THE IRON-CARBON PHASE DIAGRAM

In their simplest form, steels are alloys of Iron (Fe) and Carbon (C). The study of the constitution
and structure of iron and steel start with the iron-carbon phase diagram. It is also the basis
understanding of the heat treatment of steels. The Iron Carbon diagram is

Iron Carbon phase diagram

The diagram shown the actually shows two diagrams

i) the stable iron-graphite diagram (dashed lines)

ii) Metastable fe-fe3c diagram.

The stable condition usually takes a very long time to develop specially in the low
temperature and low carbon range hence the metastable diagram is of more interest.
Many of the basic features of this irpn carbon system also influence the behavior of
alloy steels.
For example, the phases available in the simple binary Fe-C system are also available
in the alloy steels, but it is essential to examine the effects of the alloying elements on
the formation and properties of these phases.
The iron-carbon diagram provides a solid base on which to build the knowledge of
both plain carbon and alloy steels.
There are some important metallurgical phases and micro constituents in the iron
carbon system. At the low-carbon end is the ferrite (?-iron) and austenite (?-iron).
Ferrite can at most dissolve 0.028 wt% C at 727 deg C and austenite (?-iron) can
dissolve 2.11 wt% C at 1148 deg C.
At the carbon-rich side there is cementite (Fe3C).
Between the single-phase fields are found regions with mixtures of two phases, such
as ferrite & cementite, austenite & cementite, and ferrite & austenite.
At the highest temperatures, the liquid phase field can be found and below this are the
two phase fields liquid & austenite, liquid & cementite, and liquid & ferrite. In heat
treating of steels, the liquid phase is always avoided
. Some important boundaries at single-phase fields have been given special names
that facilitate the understanding of the diagram.

MAIN MICRO-STRUCTURES OF IRON AND STEELS IN EQUILIBRIUM ARE

1. AUSTENITE

iron phase Austenite is a high temperature phase and has a Face Centred Cubic (FCC)
structure (which is a close packed structure). ?-iron is having good strength and toughness
but it is unstable below 723 deg C.
2. FERRITE

iron phase It is relatively soft low temperature phase and is a stable equilibrium phase.
Ferrite is a common constituent in steels and has a Body Centred Cubic (BCC) structure iron
is soft , ductile and has low strength and good toughness.
3. CEMENTITE

It is Fe3C or iron carbide. It is intermediate compound of Fe and C. It has a complex

orthorhombic structure and is a metastable phase. It is hard, brittle and has low tensile
strength, good compression strength and low toughness

4. PEARLITE

Is the ferrite-cemented phase mixture. It has a characteristic appearance and can be treated as
a micro structural entity or micro constituent. It is an aggregate of alternating ferrite and
cementite lamellae that degenerates (spheroidizes or coarsens) into cementite particles
dispersed with a ferrite matrix after extended holding below 723 deg C. It is a eutectoid and
has BCC structure. It is a partially soluble solution of Fe and C. It has high strength and low
toughness.

In case of non-equilibrium solidification of Fe-C system the following main micro structures
may be formed.

BAINITE

Bainite is a phase between pearlite and marten site. It is hard metastable micro
constituent; non lamellar mixture of ferrite and cementite on an extremely fine scale.
Upper bainite is formed at higher temperatures has a feathery appearance.
Lower bainite is formed at lower temperatures has an acicular appearance.
The hardness of bainite increases with decreasing temperature of formation.
It is having good strength and toughness.

MARTENSITE

Martensiteis formed by rapid cooling and is hard and brittle.

It is super saturated solution of C atoms in ferrite.
It has a bct structure and a hard metastable phase. It has lath morphology when 1.0 wt
% C and mixture of those in between.
It is having high strength and hardness and low toughness.

SORBITE / TROOSTITE
There are many temperatures and critical points in the Iron-C diagram which are important
both from the basic and the practical point of view.

