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

AUSTENITE iron phase – Austenite is a high temperature phase and has a Face Centred Cubic (FCC) structure (which is a close packed structure).  At the highest temperatures.  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.  The iron-carbon diagram provides a solid base on which to build the knowledge of both plain carbon and alloy steels. ?-iron is having good strength and toughness but it is unstable below 723 deg C. ductile and has low strength and good toughness.028 wt% C at 727 deg C and austenite (?-iron) can dissolve 2.The diagram shown the actually shows two diagrams i) the stable iron-graphite diagram (dashed lines) ii) Metastable fe-fe3c diagram. At the low-carbon end is the ferrite (?-iron) and austenite (?-iron). the phases available in the simple binary Fe-C system are also available in the alloy steels. FERRITE iron phase – It is relatively soft low temperature phase and is a stable equilibrium phase. but it is essential to examine the effects of the alloying elements on the formation and properties of these phases. There are some important metallurgical phases and micro constituents in the iron carbon system.  At the carbon-rich side there is cementite (Fe3C). Many of the basic features of this irpn carbon system also influence the behavior of alloy steels. the liquid phase field can be found and below this are the two phase fields liquid & austenite. Ferrite is a common constituent in steels and has a Body Centred Cubic (BCC) structure iron is soft . Some important boundaries at single-phase fields have been given special names that facilitate the understanding of the diagram. such as ferrite & cementite. In heat treating of steels. . MAIN MICRO-STRUCTURES OF IRON AND STEELS IN EQUILIBRIUM ARE 1.11 wt% C at 1148 deg C. liquid & cementite. 2.  Ferrite can at most dissolve 0. austenite & cementite. Between the single-phase fields are found regions with mixtures of two phases.  For example. and liquid & ferrite. the liquid phase is always avoided  . and ferrite & austenite.

 It is super saturated solution of C atoms in ferrite. It has a complex orthorhombic structure and is a metastable phase.  It is having good strength and toughness. It is a partially soluble solution of Fe and C. PEARLITE Is the ferrite-cemented phase mixture. MARTENSITE  Martensiteis formed by rapid cooling and is hard and brittle. It has a characteristic appearance and can be treated as a micro structural entity or micro constituent.  Upper bainite is formed at higher temperatures has a feathery appearance. In case of non-equilibrium solidification of Fe-C system the following main micro structures may be formed. good compression strength and low toughness 4. It is hard. 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. non lamellar mixture of ferrite and cementite on an extremely fine scale.  It has a bct structure and a hard metastable phase.  The hardness of bainite increases with decreasing temperature of formation. brittle and has low tensile strength.0 wt % C and mixture of those in between. It has high strength and low toughness.  It is having high strength and hardness and low toughness. It has lath morphology when 1. SORBITE / TROOSTITE . It is a eutectoid and has BCC structure.3. BAINITE  Bainite is a phase between pearlite and marten site.  Lower bainite is formed at lower temperatures has an acicular appearance. It is hard metastable micro constituent. It is intermediate compound of Fe and C. CEMENTITE It is Fe3C or iron carbide.

with the c being derived from the French chaffing. but no change in crystal structure is involved. Ae3 are the temperatures of phase changes at equilibrium.ferrite transformation . The austenite. All of the changes. the Fe3C boundary (Pearlite boundary). C for pure iron. The carbon content at which the minimum austenite temperature is attained is called the eutectoid carbon content (0.  Ar4 is the temperature at which delta ferrite transforms to austenite during cooling. occur at lower temperatures during cooling than during heating and depend on the rate of change of temperature. except the formation of martensite. which is 723 Deg.  Ar3 is the temperature at which austenite begins to transform to ferrite during cooling.  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.  Ac3 is the temperature at which transformation of ferrite to austenite is completed during heating.  Arcm is the temperature when in hypereutectoid steel.  Accm is the temperature when in hypereutectoid steel at which the solution of cementite in austenite is completed during heating.  Ar1 is the temperature at which transformation of austenite to ferrite or to ferrite plus cementite is completed during cooling. with the r being derived from the French refroidissant. 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. Aecm.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. 1390 Deg. the temperature at which precipitation of cementite starts during cooling. This temperature is 769 Deg.  Ms (or Ar”) is the temperature at which transformation of austenite to martensite starts during cooling. C in the diagram A1 is called eutectoid temperature and is the minimum temperature for austenite.77 wt% C). that is. Ae1.  Ac1 is the temperature at which austenite begins to form during heating.  Mf is the temperature at which martensite formation finishes during cooling.  The A4 temperature at which austenite transforms to ?-iron.  The A1 temperature at which the eutectoid reaction occurs.

