Iron-Iron Carbide Phase Diagram: Effect of Pressure On Allotropy of Iron

Iron-Iron carbide Phase Diagram
Pure iron has two crystalline forms, one BCC, commonly called - iron which remains stable
from low temperatures upto 910C (1414F) when it changes to FCC called iron. The - iron
remains stable upto 1394C (2554F), when it reverts to BCC form now called as - iron, which
is stable upto the melting point of iron (1539C or 2802F).All the allotropic changes give off
heat (exothermic) when iron is cooled and absorb heat (endothermic) when iron is heated.
Effect of pressure on allotropy of iron

Increse in pressure lowers the - Fe to - Fe transition temperature and increses the - Fe to -
Fe traqnsition temperature. This is according to the lechatliers principle as volume of FCC ( -
Fe) is lower than that of BCC. A volume change of FCC to BCC is 8.8%.
Iron Iron carbide diagram
The temperature at which allotrophic change (critical temperatures)

takes place is influenced by alloying elements. The curie
temperature is not effected by alloying elements. Carbon is the most
common alloying element in the iron which significantly affects the
allotrophy, structure and properties of iron. Conventionally, the
complete Fe C diagram should extend from 100% Fe to 100 %
carbon (graphite), but it is normally studied upto 6.67% carbon
(Fe3C) because iron alloys of practical industrial importance contain
not more than 5% carbon. Fe Fe3C is not a true equilibrium
diagram, since Fe3C (meta stable) decomposes into Iron and Carbon
which take a very long time at room temperature and even at 700C
it takes several years to form graphite. When the carbon content
becomes more than solubility limits of iron though carbon should be
present as Graphite (lower free energy than cementite) , yet
cementite forms beacause the formation of cementite is most
probable kinetically i.e. it is easier to from it, as only 6.67% C has to
diffuse to segregate to form cementite whereas 100% C segregation
is required to nucleate graphite..
Definition of structures or phases in Fe Fe 3C diagram

Ferrite: it is an interstitial solid solution of carbon in - iron (BCC). The maximum solubility of
carbon in ferrite is 0.02 wt% at 727C and the minimum is 0.00005 wt% at 20C. the size of the
largest atom that can fit in octahedral void is 0.19 A, which is much smaller than carbon atom
(0.71A). so the solubility is exremely limited. It is soft and ductile. Ferrite is ferromagnetic
upto 768C becomes paramagnetic above this temperature.
Austenite: it is an interstitial solid solution of carbon in - iron (FCC). The maximum solubility
of carbon is 2.1 wt% at 1146C which decreses to 0.77 wt% at 727C. the size of the largest
atom that can fit in octahedral void is 0.52 A. correspondingly the solubility is larger here
compared to ferrite. It is soft, ductile, malleable, tough and non-magenetic. It is stable above
727C in plain carbon steels but can be obtained even at room temperature by adding elements
like Ni or Mn in steels.
- ferrite: it is an interstitial solid solution of carbon in - iron (BCC). The maximum solubility
of carbon is 0.09 wt% at 1495C. it is paramagnetic. It is high temperature version of -iron.
Cementite (Fe3C): It is an interstitial intermetllic compound havinbg fixed carbon content of

6.67wt%. it has a complex orthorhombic structure, with 12 Fe atoms and 4 C atoms per unitcell.
High hardness, brittle, very low tensile strenght and high compressive strength. It is the hardest
phase that appears on the phase diagram.
Ledeburite: it is eutectic mixture of austenite and cementite. It contains 4.3wt% C and is formed
at 1146C. this is very fine mixture.
Pearlite: it is eutectoid mixture of ferrite and cementite containing 0.8wt% C and is formed at
727C. it is a very fine platelike or lamellar mixture.
Invariant reactions in Fe Fe3C diagram

1. Peritectic reaction
Composition wt% 0.09 0.53 0.17
2. Eutectic reaction
3. Eutectoid reaction
Critical temperature in Fe Fe3C diagram

The temperatures at which phase transformations occurs during
heating or cooling an alloy. certain symbols are used to denote the
critical temperature in steels. The upper and lower critical lines
under equilibrium are indicated by Ae3 and Ae1 etc.
It is found that in actual practice the critical line on heating and the critical line on cooling are
not occur at same temperature. The critical line on heating is always higher than the critical line
on cooling. The former is denoted by Ac and the later is denoted by Ar. A for arret (means
arrest), C for chauffage (means heating), R for Refroidissement (means cooling), e for
equilibrium.
If extremely slow rates of heating or cooling are employed then critical temperatures are nearly
equal i.e. Ac1 = Ar1 = Ae1.
The curie temperature (magnetic to non-megnetic change) of cementite is called A0. Ae1 or A1 is
eutectoid tempersture line (727C). Ae2 or A2 is curie temperature line (768C) and this is
constant for all Fe C alloys.
Hypo-eutectoid side
Upper critical temperature (Ae3 , Ac3 , Ar3): It is the temperature at which Austenite to ferrite
transformation begins on cooling (or) at which ferrite to austenite transformation ends on
heating. This is denoted by A3 line. (Ac3 > Ar3)
Lower critical temperature: It is the temperature at which Austenite to ferrite transformation ends
on cooling (or) at which ferrite to austenite transformation starts on heating. (Ac1 > Ar1).
Hypo-eutectoid side
Lower critical temperature (Ae3,1 Ac3,1 Ar3,1) : It is the temperature at which precipitation of
cementite from austenite ends uopn cooling (or) at which dissolution of cementite in austenite
begins upon heating.
Upper critical temperature (Aem , Acm , Arm): It is the temperature at which precipitation of
cementite from austenite begins uopn cooling (or) at which dissolution of cementite in austenite
ends upon heating.
Effect of alloying elements on the Fe C diagram

Ferrite stabilizers: some alloying elements tend to stabilize the ferrite phase in preference to
austenite. Many of these elements have same crystal structure as ferrite (BCC). They reduce the
extent of the austenite area on the equilibrium diagram by forming a gamma loop. Austenite is
enclosed within the loop. eg: Cr, Si, Mo, W, V, Ti etc.
Austenite stabilizers: These enlarge the area of the austenite phase on the phase diagram.
critical amount of these alloying elements results in Austenite even at room temperture. eg: Mn,
Ni, C, N etc.
Effect on eutectoid temperature and composition

Ferrite stabilizers raises the eutectoid temperatute to above 727C, Austenite stabilizers lowers
the euctectoid tempersture to below 727C. Both Ferrite and Austenite stbilizers decrease the
eutectoid composition from 0.77% to lower values.

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How does carbon affect the structure and properties of iron?

What are the different phases present in the Fe-Fe3C diagram?

Iron-Iron carbide Phase Diagram

Effect of pressure on allotropy of iron

Iron Iron carbide diagram

The temperature at which allotrophic change (critical temperatures)

Definition of structures or phases in Fe Fe 3C diagram

Cementite (Fe3C): It is an interstitial intermetllic compound havinbg fixed carbon content of

Invariant reactions in Fe Fe3C diagram

Composition wt% 0.09 0.53 0.17

Composition wt% 4.3 2.11 6.67

Critical temperature in Fe Fe3C diagram

Effect of alloying elements on the Fe C diagram

Effect on eutectoid temperature and composition

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