The A1 temperature at which the eutectoid reaction occurs, which is 723 Deg. C in
the diagram A1 is called eutectoid temperature and is the minimum temperature for
austenite.
At the lower-temperature boundary of the austenite region at low carbon contents is
the boundary
Acm is the counterpart boundary for high carbon contents, that is, the Fe3C boundary
(Pearlite boundary). The carbon content at which the minimum austenite temperature
is attained is called the eutectoid carbon content (0.77 wt% C).
The A4 temperature at which austenite transforms to ?-iron, 1390 Deg. C in pure iron
but this temperature is increased as carbon is added
The A2 temperature is the Curie point when iron changes from the ferro to the
paramagnetic condition. This temperature is 769 Deg. C for pure iron, but no change
in crystal structure is involved.
Accm is the temperature when in hypereutectoid steel at which the solution of
cementite in austenite is completed during heating.
Ac1 is the temperature at which austenite begins to form during heating, with the c
being derived from the French chaffing.
Ac3 is the temperature at which transformation of ferrite to austenite is completed
during heating. Aecm, Ae1, Ae3 are the temperatures of phase changes at equilibrium.
Arcm is the temperature when in hypereutectoid steel, the temperature at which
precipitation of cementite starts during cooling, with the r being derived from the
French refroidissant.
Ar1 is the temperature at which transformation of austenite to ferrite or to ferrite plus
cementite is completed during cooling.
Ar3 is the temperature at which austenite begins to transform to ferrite during
cooling.
Ar4 is the temperature at which delta ferrite transforms to austenite during cooling.
Ms (or Ar) is the temperature at which transformation of austenite to martensite
starts during cooling.
Mf is the temperature at which martensite formation finishes during cooling.
All of the changes, except the formation of martensite, occur at lower temperatures
during cooling than during heating and depend on the rate of change of temperature.
The austenite- ferrite transformation
 Under equilibrium conditions, pro-eutectoid ferrite will form in iron-carbon alloys
containing up to 0.8 per cent carbon. The reaction occurs at 910 Deg. C in pure iron, but
takes place between 910 Deg. C and 723 Deg.
C in iron-carbon alloys.
However, by quenching from the austenitic state to temperatures below the eutectoid
temperature Ae1, ferrite can be formed down to temperatures as low as 600 Deg. C.
There are pronounced morphological changes as the transformation temperature is
lowered, which it should be emphasized apply in general to hypo-and hyper-eutectoid
phases, although in each case there will be variations due to the precise crystallography
of the phases involved.
For example, the same principles apply to the formation of cementite from austenite, but
it is not difficult to distinguish ferrite from cementite morphologically.
The austenite-cementite transformation
The Dube classification applies equally well to the various morphologies of cementite
formed at progressively lower transformation temperatures.
The initial development of grain boundary allotriomorphs is very similar to that of ferrite,
and the growth of side plates or Widmanstaten cementite follows the same pattern.
The cementite plates are more rigorously crystallographic in form, despite the fact that
the orientation relationship with austenite is a more complex one.
As in the case of ferrite, most of the side plates originate from grain boundary
allotriomorphs, but in the cementite reaction more side plates nucleate at twin boundaries
in austenite.The austenite-pearlite reaction
Pearlite is the most familiar micro structural feature in the whole science of
metallography. It was discovered by Sorby over a century ago, who correctly assumed it
to be a lamellar mixture of iron and iron carbide.
Pearlite is a very common constituent of a wide variety of steels, where it provides a
substantial contribution to strength. Lamellar eutectoid structures of this type are
widespread in metallurgy, and frequently pearlite is used as a generic term to describe
them.
These structures have much in common with the cellular precipitation reactions. Both
types of reaction occur by nucleation and growth, and are, therefore, diffusion controlled.
Pearlite nuclei occur on austenite grain boundaries, but it is clear that they can also be
associated with both pro-eutectoid ferrite and cementite. In commercial steels, pearlite
nodules can nucleate on inclusions.
It may be seen that the normal Iron carbon equilibrium diagram represents the metastable
equilibrium between iron and iron carbide. Cementite is metastable as the true
equilibrium is between iron and graphite. Although graphite occurs extensively in cast
irons (2 to 4 wt per cent carbon), it is usually difficult to obtain this equilibrium phase in
steels (0.03 to1.5 wt per cent carbon). Therefore, the metastable equilibrium between iron
and iron carbide is normally considered, since it is relevant to the behavior of a variety of
 steels in practice.
On comparing austenite (?-iron) with ferrite (?-iron) it is noticed that solubility of carbon
is more in austenite with a maximum value of just over 2 wt per cent at 1147 Deg. C.
This high solubility of carbon in austenite is extremely important in heat treatment, when
solution treatment in the austenite followed by rapid quenching to room temperature
allows formation of a supersaturated solid solution of carbon in iron.
The ferrite phase is restricted with a maximum carbon solubility of 0.02 wt per cent at
723 Deg. C. Since the carbon range available in common steels is from 0.05 to 1.5 wt per
cent, ferrite is normally associated with cementite in one or other form. Similarly, the ?-
phase is very restricted and is in the temperature range between 1390 and 1534 Deg. C
and disappears completely when the carbon content reaches 0.5 wt per cent