and are.03 to1. who correctly assumed it to be a lamellar mixture of iron and iron carbide. and the growth of side plates or Widmanstaten cementite follows the same pattern. despite the fact that the orientation relationship with austenite is a more complex one. therefore. most of the side plates originate from grain boundary allotriomorphs. the metastable equilibrium between iron and iron carbide is normally considered. but takes place between 910 Deg. It was discovered by Sorby over a century ago. In commercial steels. C. but it is not difficult to distinguish ferrite from cementite morphologically. pearlite nodules can nucleate on inclusions. by quenching from the austenitic state to temperatures below the eutectoid temperature Ae1. Lamellar eutectoid structures of this type are widespread in metallurgy. pro-eutectoid ferrite will form in iron-carbon alloys containing up to 0. Pearlite is a very common constituent of a wide variety of steels.  As in the case of ferrite. it is usually difficult to obtain this equilibrium phase in steels (0.8 per cent carbon.  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. ferrite can be formed down to temperatures as low as 600 Deg. However. Cementite is metastable as the true equilibrium is between iron and graphite. C and 723 Deg.  It may be seen that the normal Iron carbon equilibrium diagram represents the metastable equilibrium between iron and iron carbide. Pearlite nuclei occur on austenite grain boundaries.  For example. the same principles apply to the formation of cementite from austenite.  The cementite plates are more rigorously crystallographic in form. C in pure iron. since it is relevant to the behavior of a variety of .  C in iron-carbon alloys. but it is clear that they can also be associated with both pro-eutectoid ferrite and cementite. where it provides a substantial contribution to strength.5 wt per cent carbon). although in each case there will be variations due to the precise crystallography of the phases involved. These structures have much in common with the cellular precipitation reactions. which it should be emphasized apply in general to hypo-and hyper-eutectoid phases. Both types of reaction occur by nucleation and growth.  There are pronounced morphological changes as the transformation temperature is lowered. but in the cementite reaction more side plates nucleate at twin boundaries in austenite. The reaction occurs at 910 Deg. diffusion controlled. Therefore. and frequently pearlite is used as a generic term to describe them. Under equilibrium conditions.The austenite-pearlite reaction  Pearlite is the most familiar micro structural feature in the whole science of metallography. Although graphite occurs extensively in cast irons (2 to 4 wt per cent carbon).

which result on cooling in the formation of Cementite. ferrite is normally associated with cementite in one or other form. .67% C. The diagram below shows shows the phases present when when Fe-C alloys (C up to 7%) are cooled from liquid to solid.05 to 1. 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. The ferrite phase is restricted with a maximum carbon solubility of 0. Similarly. A "Phase" is a form of material having characteristic structure and properties.5 wt per cent. C. It is a form of the material which has identifiable composition. 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 notes are based on the Iron Phase Diagram (equilibrium diagram ). This is a intermetallic compound (iron carbide-Fe3 C) which although not 100% stable is but is to all practical purposes a stable phase. C.02 wt per cent at 723 Deg. This high solubility of carbon in austenite is extremely important in heat treatment. steels in practice. structure and boundaries separating it from other phases in the material volume.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 ?- phase is very restricted and is in the temperature range between 1390 and 1534 Deg. The left side of the diagram represents pure iron and the right hand of the diagram represents an alloy with 6. Since the carbon range available in common steels is from 0. C and disappears completely when the carbon content reaches 0. The phase diagram shown is therefore a meta-stable phase.

