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CHAPTER 9

PHASE EQUILIBRIA
& PHASE DIAGRAMS
9.1

COMPONENTS AND PHASES

9.2

ONE-COMPONENT SYSTEMS

9.3

TWO-COMPONENT SYSTEMS

9.4

9.3.1

Solubility in the Solid State

9.3.2

Specification of Composition

9.5

9.6

9.7

BINARY ISOMORPHOUS SYSTEM
9.4.2

Determination of Phases Present

9.4.3

Determination of Phase Compositions

9.4.4

Determination of Phase Amounts

9.4.5

Solidification Under Equilibrium
Conditions

9.4.6

Non-Equilibrium Solidification

9.4.7

Mechanical Properties of
Isomorphous Alloys

9-1

BINARY EUTECTIC SYSTEM
9.5.1

Solidification of Eutectic Alloy

9.5.2

Solidification of Off-Eutectic Alloy

9.5.3

Alloys Without Eutectic Reactions

9.5.4

Mechanical Properties of Eutectic
Alloys

OTHER BINARY SYSTEMS
9.6.1

Invariant Reactions in Binary Systems

9.6.2

Complex Binary Phase Diagrams

IRON-IRON CARBIDE (FE-FE3C) SYSTEM
9.7.1

Transformations in Eutectoid Steels

9.7.2

Transformations in Hypoeutectoid Steels

9.7.3

Transformations in Hypereutectoid Steels

9.7.4

Mechanical Properties of Steels

9-2

9.1 COMPONENTS AND PHASES

• Note that the phases in a material refer not only to the
gaseous, liquid and solid states; within the same material,

• Most engineering materials are mixtures of elements

regions

of

different

composition,

different

crystal

and/or molecular compounds. Each element and/or

structures, or crystalline as opposed to amorphous, are

compound in the mixture is known as a component,

considered different phases, e.g. BCC iron is a distinct and

which is defined as a chemically distinct and essentially

separate phase from FCC iron.

indivisible substance; e.g. Fe, Si, NaCl, H2O.

• Microstructure is the structure of a material on the

• Material mixtures may be physical mixtures, in which the
components are unchanged chemically and remain as the
same identifiable entities. More often however, the
components interact chemically to form new constituents
or phases.

microscopic scale. It is characterized by the phases present,
their relative amounts, the composition and structure of each
phase, and size, shape and distribution of the phases.
• The microstructure depends on the overall material
composition, the external temperature and pressure, and
thermal

• A phase is a region of material that has the same
composition and structure throughout, and is separated

processing

history

of

the

material.

The

microstructure of a material has a profound influence on its
properties.

from the rest of material by a distinct interface. A phase
• A phase diagram is a graphical representation of the

may contain one or more components.

stable phases present, and the ranges in composition,
temperature, and pressure over which the phases are

• Some everyday examples of components and phases:
Material(s) present
Water
Water & ice
Salt & water
Excess salt & water

No. of components
1 (H2O)
1 (H2O)
2 (NaCl & H2O)
2 (NaCl & H2O)

No. of phases
1 (liquid)
2 (liquid & solid)
1 (salt solution)
2 (saturated solution &
solid salt)

stable.
• A phase diagram describes the equilibrium (lowest energy)
state of a system: the compositions, structures and
amounts of the equilibrium (stable) phases do not vary
with time.

9-3

9-4

9.2 ONE-COMPONENT SYSTEMS

9.3 TWO-COMPONENT SYSTEMS

• Unary (1 component) system; e.g. H2O (Fig. 9.2-1).

• When

two

components

are

mixed,

they

may

be

completely soluble, partially soluble or insoluble in each
other, or react to form a new compound (Fig. 9.3-1).

Fig. 9.2-1 Schematic phase diagram for H2O.

• The stable phase (whether ice, water or steam) depends on
the temperature and pressure.
• Phase boundaries separate the 3 different regions over
which each phase is stable; the boundaries also indicate
conditions under which 2 phases coexist.
• Under very restricted conditions, all 3 phases coexist (triple
point).

Fig. 9.3-1 Two component mixtures in the liquid state.

• The phase diagram identifies the stable phase(s) at any
given pressure and temperature.
9-5

9-6

which the solute atoms substitute 4. The solubility of solubility are expressed by the Hume-Rothery rules: uniformly and randomly dispersed throughout.3-3 Interstitial solid solution. • If the solute and solvent atoms are solution. solid an extent only.2 Fig. The original crystal structure is maintained. Crystal structures must be the same.3. in which the solute atoms CA = weight (mass) of A x 100 reside in the interstitial spaces total weight between solvent atoms (Fig. Difference in atomic radii < 15%. of moles no.3. of moles of A = x 100 at% no.3-3). excess solute may combine with the percent (at%). of moles of A + no. the Periodic Table to prevent compound formation. an solution is Specification of Composition Composition is specified in weight percent (wt%) or atom • If the solute atom is much smaller than • The necessary (but not sufficient) conditions for unlimited 2. the composition of A is: formed. 9.9. the interstitial solvent solid atom.3-2 Substitutional solid solution. a substitutional is interstitial atoms is always limited (rule 1 below). CA = no. In a system containing components A and B. Valences must be the same. 9-7 weight of A x 100 weight of A + weight of B ! ! wt% wt% at% total no. solvent to form a separate new phase. of moles of B 9-8 .1 Solubility in the Solid State • Limited solubility: solute atoms dissolve in the solvent to • A solid solution is a homogeneous single phase formed by the incorporation of solute atoms (either substituting for solvent atoms or in interstitial sites) into a host crystal. in 3. Must belong to the same group or adjacent groups in of similar size. 9. with solute atoms formed. 9. = ! Fig. 9. for the solvent atoms (Fig. 1. of moles of A x 100 ! • Unlimited solubility: the components form a substitutional solid solution when mixed in any amounts.3-2). 9.