INTRODUCTION

This page includes notes on iron and what happens when iron /carbon mixtures are cooled from
liquid to solid. The notes are based on the Iron Phase Diagram (equilibrium diagram ).

A "Phase" is a form of material having characteristic structure and properties. It is a form of the
material which has identifiable composition, structure and boundaries separating it from other
phases in the material volume.

The diagram below shows shows the phases present when when Fe-C alloys (C up to 7%) are
cooled from liquid to solid.

The left side of the diagram represents pure iron and the right hand of the diagram represents an
alloy with 6,67% C. which result on cooling in the formation of Cementite.

This is a intermetallic compound (iron carbide-Fe3 C) which although not 100% stable is but is
to all practical purposes a stable phase. The phase diagram shown is therefore a meta-stable
phase.
Note: Different reference sources indicate the Eutectoid point at 0,8% C and 0,77% C.

Iron Forms

Iron can exist in three forms:

... BCC crystal with crystal dimension a = 2,86 Angstrom exists at temperatures up to
910oC
... FCC crystal with crystal dimension a = 3,65 Angstrom exists at temperature range 910oC to
1403oC
... BCC crystal with crystal dimension a = 2,93 Angstrom exists at temperature range 1403oC to
1535oC

SOLID PHASES

The phased diagram includes four solid phases

FERRITE

The solid solution of carbon in iron

 At 0% C this is pure iron.
BCC crystal structure.
The maximum solubility of carbon in iron is 0,02% at 723oC.
At 0 oC temperature the solubility falls to 0,008%.
The carbon atoms are located in the crystal interstices.

AUSTENITE

The solid solution of carbon in iron is called austenite .

This has a FCC crystal structure with a high solubility for carbon compared
with ferrite.
The solubility reaches a maximum of 2,08% at 1148oC .
The solubility decreases to 0,8% at 723 oC The carbon atoms are dissolved interstitially.
The difference in solubility between the austenite and Ferrite is the basis for the
hardening of steels

CEMENTITE

This is an intermetallic compound which contains 6,67% C and 93,3% Fe.

Cementite is a hard brittle compound with and orthorhombic crystal structure each
unit cell has 12 Fe atoms and 4 C atoms

FERRITE..

This is a solid solution of carbon in iron and has a BCC crystal structure.
The maximum solubility or C in Fe is 0,09% at 1495oC.
This has no real practical significance in engineering.