Iron Forms Iron can exist in three forms: α.. BCC crystal with crystal dimension a = 2..8% C and 0.65 Angstrom exists at temperature range 910oC to 1403oC δ..86 Angstrom exists at temperatures up to 910oC γ.77% C. BCC crystal with crystal dimension a = 2... FCC crystal with crystal dimension a = 3.93 Angstrom exists at temperature range 1403oC to 1535oC SOLID PHASES The phased diagram includes four solid phases α FERRITE  The solid solution of carbon in iron .Note: Different reference sources indicate the Eutectoid point at 0..

 At 0% C this is pure iron.  The difference in solubility between the austenite and α Ferrite is the basis for the hardening of steels CEMENTITE  This is an intermetallic compound which contains 6.008%.  The solubility reaches a maximum of 2.09% at 1495oC.  At 0 oC temperature the solubility falls to 0.02% at 723oC.  This has no real practical significance in engineering. .  The carbon atoms are located in the crystal interstices. The maximum solubility of carbon in iron is 0. AUSTENITE  The solid solution of carbon in γ iron is called austenite ..  This is a solid solution of carbon in iron and has a BCC crystal structure.  The solubility decreases to 0.  BCC crystal structure.8% at 723 oC The carbon atoms are dissolved interstitially.  Cementite is a hard brittle compound with and orthorhombic crystal structure each unit cell has 12 Fe atoms and 4 C atoms Δ FERRITE.  This has a FCC crystal structure with a high solubility for carbon compared with α ferrite.08% at 1148oC .67% C and 93.  The maximum solubility or C in Fe is 0.3% Fe. 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.

2% C are very brittle.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.8% then the solid is a hypereutectoid steel.80% C at 723oC ) Wt% Ferrite = 100 (6.  Few steels are made with carbon contents over 1.0.8.0.  If the carbon content is more then 0.Applying the lever rule to the eutectoid point (0.8)/ 6.67. .2%.67.0.  Hypereutectoid steels with carbon content over 1.02) = 88% Wt% Cementite = 100 (0.02) /6.67 -0.

As calculated above pearlite consists of 88% (mass) ferrite and 12% (mass) cementite  Transformation of a hypereutectoid steel (> 0. Transformation of a hypoeutectoid steel (< 0.  If this solid is then slowly cooled the entire structure will change to a lamellar structure of alternate plates of ferrite and cementite. 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.8% C ) will result in pearlite in a matrix of α Ferrite. .  This structure is called pearlite because of its mother-of-pearl appearance.8% C) will result in pearlite in a matrix of cementite.

stronger and tougher than ferrite-pearlite structures at lower temperatures. as above coarse pearlite is formed.  It can be seen that if the transformation is allowed to take place at a higher temperature then.  If the test piece is cooled rapidly at a temperature between 220oC and 525oC a phase structure between pearlite and martensite is formed. held for a time and then water quenched.  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. and Transformation) curve for a eutectoid steel test piece which has been rapidly cooled in a bath at a set temperature. Temperature. Bainite is harder.  (Featherlike constituent in upper temperature range and lens like in the lower temperature range).  If the test piece is cooled to a lower temperature in a bath a finer pearlitic structure results. This is called Bainite  BAINITE  Bainite is a constituent which forms from austenite in a temperatures range below 530 oC and above Ms .  Bainite is like pearlite a mixture of ferrite and iron carbide but in a different form. MARTENSITE . The bainite structure varies from a featherlike pattern to pattern of lens shaped particles depending on the temperature range of formation.  Martensite is a supersaturated solid solution of carbon in ferrite. also called a TTT (Time.TRANSFORMATION ON HIGH COOLING RATES Below is an Isothermal Transformation (IT) diagram. Bainite forms together with pearlite in steel which are cooled somewhat too fast to form a complete pearlite structure.