Cu-Ni (Fig. solid solution !. at all other points. the solid phase is stable.4 BINARY ISOMORPHOUS SYSTEM • The left edge of the phase diagram represents pure Cu (100wt%Cu-0wt%Ni). in both liquid and solid states. the variables are now the temperature (vertical accompanied by changes in the relative amounts and axis) and composition of the alloy (horizontal axis). At all other compositions containing both Cu and Ni.g. there is complete solubility (isomorphous) of 2 components (binary) over the entire composition range 100wt%Ni). 9. and 2-phase ! + L. while below the solidus. • Within single-phase fields (L or !). the temperature may be varied without changing the equilibrium phase or its composition. e. are then of interest. the liquid phase is stable. Above the liquidus. their compositions and their relative amounts. so the only external variable is temperature. • There are three distinct phase fields: liquid L. 9. melting/solidification occurs over a temperature range. • Melting/solidification in pure Cu and Ni occurs isothermally at unique melting temperatures. changes in temperature are 1 atm).e. • In 2-phase fields (! + L). the effects of temperature on the phases present. • Since most materials are used under constant pressure (i. the right edge pure Ni (0wt%Cu- • In this system.4-1). In between these boundaries. Fig. compositions of ! and L (details later). liquid and solid coexist.9. • The composition of an alloy is usually fixed.4-1 The Cu-Ni phase diagram. there are varying amounts of Cu and Ni. 9-9 9-10 .

T0 (this point of interest is known as the state point) and see which phase field (single phase L. denoted as !. an alloy with composition 60wt%Ni40wt%Cu at 1100°C (point A) is a single-phase solid solution of Cu in Ni. point A). The compositions of the phases are given by the horizontal coordinates (on the composition axis) of these intersections.4-2 Determining phase compositions in any 2-phase field. Extend an isotherm (known as the tie line) at C0 at temperature T0. through the state point. • If the point lies in a single-phase field (e.4-1) with the coordinates C0.g. 9-11 9-12 . 2. The composition of each phase depends on the temperature.4-2) is located in the 2-phase (! + L) field. while a 35wt%Ni65wt%Cu alloy at 1250°C (point B) consists of both solid ! and liquid phases. 3. the phase composition is identical to the overall alloy composition C0. Note the intersections between the tie line and the phase boundaries on either side. 9. • For example. 9.2 Determination of Phases Present • To find the composition of each phase in any 2-phase field: • To identify the phases present for an alloy of composition 1. and across the diagram (Fig.4.4. locate the point on the phase temperature T0. point B).3 2-phase field. the compositions of the liquid L phase and the solid ! phase are CL and C!.9. respectively.g. Fig. • For example. !. point B Determination of Phase Compositions (Fig 9. 9. the phase compositions differ from each other and also from the original overall alloy composition C0. • Locate the state point on the phase diagram (Fig.4-1). or 2-phase ! + L) the point lies in. 9. • When the point lies in a 2-phase field (e.

Locate the overall alloy composition C0 on the tie line. 9. !ƒ! = M" = o Mo C# " C L ML = C" # C o Mo C" # C L Mass fraction of L phase.9.4-4 Schematic illustration of the lever rule. • If the point lies in a 2-phase field (e. the amount of the single phase is 100%. 2.4-3 Determine phase amounts in any 2-phase field using the lever rule.4-3 & 9. The tie line may be thought of as a ‘lever’ pivoted at alloy composition C0 (Fig.!ƒL = ! ! Fig. 3.4-1). The mass fraction of Fig.4-4). 9. Mass fraction = Mass of phase = Opposite lever arm Total mass Total lever length C " CL ! Mass fraction of ! phase.4. point B). any phase is proportional to the length of the opposite lever arm. the relative amounts of the phases are calculated by the lever rule: 1.g.4 Determination of Phase Amounts • Locate the state point on the phase diagram (Fig. 9. Draw a tie-line through the state point. ! 9-13 9-14 . • If the point lies in a single-phase field (e.g. point A). 9.