LEVER RULE

The lever rule can be applied to any phase region and provides an indication of the proportions
of the constituent parts at any point on the phase diagram.
Applying the lever rule to the eutectoid point (0,80% C at 723oC )

Wt% Ferrite = 100 (6,67 -0,8)/ 6,67- 0,02) = 88%

Wt% Cementite = 100 (0,8- 0,02) /6,67- 0,02) = 12%

STEELS

If the carbon content of the cooled solid is less than Eutectoid (about 0,8% C) the solid is
identified as a hypoeutectoid steel: most steels are this form.
If the carbon content is more then 0,8% then the solid is a hypereutectoid steel.
Hypereutectoid steels with carbon content over 1,2% C are very brittle.
Few steels are made with carbon contents over 1,2%.
 Generally in order to increase the strength of steel other alloying elements are added
which increase the strength while retaining toughness and ductility

A eutectoid solid raised to a temperature just above 723oC and held at this temperature
for some time will become a homogeneous austenite phase.
If this solid is then slowly cooled the entire structure will change to a lamellar structure of
alternate plates of ferrite and cementite.
This structure is called pearlite because of its mother-of-pearl appearance. As calculated
above pearlite consists of 88% (mass) ferrite and 12% (mass) cementite
Transformation of a hypereutectoid steel (> 0,8% C) will result in pearlite in a matrix of
cementite. Transformation of a hypoeutectoid steel (< 0,8% C ) will result in pearlite in a
matrix of Ferrite.
TRANSFORMATION ON HIGH COOLING RATES

Below is an Isothermal Transformation (IT) diagram, also called a TTT (Time, Temperature, and
Transformation) curve for a eutectoid steel test piece which has been rapidly cooled in a bath at a
set temperature, held for a time and then water quenched.

It can be seen that if the transformation is allowed to take place at a higher temperature
then, as above coarse pearlite is formed.
If the test piece is cooled to a lower temperature in a bath a finer pearlitic structure
results.
If the test piece is rapidly cooled to a temperature below a value Ms (which varies with
the carbon content then a new metastable phase is produced called Martensite.
Martensite is a supersaturated solid solution of carbon in ferrite.
If the test piece is cooled rapidly at a temperature between 220oC and 525oC a phase
structure between pearlite and martensite is formed. This is called Bainite

BAINITE

Bainite is a constituent which forms from austenite in a temperatures range below 530 oC
and above Ms . Bainite forms together with pearlite in steel which are cooled somewhat
too fast to form a complete pearlite structure.
Bainite is like pearlite a mixture of ferrite and iron carbide but in a different form. The
bainite structure varies from a featherlike pattern to pattern of lens shaped particles
depending on the temperature range of formation.
(Featherlike constituent in upper temperature range and lens like in the lower temperature
range). Bainite is harder, stronger and tougher than ferrite-pearlite structures at lower
temperatures.

MARTENSITE
 Martensite is the hardest structure formed from austenite. It is a distorted BCC
(tetrogonal) it is a body centred tetrogonal structure.
The distortion is caused by trapped carbon atoms which have not been able to nucleate
into cementite

SOME FEATURES OF MARTENSITE ARE LISTED BELOW

The crystal structure is a stressed structure which is resistance to

dislocation movement it is therefore strong and relatively brittle.
There are various types of martensite depending on the carbon
content:
for C <0,2% the martensite is in the form of well defined thin strips
(laths),
for C <= 0,6% plates of martensite are formed ,
for C < = 1,2% the martensite is in the form of arrays of well defined
plates
The martensite phase initiates at a temperature Ms and is complete at
a temperature Mf.
Ms varies from 500oC for C <= 0,1% to 200oC for C <= 1,2%

PROPERTIES OF CARBON

Properties and Uses Physical properties:

Commercial carbon disulfide often possesses a strong disagreeable and fetid odor due to
the presence of very small amounts of strong smelling organic sulfur compounds.
The pure product has an odor that is somewhat pleasing and ethereal in nature.
Carbon disulfide is highly flammable, having an explosive range, percent by volume in
air, from 1.25 to 50.
The flash point is 30 C and auto ignition occurs at 100C or even lower under certain
conditions.
Thus carbon disulfide will flash if the liquid is brought into contact with open steam
pipes. Its solubility in water is 0.22 g/100 ml at 22 C.
It is an effective solvent for many organic compounds. Thermally, carbon disulfide is a
rather stable compound, as would be inferred from its thermodynamic properties.
The strength of the CS bond is 131.7 Kcal.
The compound is quite sensitive to light, especially if impurities are present, and will
change to a yellowish color in a few days if left in diffuse sunlight