as would be inferred from its thermodynamic properties.  The pure product has an odor that is somewhat pleasing and ethereal in nature.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. and will change to a yellowish color in a few days if left in diffuse sunlight PHYSICAL CONSTANTS FOR CARBON DISULFIDE : . Ms varies from 500oC for C <= 0. percent by volume in air.  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.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. carbon disulfide is a rather stable compound. from 1.  The strength of the C–S bond is 131.22 g/100 ml at 22º C. for C < = 1.7 Kcal.  The flash point is –30º C and auto ignition occurs at 100C or even lower under certain conditions. especially if impurities are present.2% the martensite is in the form of well defined thin strips (laths).1% to 200oC for C <= 1. having an explosive range.  Carbon disulfide is highly flammable. Thermally. Its solubility in water is 0. for C <= 0.  There are various types of martensite depending on the carbon content: for C <0.  Martensite is the hardest structure formed from austenite.6% plates of martensite are formed .25 to 50.  It is an effective solvent for many organic compounds. It is a distorted BCC (tetrogonal) it is a body centred tetrogonal structure.  Thus carbon disulfide will flash if the liquid is brought into contact with open steam pipes.  The compound is quite sensitive to light.

580 cal/g-mol  Entropy. and sulfur monochloride (S2Cl2) are used as chlorinating agents.6º C  Boiling Point 46.900 cal/g-mol  Heat of combustion. The reaction proceeds in two steps. 3CS2 + 6 KOH Æ K2CO3 + 2 K2CS3 + H2O With alcoholic alkali.º C 33. g/ml 1. reaction with carbon disulfide takes place readily with the formation of xanthates. Another important reaction is the chlorination of carbon disulfide to produce carbon tetrachloride.6294  Latent heat of fusion. cP (at temp. sulfur dichloride (SCl2).º C).º C). g/ml 1.2632(15) 1.25 º C  Critical volume 1.  Property Numerical Value Freezing Point – 111.3453(0) 0. CS2 + NaOH + C2H5OH Æ SC(OC2H5)(SNa) + H2O Alkali phenolates react with carbon disulfide to form alkali xanthates (sodium cellulose dithiocarbonate).550 cal/g-mol  Heat of formation.3032(15) 0.2916(20) 0. SM 298º K 20.2559(25) 1.84 cal/g-mol  Viscosity. thus formed. as follows: CS2 + 3 Cl2 Æ CCl4 + S2Cl2 CS2 + 2 S2Cl2 Æ CCl4 + 6 S .25) CHEMICAL PROPERTIES: Carbon disulfide reacts to some extent with aqueous alkali to form a mixture of carbonate and thiocarbonate.050 cal/g-mol  Latent heat of vaporization.º C) 0.745 ml/g  Vapor density (air = 1) 2.2931(0)  Density at (temp. H m 1.2250(46. H C 56.25(30) 30.79(40)  Density at (temp. Rcellulose ONa + CS2 Æ SC(ORcellulose)(SNa) The solid xanthate. dyne/cm at temp. is dissolved in caustic soda solution to form “viscose” solution. Chlorine in the presence of iron as a catalyst. Hv 298º K 6. H f 298º K 27.62  Refractive index (25º C) 1. From this solution regenerated cellulose (viscose rayon) is prepared by neutralization with acid.07(20) 33.2660(35)  Surface tension.

CSCl2. OC(NH2)2 + CS2 Æ COS + NH4SCN Carbon disulfide is partially desulfurized by an alkyl mercuric hydroxide. 2 NH3 + CS2 Æ NH2CSSNH4 Sodium dimethyl dithiocarbamate is manufactured by the reaction of carbon disulfide with dimethylamine and caustic.Carbon tetrabromide is formed in a similar fashion by the action of bromine on carbon disulfide. Carbon disulfide reacts with boiling aniline to form thiocarbanilide according to the equation. RMgBr + CS2 Æ RCSSMgBr Æ RCSSH . Treatment of carbon disulfide with chlorine and trace of iodine gives trichloromethanesulfenyl chloride. CS2 + MgO Æ COS + MgS Sulfur trioxide or chlorosulfonic acid oxidizes carbon disulfide according to the following reaction: CS2 + ClSO3H Æ COS + HCl + SO2 + S Urea and carbon disulfide react at 110º C to give carbon oxysulfide and ammonium thiocyanate. Ammonium dithiocarbamate is prepared by the addition of carbon disulfide to a solution of alcoholic ammonia. etc. carbon oxysulfide is formed by heating magnesium oxide with carbon disulfide. as a vulcanization accelerator. This compound is useful as an intermediate of many organic sulfur compounds. CCl3SCl. (CH3)2NH + CS2 + NaOH Æ (CH3)2NC(S)SNa + H2O Carbon disulfide reacts with various compounds to produce carbon oxysulfide. CS2 + RHgOH Æ COS + NH4SCN Dithio acids (RCSSH) are formed from carbon disulfide through reaction with Grignard reagents. RNHCS-SNH3R and R2NCSSNH2R2. Thus. and in synthetic organic pharmaceuticals. CS2 + 2 C6H5NH2 Æ SC(NHC6H5)2 + H2S Thiocarbanilide is used in dyes. carbon disulfide also reacts with primary and secondary amines to give substituted ammonium salts of N-substituted dithiocarbamic acids. Reduction of the latter compound with stannous chloride or tin and hydrochloric acid produces thiophosgene.