Mass fraction of L. Fig. At 1270°C.0. 1.4-6 Tie line at 1250°C for determining phase amounts using lever rule.38 = 0. and 1200°C. 9.ƒL = 1.77 = 0.Worked Example Using the lever rule: Determine the phases. ƒ = Co " CL = 40 " 32 = 0. 9.23 (23%) ! C# " C L ! ! ! ! 50 " 37 (or simply.38 (38%) C" # C L 45 " 32 Mass fraction of !. their compositions and relative amounts in a 40 wt%Ni-60wt%Cu alloy at 1300°C.0.4-5 Tie lines and phase compositions for a 40 wt%Ni-60wt%Cu alloy at several temperatures.4-6) Mass fraction of L. 1250°C.62) As above Read directly 9-15 9-16 . ƒL = C" # Co = 50 " 40 = 0. 9.77 (77%) C" # C L 50 " 37 Mass fraction of !.ƒL = 1. 1. Temperature Phase Composition (wt%Ni) Amount (%) 1300 L 40 100 Read directly 77 Draw tie-line – read from intersection with liquidus (for L) and solidus (for !) L 37 1270 1250 1200 ! 50 23 L 32 38 ! 45 62 ! 40 100 Fig.62 (62%) ! C# " C L ! ! ! ! 45 " 32 (or simply. ƒL = C" # Co = 45 " 40 = 0. 1270°C. Remarks Use lever rule for phase amounts (Fig. 9.4-6). ƒ = Co " CL = 40 " 37 = 0.23) At 1250°C (Fig.

C0) • Point b: solidification starts at the liquidus temperature Phases: L (35%Ni) + ! (46%Ni) Amounts:<100% L + > 0% ! • Point c: the proportion of ! increases.4.9. 9.4-7): • Point a: 100% liquid L Phase: L (35 wt% Ni = alloy composition.4-7 The development of microstructure during the equilibrium solidification of a 35 wt% Ni-65 wt% Cu alloy. 9. following the liquidus and solidus respectively Phases: L (32%Ni) + ! (43%Ni) Amounts: 73% L + 27% ! • Point d: solidification is almost complete at the solidus temperature Phases: L (24%Ni) + ! (35%Ni) Amounts: > 0% L + < 100% ! • Point e: 100% solid ! Phase: ! (35%Ni = alloy composition.5 Solidification Under Equilibrium Conditions Consider the cooling of an alloy of composition 35 wt%Ni65wt% Cu from 1300°C (Fig. C0) Fig. the compositions of L and ! change with temperature. 9-17 9-18 .

cooling is too fast for the diffusing atoms to establish equilibrium phases and compositions in the solid state (Fig. the overall ! composition is higher than the solidus and does not follow the solidus Fig. A cored structure is obtained after solidification. C0) • Point b’: solidification starts at the liquidus temperature Phases: L (35%Ni) + ! (46%Ni) • Point c’: the diffusion in liquid L is assumed to be rapid enough for the composition of L to follow the liquidus. Since diffusion is too slow for the ‘old’ ! to reach the ‘new’ ! composition of 40%Ni. in most practical situations. Phases: L (29%Ni) + ! (40%Ni!C!!46%Ni.6 Non-Equilibrium Solidification • During solidification. 9. • Point a’: 100% liquid L Phase: L (35%Ni = alloy composition. These changes are accomplished by diffusion.9. the composition of ! and L changes constantly according to the solidus and liquidus as the temperature drops. overall C!"42%Ni) 9-19 9-20 .4-8). the composition of the ‘new’ layer of ! (40%Ni) formed is different from the ‘old’ ! (46%Ni) formed earlier at point b’. however.4-8 The development of microstructure during the non-equilibrium solidification of a 35 wt% Ni-65 wt% Cu alloy. 9.4. Since diffusion in solids is usually very slow.

overall C!"35%Ni"Co) • The shift of the solidus from the equilibrium depends on the cooling rate. • Point f’: 100% solid ! Phase: # with cored structure as a result of segregation (i. 9-21 9-22 . overall C!"38%Ni) compositions. (a) solid solution strengthening with alloying addition.4-9). 9. but its ductility will exhibit the opposite trend (Fig. • The component with the higher melting point segregates at the centre of the solid while regions between the grains are rich in the lower-melting point component. more liquid 9. This coring phenomenon causes hot shortness. 9.• Point d’: because of the shift in the solidus.4-9 For the copper-nickel system.e. where regions around the grain boundaries melt before the equilibrium solidus temperature of the alloy is reached. but (b) opposite trend in ductility. the strength of the alloy will be a maximum.7 Mechanical Properties of Isomorphous Alloys remains than in the equilibrium case Phases: L (24%Ni) + • Since isomorphous alloys form a single solid phase at all ! (35%Ni!C! !46%Ni. the non-equilibrium variation in composition within a phase) (31%Ni!C!!46%Ni. overall C!"35%Ni) • At some intermediate composition.4. Fig. each component will experience solidsolution strengthening by additions of the other component [note that grain-size strengthening is also possible in polycrystals]. • Point e’: solidification is almost complete Phases: L (21%Ni) + ! (31%Ni!C!!46%Ni. Faster cooling results in greater deviation.