PHYSICAL CONSTANTS FOR CARBON DISULFIDE :

 Property Numerical Value Freezing Point 111.6 C
Boiling Point 46.25 C
Critical volume 1.745 ml/g
Vapor density (air = 1) 2.62
Refractive index (25 C) 1.6294
Latent heat of fusion, H m 1,050 cal/g-mol
Latent heat of vaporization, Hv 298 K 6,550 cal/g-mol
Heat of formation, H f 298 K 27,580 cal/g-mol
Entropy, SM 298 K 20,900 cal/g-mol
Heat of combustion, H C 56.84 cal/g-mol
Viscosity, cP (at temp, C) 0.3453(0) 0.3032(15) 0.2916(20) 0.2660(35)
Surface tension, dyne/cm at temp, C 33.07(20) 33.25(30) 30.79(40)
Density at (temp, C), g/ml 1.2931(0)
Density at (temp, C), g/ml 1.2632(15) 1.2559(25) 1.2250(46.25)

CHEMICAL PROPERTIES:

Carbon disulfide reacts to some extent with aqueous alkali to form a mixture of carbonate and
thiocarbonate,

3CS2 + 6 KOH K2CO3 + 2 K2CS3 + H2O

With alcoholic alkali, reaction with carbon disulfide takes place readily with the formation of
xanthates,

CS2 + NaOH + C2H5OH SC(OC2H5)(SNa) + H2O

Alkali phenolates react with carbon disulfide to form alkali xanthates (sodium cellulose
dithiocarbonate), Rcellulose

ONa + CS2 SC(ORcellulose)(SNa)

The solid xanthate, thus formed, is dissolved in caustic soda solution to form viscose solution.

From this solution regenerated cellulose (viscose rayon) is prepared by neutralization with acid.

Another important reaction is the chlorination of carbon disulfide to produce carbon

tetrachloride.

Chlorine in the presence of iron as a catalyst, sulfur dichloride (SCl2), and sulfur monochloride
(S2Cl2) are used as chlorinating agents.

The reaction proceeds in two steps, as follows:

CS2 + 3 Cl2 CCl4 + S2Cl2 CS2 + 2 S2Cl2 CCl4 + 6 S

Carbon tetrabromide is formed in a similar fashion by the action of bromine on carbon disulfide.
Treatment of carbon disulfide with chlorine and trace of iodine gives trichloromethanesulfenyl
chloride, CCl3SCl. Reduction of the latter compound with stannous chloride or tin and
hydrochloric acid produces thiophosgene, CSCl2.

This compound is useful as an intermediate of many organic sulfur compounds. Carbon disulfide
reacts with boiling aniline to form thiocarbanilide according to the equation,

CS2 + 2 C6H5NH2 SC(NHC6H5)2 + H2S

Thiocarbanilide is used in dyes, as a vulcanization accelerator, and in synthetic organic

pharmaceuticals, etc. carbon disulfide also reacts with primary and secondary amines to give
substituted ammonium salts of N-substituted dithiocarbamic acids, RNHCS-SNH3R and
R2NCSSNH2R2. Ammonium dithiocarbamate is prepared by the addition of carbon disulfide to
a solution of alcoholic ammonia,

2 NH3 + CS2 NH2CSSNH4

Sodium dimethyl dithiocarbamate is manufactured by the reaction of carbon disulfide with

dimethylamine and caustic,

(CH3)2NH + CS2 + NaOH (CH3)2NC(S)SNa + H2O

Carbon disulfide reacts with various compounds to produce carbon oxysulfide. Thus, carbon
oxysulfide is formed by heating magnesium oxide with carbon disulfide,

CS2 + MgO COS + MgS

Sulfur trioxide or chlorosulfonic acid oxidizes carbon disulfide according to the following
reaction:

CS2 + ClSO3H COS + HCl + SO2 + S

Urea and carbon disulfide react at 110 C to give carbon oxysulfide and ammonium thiocyanate,

