstructure for eutectoid steel that is slowly cooled through the
eutectoid temperature consists of alternating layers or lamellae of the two
phases ( and Fe3C) that form simultaneously during the transformation.
● This microstructure, point b, is called pearlite because it has the
appearance of mother of pearl when viewed under the microscope at low
magnifications.
● The pearlite exists as grains, often termed “colonies”; within each colony
the layers are oriented in essentially the same direction, which varies from
one colony to another.

• The thick light layers are the

ferrite phase, and the
cementite phase appears as
thin lamellae most of which
appear dark.
Mechanically, pearlite has
properties intermediate
between t he so ductile
● The alternating  and Fe3C layers in pearlite form as such for the same
reason that the eutectic structure forms, because the composition of
the parent phase [in this case austenite (0.76 wt% C)] is different from
either of the product phases [ferrite (0.022 wt% C) and cementite (6.7
wt%C)], and the phase transformation requires that there be a
redistribution of the carbon by diffusion.
● The directions of carbon diffusion are indicated by arrows. Carbon
atoms diffuse away from the 0.022 wt% ferrite regions and to the 6.7
wt% cementite layers, as the pearlite extends from the grain
boundary into the unreacted austenite grain. The layered pearlite
forms because carbon atoms need diffuse only minimal distances
with the formation of this structure.
● Consider a composition C0 to the left of the eutectoid, between 0.022 and
0.76 wt% C; this is termed a h ypoeutectoid (less than eutectoid) alloy.
● Cooling an alloy of this composition is represented by moving down the
vertical line yy’
● At about 875C, point c, the microstructure will consist entirely of grains
of the  phase, as
● In cooling to point d, about 775°C, which is within the + phase region,
both these phases will coexist as in the schematic microstructure.
● Most of the small  particles will form along the original  grain
boundaries.
●On the other hand, the change in composition of the austenite is more dramatic,
proceeding along the (+) -  boundary, line MO, as the temperature is reduced.
• ● Cooling from point d to e, just above the eutectoid but still in the
• + region, will produce an increased fraction of the  phase and a microstructure
similar to that also shown: the  particles will have grown larger. The  phase will
contain 0.022 wt % C, while the  phase will be of the eutectoid composition, 0.76
w t % C.
• ●As the temperature is lowered just below the eutectoid, to point f, all the  phase
that was present at temperature Te (and having the eutectoid composition) will
transform to pearlite.
• ● There will be virtually no change in the  phase that existed at point e in
crossing the eutectoid t e m p e r a t u r e — i t will normally be present as a continuous
matrix phase surrounding the isolated pearlite colonies. Thus the ferrite () phase
will be present both in the pearlite and also as the phase that formed while
cooling through the + phase region.
• ●The ferrite that is present in the pearlite is called eu t ec toi d ferrite,
whereas the other, that formed above Te, is termed proeutec toid (meaning
pre- or before eutectoid) ferrite.
ISOTHERMAL TRANSFORMATION DIAGRAMS
(TTT DIAGRAMS)
• There are several restrictions for the phase diagram, even
though they are useful in the interpretations of metallic
and ceramic materials.
• It presents only compositional data, limited
information on the structural form.
• Phase diagram gives only equilibrium states.
• Alloys are rarely cooled at very slow rates or at equilibrium
cooling.
• To overcome these difficulties isothermal transformation
diagrams are used.
● Temperature and cooling rate play a v e r y i m p o r t a n t role in austenite t o
pearlite transformation in steel

● Upon cooling, austenite, having an i n t e r m e d i a t e carbon concent rat ion,

t ransf orms t o a ferrite phase, h a v i n g a m u c h lower ca rb on content, and also
c e m e n t i t e , w i t h a m u c h higher carbon concent rat ion . Pearlite is one
microst ruct ural product of transformation
● Temperature plays an important role in the rate of the austenite-to- pearlite
transformation.
● The temperature dependence for an iron–carbon alloy of eutectoid composition
is indicated in Figure , which plots S-shaped curves of the percentage
transformation versus the logarithm of time at three different temperatures.
● For each curve, data were collected after rapidly cooling a specimen composed
of 100% austenite (heated >727C, depending on the composition of Carbon)
to the indicated temperature; maintained at this constant temperature during
the course of the reaction.
● The time required for austenite to pearlite transformation is noted. As the
temperature to which the samples are cooled increases, the time required for
transformation (t) increases (i.e., t 6 0 0 <t 6 5 0 <t 6 7 5 )
TTT Diagram
▪ TTT diagram stands for “time-temperature- transformation” diagram.
▪ It is also called isothermal transformation diagram.
▪ TTT diagrams give the kinetics of isothermal transformations.
▪ The iron-iron carbide equilibrium diagram is having little value in the study of
the steels cooled under non equilibrium conditions.
▪ It has been found in the study of steel that, Austenite is unstable below the
lower critical temperature A1.
▪ Below A1 temperature austenite may transform to pearlite, bainite or
martensite.
▪ It is necessary to know that, How these transformation occurred.

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• This diagram indicates the phases existing in steel of
a specific composition at various temperatures and
times.
• It is helpful to obtain desired microstructure and hence
to design properties of the alloy.
Continuous Cooling Transformation (CCT) Diagram
• A cooling curve is drawn with the experimentally determined data by
placing a thermocouple at a definite location in steel sample and then
measuring the variation of temperature with time.
• Since the coordinates of the TTT and CCT diagram are same those for a
cooling curve.
• It is possible to superimpose variation cooling curve on them.