e. • At the eutectic point. i.3 wt% at 183°C.2 wt%. 9-24 . E (Fig.. CE. • When an alloy of eutectic composition. it exists only at a specific temperature and alloy composition that cannot be varied.9. • An alloy of eutectic composition. !. a eutectic reaction occurs: L cooling """"""""# !" """" heating !+" • During the eutectic reaction. forming singlephase solid solutions ! and " respectively.. while that of a hypereutectic alloy is higher than the eutectic composition.e. • The composition of a hypoeutectic alloy is lower than the • For all other intermediate alloy compositions. temperature lower than the melting points of either • Sn is soluble in Pb up to maximum 18. The eutectic point is invariant.5-1). The eutectic isotherm represents the lowest temperature at which the liquid phase exists. as seen in other alloy compositions. CE.5-1) from the 2-phase ! + " solid region. The eutectic point is similar to the triple point in one-component systems. 9. melting/solidification occurs isothermally at one temperature instead of over a range of temperatures. component.5 BINARY EUTECTIC SYSTEM • The solvus separates the single phase solid regions (! or ") • In this system. " and L coexist in equilibrium. Pb-Sn (Fig. melts/solidifies at a Fig. 9-23 eutectic composition. 9. a 2-phase mixture of ! + " exists. The solvus corresponds to the solubility limit of Pb in Sn and vice versa.g. 9. CE. while Pb is soluble in Sn up to 2. is cooled through the eutectic temperature.5-1 The Pb-Sn phase diagram. the two components are only partially soluble in the solid state.

5-5 Schematic illustration of various eutectic structures: (a) lamellar.5-4). Fig.1 Solidification of Eutectic Alloy • During the eutectic reaction. • Point h: 100% liquid L Phase: L (61.9 wt% Sn (Fig. 9. 9.5-2 The development of microstructure in a eutectic alloy.5-4 The eutectic lamellae structure in the Pb-Sn system.5-2): redistributed via diffusion to form simultaneously a high Pblow Sn ! phase and a low Pb-high Sn " phase.8%Sn) Fig. and (d) acicular. 9.3%Sn) + " (97. 9.5-3 Simultaneous diffusion of Pb and Sn atoms to form eutectic lamellae.9%Sn) !183°C !!!!" ! (18.9.5. (b) rodlike. • Point i: 100% solid (overall composition = CE = 61. 9. Fig.3%Sn) + " (97. • Alternating layers (lamellae) of ! and " are formed because such a structure requires Pb and Sn atoms to diffuse only over relatively short distances (Figs.5-3 and 9.9%Sn) Phases: eutectic ! (18. (c) globular. CE) • Eutectic point: eutectic reaction L (61. 9. Pb and Sn atoms must be Consider the cooling of an alloy of eutectic composition 61.9%Sn = eutectic composition. Fig.8%Sn) lamellae 9-25 9-26 .

• Point j: 100% liquid L • To determine the relative amount of eutectic ! (i. Fig. ! Phase: L (40%Sn = overall composition) • Point k: ! solidifies and increases in proportion as the alloy cools. the compositions of L and ! increase with decreasing temperature. the lever rule is applied in the 2-phase ! + L region at point l. the remaining L undergoes the eutectic reaction and transforms to the composition 40 wt% Sn (Fig.5-6 The development of microstructure in a hypoeutectic alloy.9. using the composition of ! at one end of the tie-line and the composition of " at the other end. This gives the total amount of !. at the other end. therefore. just above the eutectic temperature.5. 9-27 9-28 . • To determine the relative amount of proeutectic !. following the liquidus and solidus respectively mixed in the eutectic ! + " lamellae).e.5-6): eutectic ! + " lamellae.9%Sn) + ! (18.8%Sn) lamellae • The ! that forms prior to the eutectic reaction is known as proeutectic or primary !.3%Sn) + eutectic ! (18. • Point m: 100% solid (overall composition = 40%Sn) Phases: proeutectic ! (18. the lever rule is first applied in the 2-phase ! + " region at point m. just below the eutectic temperature. 9. Phases: L (47%Sn) + ! (16%Sn) eutectic ! = total ! – proeutectic !. CE.2 Consider Solidification of Off-Eutectic Alloy the cooling of an alloy of hypoeutectic • Point l: Phases: L (61. to distinguish it from the eutectic ! lamellae formed during the eutectic reaction.3%Sn) • Just below the eutectic temperature. using the composition of ! at one end of the tie-line and the eutectic composition. 9.3%Sn) + " (97.

184°C and 182°C and 0°C. proeutectic ! (from 184°C) = 74%. their compositions and relative amounts in a 30 wt%Sn-70wt%Pb alloy at 300°C. 9. i. • Only alloys with compositions exceeding either maximum solid solubility limits at the eutectic temperature. with microstructure and solidification characteristics identical to the isomorphous alloys (Fig.5-7). Total ! @ 182°C = 86%. • Alloys within the solubility limit at room temperature form a single-phase solid solution.3 Worked Example Alloys Without Eutectic Reactions Determine the phases. 9. undergo the eutectic reaction during solidification. Fig.e.8 wt% Sn.9. $ eutectic ! @ 182°C = 86-74 = 12% 9-29 9-30 . 18.5.5-7 Solidification in an alloy of composition C1. 200°C. which lies within the roomtemperature solubility limit This alloy does not undergo a eutectic reaction.3 wt% Sn < C0 < 97.