OC(NH2)2 + CS2 COS + NH4SCN

Carbon disulfide is partially desulfurized by an alkyl mercuric hydroxide,

CS2 + RHgOH COS + NH4SCN

Dithio acids (RCSSH) are formed from carbon disulfide through reaction with Grignard
reagents,

RMgBr + CS2 RCSSMgBr RCSSH

Liquid carbon disulfide reacts at 40-50 C with aqueous solutions of sodium azide to form
sodium azidodithiocarbonate,

CS2 + NaN3 NaSCSN3

This reaction has been used to detect small concentrations of carbon disulfide in air or other
media. The main reactions involved in the reduction of carbon disulfide at high temperatures are
the following:

CS2 + 2 H2 2 H2S + C CS2 + 4 H2 2H2S + CH4

At lower temperatures the reduction of carbon disulfide yields various organic sulfur compound.
Eg:

CS2 + 2 H2 CH2(SH)2

Carbon disulfide reacts almost quantitatively with water vapour at high temperatures to form
hydrogen sulfide,

CS2 + H2O COS + H2S

USES:

Formerly, the principal use of carbon disulfide was as a solvent for the extraction of oils,
fats,waxes and other substances from various materials.
This use, however has decreased greatly in recent years due to the flammability and
toxicity of the compound.
Other solvents, including carbon tetrachloride and other chlorinated hydrocarbons such as
trichloroethane, have largely replaced carbon disulfide in this field.
The greater part of the carbon disulfide produced today is used as a raw material for the
manufacture of regenerated cellulose
. The two major products manufactured from regenerated cellulose are viscose rayon and
cellophane
. A considerable amount of carbon disulfide is also used in manufacturing carbon
tetrachloride. Carbon disulfide is also used in the cold vulcanization of rubber and in
making rubber accelerators and resins.
The manufacture of xanthates and the use of carbon disulfide as an insecticide are among
other applications of carbon disulfide.

MANUFACTURE OF VISCOSE RAYON:

Carbon disulfide is used majorly for the manufacture of viscose rayon. Viscose is manufactured
by the action of carbon disulfide and caustic soda on cellulose. Cotton linters or wood pulp are
steeped with caustic soda solution and then xanthating the alkali cellulose with carbon disulfide.
In the first step the hydroxy methyl group of the cellulose undergoes the following reaction:
CH2OH + NaOH CH2ONa + H2O The alkali cellulose thus formed is aged and treated
with carbon disulfide, CH2ONa + CS2 CH2OCSSNa The resulting cellulose xanthate is
treated with dilute sodium hydroxide solution to form a colloidal viscose solution which is
filtered and aged. The final product, regenerated cellulose, is produced by extruding the aged
solution through suitable orifices into an acid bath (sulfuric acid and sodium sulfate) to form the
regenerated cellulose as filaments or sheeting, sodium sulfate and carbon disulfide. Manufacture
of Carbon Tetrachloride : Carbon disulfide has an advantage in carbon tetra chloride production
in that essentially no by products are formed. The chlorination of methane on he other hand
produces other chlorinated methanes and hydrogen chloride as by products. Carbon disulfide in
the Rubber industry : carbon disulfide is also used in the cold vulcanization of rubber and in
making rubber accelerators and floatation chemicals. A large number of patents and publications
have appeared which deal with the production of resinous materials from condensation reactions
of carbon disulfide, amines and other compounds such as aldehydes, dienes, carboxylic acids and
isocyanates. Carbon disulfide as a fumigant : Various mixtures of carbon disulfide have been
used fumigation e.g, with pyridine and nitrobenzene, with potassium thiocarbonate, with CCl4
and monochlorobenzene emulsions with water etc. Typically, carbon disulfide is employed in
fumigants in admixture with chlorinated hydrocarbons. Recently, carbon disulfide has been used
as a solvent in oil wells plugged with wax or with iron sulfide and free sulfur. In the latter
application, the wel is first acidized to remove iron salts, after which carbon disulfide is used to
dissolved the remaining free sulfur.