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• In interpreting this diagram, note first that the eutectoid temperature [727C] is
indicated by a horizontal line; at temperatures above the eutectoid and for all
times, only austenite will exist.
• The austenite-to-pearlite transformation will occur only if an alloy is super cooled to
below the eutectoid, the time necessary for the transformation to begin and then end
depends on temperature.
• The start and finish curves are nearly parallel, and they approach the eutectoid line
asymptotically. To the left of the transformation start curve, only austenite (which is
unstable) will be present, whereas to the right of the finish curve, only pearlite will exist.
• In between, the austenite is in the process of transforming to pearlite, and thus both
microconstituents will be present.
• The transformation rate at some particular temperature is inversely proportional to
the time required for the reaction to proceed to 50% completion (to the dashed line
in Figure ).
• That is, the shorter the time, the higher is the rate. Thus, at temperatures just below the
eutectoid (corresponding to just a slight degree of undercooling) very long times (on the
order of 10 5 s) are required for the 50% transformation, and therefore the reaction rate
is very slow.
• The transformation rate increases with decreasing temperature such that at 540C only
about 3 s is required for the reaction to go to 50% completion.
● At temperatures just below the eutectoid, relatively thick
layers of both the -ferrite and Fe3C phases are produced; this
• microstructure is called c o a r s e pearlite,
● At these temperatures, diffusion rates are relatively high, such
t hat during the transformation carbon atoms can diffuse
relatively long distances, which results in the formation of thick
lamellae.
● With decreasing temperature, the carbon diffusion rate
decreases, and the layers become progressively thinner.
● The t h in-lay ered st ructu re produced is termed fine
pearlite.
● Fine pearlite leads to better hardness and strength
• Ba i nite
• In addition to pearlite, other microconstituents that
are products of the austenitic transformation exist;
one of these is called bainite.
• The microstructure of bainite consists of ferrite and
cementite phases, and thus diffusional processes are
involved in its formation.
• Bainite forms as feather or needles or plate like
cementite
Differentiate between bainite and pearlite
• Bainite leads to more strength and hardness
compared to pearlite.
• This is due to smaller ferrite particles.
• There will be an increase in strength associated
decrease in ductility
• The t i m e – t e m p e r a t u r e dependence of t he bainite transformation
can be represented on t he isothermal transformation diagram.
• It occurs a t temperatures below those a t which pearlite forms; begin-,
end, and half-reaction curves are just extensions of those for t he
pearlitic transformation.
• The isothermal transformation diagram for an iron–carbon alloy of
eutectoid composition t h a t has been extended t o lower temperatures.
• All three curves are C-shaped and have a “ n o s e ” a t point N, where t he rate
of transformation is a m a x i m u m .
• Pearlite forms above the nose [i.e., over the temperat ure range of about 540
t o 727 C, a t temperatures bet ween about 215 and 540 C, bainite is t he
transformation product.
• Temperatures just below t he nose TTT curve is called u p p e r bainite wit h
feathery cement it e appearance.
• At lower temperatures, t he cement it e grains become too fine and an acicular
needle like pat t ern is observed. This is lower bainite which is also called
acicular bainite.

U p p e r bainit e Acicular bainite

● On rapid cooling (quenching) to low temperatures ( < 2 1 5 C), the
austenite transforms to another microstructure called Martensite.
● Martensite forms when the rate of cooling is rapid enough to
prevent diffusion.
● The formation of martensit grains nucleate and grow at a very rapid
rate.
● Being a nonequilibrium phase, martensite does not appear on the iron–iron carbide phase
diagram.
● The austenite-to-martensite transformation is, however, represented on the
isothermal transformation diagram.
● The martensitic transformation is diffusionless and instantaneous, it is not depicted in
this diagram as the pearlitic and bainitic reactions.
● The beginning of this transformation is represented by a horizontal line designated
M(start). Two other horizontal and dashed lines, labeled M(50%) and M(90%), indicate
percentages of the austenite-to-martensite transformation.
● The temperatures at which these lines are located vary with alloy composition but,
nevertheless, must be relatively low because carbon diffusion must be low.
● The horizontal and linear character of these lines indicates that the martensitic
transformation is independent of time; it is a function only of the temperature to which
the alloy is quenched or rapidly cooled.
● Transformation to martensite an a t h e r m a l t ransfor mat i on.
• In martensite transformation, a sudden orientation of carbon
and iron atoms from FCC solid solution (Austenite) into a body
centered tetragonal (BCT) solid solution happens here.
• Compared to other microstructures observed in steel,
martensite is the strongest and hardest.
• These properties are due to the presence of Interstitial
carbon atoms.
• The interstitial impurities acts as barriers to dislocation
motion.
Critical Cooling Rate
• The minimum rate of continuous cooling just sufficient to prevent undesired
transformations.
• For steel, the slowest rate at which it can be cooled from above the upper
critical temperature to prevent the decomposition of austenite at any
temperature above when Martensite forms (MS), around 315°C.
• When cooling curve tangent to the nose of TTT curve, it is called as critical
cooling rate(CCR).
• CCR can be defined by two ways ‘The slowest cooling rate at which unstable
austenite can be transformed into martensite.’
• ‘The faster cooling rate or within minimum time at which unstable austenite
can be transformed into perlite.’

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Critical Cooling Rate

43
Factors influencing Cooling Rate
✓Carbon content.
✓Austenite temperature.

1) Carbon content:-
▪ With higher carbon content or alloying element, decrease critical cooling
rate and shift TTT curve towards right.
▪ It rated the transformation of austenite to perlite or bainite.

2) Austenite temperature:-
▪ Higher the austenitic temperature, it will coarsen the structure and make it
softer.
▪ Higher austenitic temperature gives lower critical cooling time and increase
CCR.

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