The compositions of ! and " will change with decreasing temperature. the compositions of L and ! increase with decreasing temperature. " particles precipitate within !. This alloy does not undergo a eutectic reaction. 9-31 9-32 .5-8 Solidification and precipitation in an alloy of composition C2. following Fig. with the " precipitates growing in size as the alloy cools. following the liquidus and solidus respectively Phases: L + ! • Point f: 100% solid ! (C2%Sn = overall composition) • Point g: solid solubility of ! is exceeded upon crossing the solvus.• Alloys exceeding the solubility limit at room-temperature. but within the maximum solubility limit at the eutectic temperature forms a two-phase microstructure that has a different morphology (size/shape/distribution) from the two-phase microstructure containing the eutectic. their respective solvus.5-8): • Point d: 100% liquid L Phase: L (C2%Sn = overall composition) • Point e: ! solidifies and increases in proportion as the alloy cools. 9. but is dispersed within a matrix of ! 100% solid (overall composition = C2%Sn) Phases: ! + " (non-lamellae dispersion) • Because the solubility of ! drops with temperature. 9. the mass fraction of " increases. " does not form lamellae with !. Consider the cooling of an alloy of composition C2 wt% Sn (Fig.

Fig.5-9). the greater the strengthening effect. 9.5-9 The effect of composition and strengthening mechanism on the strength of lead-tin alloys. 9. • The maximum number of interphase boundaries in a slowly solidified eutectic alloy occurs when the microstructure is wholly eutectic. 9-33 9-34 .9.4 Mechanical Properties of Eutectic Alloys • The boundary between the two phases (also known as interphase boundary) is an obstacle to dislocation motion – the greater the number of boundaries. thus. the larger the amount of eutectic. the stronger the alloy (Fig.5.

". 9.. • The components in a binary system may react chemically to form intermediate phases.6 OTHER BINARY SYSTEMS 9. All invariant reactions are reversible if cooling/heating is carried out under equilibrium conditions.2 • Intermediate solid solutions exist over a range of compositions.6. 9. & (Fig. 9. which are single phases formed at alloy compositions away from the ends of the phase diagram.6-2).6-2 The Cu-Zn phase diagram. 9. 9-35 9-36 .6. Fig. shown as straight lines Complex Binary Phase Diagrams on the phase diagram.6-2). • The solid solutions ! and # are called terminal solid solutions because they appear at the ends (terminus) of the phase diagram (Fig. Fig. $. e. i. Mg2Ni and MgNi2 (Fig.6-1 Some important three-phase reactions in binary systems.g.6-3). Intermediate com- pounds have fixed compositions.e. 9.9. 9. 9.1 Invariant Reactions in Binary Systems Fig. %.6-3 The Mg-Ni phase diagram.

9-37 during the eutectoid reaction. tough and ductile.7 IRON-IRON CARBIDE (FE-FE3C) SYSTEM • Peritectic reaction at 1493°C (important for casting): %+L cooling """"""""# !" """" heating $ • Eutectic reaction at 1147°C (important for cast irons): L cooling """"""""# !""""" heating $ + Fe3C • Eutectoid reaction at 727°C (important for the heat treatment of steels): cooling $ """"""""# !""""" heating ! + Fe3C • Ferrite (!): solid solution of carbon in BCC iron (max.9. solubility = 2. austenite. soft and ductile. • Although Fe3C forms one terminus of the phase diagram. the composition is still measured in terms of wt% C. 9. • Fe3C is an intermediate compound of iron and carbon. • Cementite (Fe3C): intermediate compound of 4 C and 12 Fe atoms (6. by convention and for convenience. solubility = 0.7-1 Fe-Fe3C phase diagram. hard and brittle.67 wt%C). cementite and pearlite are used in the Fe-Fe3C system only.67 wt% C = 100 wt% Fe3C. and is represented by a straight line at the right terminus of the metallic-covalent bonding.022 wt% C at 727°C). • The terms ferrite. orthorhombic crystal structure with • This system forms the basis for steels and cast irons. Fig. • Pearlite: 2-phase mixture of alternating layers (lamellae) of ferrite and cementite (! + Fe3C) formed simultaneously phase diagram. 6. • Austenite ($): solid solution of carbon in FCC iron (max.14 wt% C at 1147°C). 9-38 .

7-3 and 9.76%C) • Eutectoid point: eutectoid reaction: $ (0. • During the eutectoid reaction.67%C) lamellae 9-39 9-40 . 9.7-3 Schematic representation of pearlite formation (arrows indicate direction of C diffusion).7-2). Fig. • Point a: 100% $ (0.7-4). 9. Fig.7-4 Pearlite in eutectoid steel.1 Transformations in Eutectoid Steels Consider the cooling of a eutectoid steel (0. C atoms must be redistributed by diffusion such that $ (0.9.022%C) and high-C Fe3C (6.022%C) + Fe3C (6.67%C) Fig. 9.7-2 The development of microstructure in a eutectoid steel. • Point b: 100% pearlite eutectoid ! (0.67%C) simultaneously. 9. 9. consisting of alternating layers of # (light phase) and Fe3C (thin layers that look dark). • Alternating layers (lamellae) of ! and Fe3C are formed because such a structure requires C atoms to diffuse only over relatively short distances (Figs.76%C) 727°C !! !!!" ! (0.022%C) + Fe3C (6.7.76 wt% C) from 800°C (Fig.76%C) is transformed to low-C ! (0.