MANUFACTURE OF VISCOSE RAYON: Carbon disulfide is used majorly for the manufacture of viscose rayon.Liquid carbon disulfide reacts at 40-50º C with aqueous solutions of sodium azide to form sodium azidodithiocarbonate.waxes and other substances from various materials. Carbon disulfide is also used in the cold vulcanization of rubber and in making rubber accelerators and resins.  The greater part of the carbon disulfide produced today is used as a raw material for the manufacture of regenerated cellulose  . A considerable amount of carbon disulfide is also used in manufacturing carbon tetrachloride. CS2 + H2O Æ COS + H2S USES:  Formerly. the principal use of carbon disulfide was as a solvent for the extraction of oils.  This use. The two major products manufactured from regenerated cellulose are viscose rayon and cellophane  . CS2 + NaN3 Æ NaSCSN3 This reaction has been used to detect small concentrations of carbon disulfide in air or other media. Viscose is manufactured by the action of carbon disulfide and caustic soda on cellulose. have largely replaced carbon disulfide in this field. however has decreased greatly in recent years due to the flammability and toxicity of the compound. fats.  The manufacture of xanthates and the use of carbon disulfide as an insecticide are among other applications of carbon disulfide. including carbon tetrachloride and other chlorinated hydrocarbons such as trichloroethane. .  Other solvents. The main reactions involved in the reduction of carbon disulfide at high temperatures are the following: CS2 + 2 H2 Æ 2 H2S + C CS2 + 4 H2 Æ 2H2S + CH4 At lower temperatures the reduction of carbon disulfide yields various organic sulfur compound. Eg: CS2 + 2 H2 Æ CH2(SH)2 Carbon disulfide reacts almost quantitatively with water vapour at high temperatures to form hydrogen sulfide. 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 Æ —CH2ONa + H2O The alkali cellulose thus formed is aged and treated with carbon disulfide. regenerated cellulose. Manufacture of Carbon Tetrachloride : Carbon disulfide has an advantage in carbon tetra chloride production in that essentially no by products are formed. carbon disulfide is employed in fumigants in admixture with chlorinated hydrocarbons. Carbon disulfide as a fumigant : Various mixtures of carbon disulfide have been used fumigation e. amines and other compounds such as aldehydes. 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. . CH2ONa + CS2 Æ CH2OCSSNa The resulting cellulose xanthate is treated with dilute sodium hydroxide solution to form a colloidal viscose solution which is filtered and aged. 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. In the latter application. with CCl4 and monochlorobenzene emulsions with water etc. Typically. after which carbon disulfide is used to dissolved the remaining free sulfur.g. A large number of patents and publications have appeared which deal with the production of resinous materials from condensation reactions of carbon disulfide. carboxylic acids and isocyanates. The chlorination of methane on he other hand produces other chlorinated methanes and hydrogen chloride as by products. dienes. with pyridine and nitrobenzene. The final product. the wel is first acidized to remove iron salts. with potassium thiocarbonate. carbon disulfide has been used as a solvent in oil wells plugged with wax or with iron sulfide and free sulfur. Recently.