7.67%C) } • Point i: Phases: proeutectoid Fe3C (6.7.022%C) + pearlite Fe3C (6. composition C0 (< 0.67%C) • Point e: Phases: ! (0.022%C) + eutectoid ! (0.022%C) + $ (0. • Point c: all $ (compositionC0) • Point g: all $ (composition C1) • Point d: proeutectoid ! • Point h: proeutectoid Fe3C forms along $ boundaries forms along $ boundaries and increases in pro- and increases in portion as the steel proportion as the steel cools. the compositions cools. according to Phases: ! (0.3%C) Phases: $ (1. $ (0. to the eutectoid ! + Fe3C pearlite. temperature. that of $ decreases with according to the solvus.022%C) + the solvus.76 wt% C) from 875°C.76%C) undergoes the eutectoid reaction and transforms to the eutectoid ! + Fe3C pearlite.9.0%C) + Fe3C (6.67%C) + eutectoid ! (0.022%C) + Fe3C (6.2 Transformations in Hypoeutectoid Steels • Consider the cooling of a hypoeutectoid steel of 9. the composition of of ! and $ increase with Fe3C remains constant but decreasing temperature. • Point f: Phases: proeutectoid ! (0. the remaining $ • Just below the eutectoid temperature.76%C) • Just below the eutectoid temperature.67%C) 9-41 } pearlite 9-42 . the remaining $ (0.76%C) undergoes the eutectoid reaction and transforms (0.76 wt% C) from 915°C.3 Transformations in Hypereutectoid Steels • Consider the cooling of a hypereutectoid steel of composition C1 (> 0.

Fig. (b) ductility and impact energy with carbon content for plain carbon steels with fine pearlite structure.7-7). 9. 9-43 . cementite. • In addition. such that dislocation movement can occur only within the ferrite phase. which contains complex metalliccovalent bonding. Therefore. the greater the strengthening.7. 9. the more cementite a steel contains (i. the higher its strength (Fig.e.9. the higher the carbon content).4 Mechanical Properties of Steels • The interphase boundary between ferrite and cementite is an obstacle to dislocation movement – the greater the number of boundaries. does not undergo plastic deformation at room temperatures.7-7 (a) Variation of strength and hardness.

CHAPTER 10 10. the time required).1 10. The phase diagrams do not indicate the time required for equilibrium microstructures ISOTHERMAL TRANSFORMATION DIAGRAMS 10.3 Growth diagrams are obtained only when the temperature is 10. crystal structure and/or the number of phases present. • Under non-equilibrium conditions.2 Hypoeutectoid and Hypereutectoid Steels to develop.1. The transformation from one phase to another involves a change in composition. CONTINUOUS COOLING TRANSFORMATION DIAGRAMS 10.1 Transformations in Eutectoid Steel 10. Continuous Cooling in Steels • The desired microstructure may be therefore be tailored by controlling the rate (kinetics) of phase transformations.2 10. which PHASE TRANSFORMATIONS requires a finite amount of time. 10-1 10-2 .1 KINETICS OF PHASE TRANSFORMATIONS • Phase PHASE TRANSFORMATIONS transformations are not instantaneous.1 The Driving Force for Transformation 10.2 Nucleation 10.2. This is achieved through the 10.3 rearrangement of atoms (often via diffusion).1 These factors also determine the rate of phase transformation (and hence.1.4 Kinetics of Phase Transformation changed extremely slowly. 10.3.1. the resultant microstructure depends on the rate of heating/cooling and the actual temperature at which phase transformations occur.2.1. such that a state of equilibrium • The microstructures characterized by the equilibrium phase is maintained at all times.

The system can lower its free energy by changing water into ice (Gice . 10-3 10-4 .1-1 Gibbs free energy as a function of temperature for ice and water. TE – T = !T is known as the undercooling. which is a measure of the internal !G = 0). A change from water to ice or vice versa would not lower G. followed by the growth of the new phase.1 The Driving Force for Transformation • At the equilibrium transformation temperature.e. becomes larger and larger as T falls further and further below TE. i. and the higher the driving force. 10. TE = 0°C. The greater the degree of undercooling. Fig. the larger the magnitude of !G. • !G may be thought of as the ‘driving force’ for the • Consider the solidification of water into ice (Fig.10.Gwater < 0 " !G < 0). • Generally. as well as the randomness in the system. !T. • When T < TE. !G. • Phase transformations are only possible if such changes lower G. The decrease in free energy. !G < 0.1-1).1. 10. so ice is the stable form. energy. G. at which G is a minimum. the free energy of ice and water are equal (Gice = Gwater " • The thermodynamic state of a system is defined by the Gibbs free energy. so no spontaneous change occurs. a phase transformation begins with the nucleation of the new phase within the parent phase. transformation. Gice < Gwater. • Equilibrium is a state of no spontaneous change.

purely by chance. nucleation becomes easier and the nucleation rate is faster with larger !T.1-2). • The net nucleation rate is therefore a balance between the ease of nucleation and atomic mobility (Fig. in order to remain stable and grow. or larger. • An increase in the degree of undercooling. !T.1-3 Variation of the net nucleation rate with temperature. r*. r*. The atoms in a liquid are in a state of continual random movement. a small group of atoms will. Since there is a higher probability of atoms randomly clustering in small groups rather than large ones. 10-5 10-6 .1-3). 10. nuclei smaller than r* would simply redissolve back into the liquid. the random clustering of atoms requires the local diffusion of atoms.1-2 The random clustering of neighbouring atoms to form a crystal nucleus. preferential nucleation sites include grain boundaries. In solid-tosolid phase transformations.1.2 Nucleation • However. phase boundaries. 10. The maximum nucleation rate occurs in the temperature range where the driving force for nucleation and diffusion are both significant. From time to time. Fig. the rate of which decreases with • Consider the nucleation of a solid in a liquid during solidification. and the surfaces of impurities and precipitates. 10. • Nucleation occurs preferentially at sites such as walls of containers or suspended impurities in a liquid. come together to form a tiny crystal nucleus (Fig. temperature.10. decreases the critical nucleus size. Fig. dislocations. 10. • The nucleus must be of critical size. required.

10. (b) Corresponding time-temperature-transformation curve or C-curve (Note: time. 1 ). 3. 10.10.3 Growth • The progress of a phase transformation with time at any • Once a nucleus of critical size or larger forms. The growth rate of the new phase decreases eventually Fig. and there is a rapid increase in the amount of new phase present. Once nucleated. 10. Transformation is slow initially as nuclei form.1-5).1-4). spontaneous and sustained growth of the nucleus occurs (Fig. 4. t # Rate because of the depletion of solute atoms or physical 10-7 10-8 impingement of the growing phase. . given temperature is described by a sigmoidal (S-shaped) curve (Fig. Fig.1-6 The fraction of transformed material as a function of time at any given temperature.4 Kinetics of Phase Transformation • The overall rate (or kinetics) of phase transformation depends on both nucleation and growth rates (Fig. • Characteristics of phase transformation: 1. 10. 2. An incubation period is required for nucleation. These processes are diffusion-controlled.1-5 (a) Variation of rate of phase transformation with temperature.1-4 Growth of a stable nucleus. There is no measurable phase transformation during this period. 10. and the growth rate increases with temperature. 10. Fig. 10.1.1. the new phase begins to grow at the expense of the parent phase. Growth involves the transport of atoms to the nucleus and the rearrangement of these atoms into the crystal structure of the nucleus.1-6).

2-1 Construction of a TTT diagram from a series ofexperimental sigmoidal curves at different temperatures.76 wt% C) (Figs. 10-9 10-10 .1 Transformations in Eutectoid Steel • Recall the eutectoid reaction in steel: ! !727°C !!!!" " + Fe3C • The upper (high-temperature) portion of the TTT diagram for eutectoid steels (0.2-1). each diagram is valid for one alloy composition only. when the steel is quenched (cooled rapidly) from the austenite • Isothermal transformation (IT) diagrams. 10. show the progress of transformation with time. which may be different from that characterized by the equilibrium phase diagrams. 10. In practical situations.2-2 Isothermal transformation of austenite to pearlite as a function of time and temperature. Fig.2-2 & 10. the rate of heating/cooling and the actual temperature of transformation (undercooling) determine the resultant microstructure. or timetemperature-transformation (TTT) diagrams. • TTT diagrams are derived from a series of experimental sigmoidal curves at different temperatures (Fig. and the final phase field and held isothermally at various temperatures below the eutectoid transformation temperature.2 I SOTHERMAL T RANSFORMATION D IAGRAMS • Equilibrium phase diagrams define only the microstructures that develop under equilibrium conditions.10.2. 10. 10.2-3) shows the decomposition of austenite to pearlite with time. 10. microstructure (including non-equilibrium phases). Fig.

2-3 The isothermal transformation of austenite to pearlite.2-4a). 10.• Above the eutectoid temperature. consisting of thick layers of ferrite and cementite with large interlamellar spacing (Fig 10. the austenite is in the process of distances quickly) produces coarse pearlite.2-4 (a) Coarse pearlite. only austenite (unstable) will be present. Fig. depends on the actual temperature of transformation. Fast nucleation (many grains) but slow diffusion (diffuse short distances only) yields fine pearlite. and small interlamellar spacing (Fig 10. showing the development of microstructures. thus both will be present.2-3). 10. with thin layers of ferrite and cementite. 10-11 10-12 . • As undercooling increases. the morphology (size and shape) of pearlite • The solid curves define the onset and completion of the transformation of austenite to pearlite. to the right of the finish curve. slow nucleation (few grains) but fast diffusion (carbon atoms diffuse over long • To the left of the start curve. • Since the transformation to pearlite during the eutectoid transformation from austenite to pearlite will occur only if reaction involves redistribution of carbon atoms via the steel is cooled below the eutectoid temperature. 10. (b) fine pearlite. diffusion. Fig. transformation to pearlite occurs earlier. • Near the eutectoid temperature. while the dashed curve represents 50% completion (Fig. incubation becomes faster and transforming to pearlite. only pearlite will exist.2-4b). In between. only austenite will exist.

However.2-6). phases upon cooling. 10.2-6 Bainite formed at (a) 450°C.2-5). 10. the pearlite or bainite remains stable upon further Fig. • Once a portion of austenite has transformed to pearlite or bainite. 10-13 10-14 . elongated cementite particles transformations occur. which is unstable below the eutectoid temperature. 10. 10. bainite due to differences in the temperature at which their consists of extremely fine. It is not possible for the pearlite to transform directly into bainite. is able to transform to other.2-7). 10. Fig. which is lamellar. Only austenite. without first reheating to form austenite. 10. or vice versa. which affect the nucleation and between ferrite plates or needles (Fig.2-7 Coarse pearlite remains stable upon cooling. as indicated in the equilibrium phase diagram. Unlike pearlite. both pearlite and bainite are still physical mixtures of ferrite and cementite. more stable. which is • The distribution and morphology (size and shape) of the an even finer distribution of ferrite and cementite than in ferrite and cementite phases in pearlite and bainite differ fine pearlite. cooling (Fig. and (b) 260°C. Fig. growth kinetics of ferrite and cementite.• Further undercooling produces bainite (Fig.2-5 The TTT diagram for eutectoid steel showing the transformation of austenite to pearlite and austenite to bainite.

Fig.• Immediately prior to the eutectoid transformation.2-8).2-11). • Since carbon atoms are trapped in the BCT structure.2-8 The complete TTT diagram for eutectoid steel. Fig. 10. not time.022 wt% C) and high-carbon cementite (6. 10. the amount of austenite that transforms to martensite depends solely on temperature.2-9 The relationship between FCC austenite and BCT martensite (c>a). Martensite begins to form only when austenite is quenched to temperature Ms.2-9 and 10.2-10 The BCT unit cell of martensite produced by the distortion of the BCC unit cell by interstitial carbon atoms. martensite has the same composition as its parent austenite (0. 10. The transformation of austenite to pearlite the BCC structure of ferrite into BCT (Figs.76 wt% C. Fig. while the M50 isotherm indicates the temperature at which 50% of austenite will transform to martensite (Fig. 10. with carbon atoms because carbon atoms remain trapped in the octahedral dissolved in the octahedral interstitial sites of the FCC interstitial positions of the original FCC austenite and distort austenite lattice. 10. • Unlike the transformation to pearlite and bainite.76 wt% C in the case of eutectoid steel). the diffusive transformation to ferrite and cementite is suppressed. and a diffusionless transformation to non-eqiuilibrium martensite takes place (Fig. • When undercooling becomes so great (isothermal transformation temperature below Ms) that carbon diffusion cannot occur. 10. or bainite requires the diffusion of carbon atoms to form low-carbon ferrite (0.67 wt% C) simultaneously. 10-15 10-16 . • Martensite has a BCT (body-centred tetragonal) structure austenite contains 0.2-10).

quenching to temperatures between Ms and MF in these steels result in untransformed austenite remaining amidst the martensite as retained austenite. 6.3-5) of cementite particles within ferrite. it is stable with time at room temperature.2-13) due to its much finer distribution (Fig. (Sec. complete (100%) transformation to atoms. stable phases of ferrite and cementite. 10. 10. but upon reheating (in a process known as tempering). However.2-12 Hardness of martensite and pearlite as a function of carbon content. • Martensite is metastable. 10.• The Ms. Fig.2-11). 10. M90 (or MF) temperatures are not fixed. martensite may require a subzero quench to below MF 10. it tends to be brittle. Fig. known as tempered martensite.2-12) as a result decrease with increases in the carbon content of the steel. martensite will decompose to the even more Fig.e.2-11 The amount of martensite formed when steel is quenched to room temperature depends on Ms and MF. but • Martensite is the hardest phase in steel (Fig. (Fig. M50.2-13 Hardness and strength of bainite and pearlite as a function of isothermal transformation temperature. • Bainite is generally harder and stronger than pearlite 10. i. of the lattice distortion caused by the trapped carbon In some steels. 10-17 10-18 .

and is completed at about 500 s. timing for the remaining 50% austenite is reset to zero. and quench to room temperature. of the TTT diagram. beginning after about Determine the final microstructure (in terms of microconstituents 10 s.Worked Example (a) At 350°C. rapid cooling to 400°C is fast enough such that virtually no transformation occurs during cooling. the present and approximate percentages) of a small specimen of specimen is 100% bainite. Therefore by 103s. 4 (a) Rapidly cool to 350°C. At 400°C. after 100 s. and quench to room temperature. so that the final microstructure is roughly 100% martensite. (b) At 250°C. the kinetics (nucleation/growth behavioiur with time) of austenite transformation is unique. because at each temperature. most of this transformation is completed (past the M90 line). hold for 10 s. even though cooling occurs through pearlite and bainite regions of the TTT diagram. For the remaining 50% austenite. (c) At 650°C. and then though the final quenching passes through the martensite region subjected to the following treatments. the remaining 50% of the specimen is 100% bainite. Quenching through the martensite region of the TTT diagram. which does not transform further. Austenite transforms to bainite. hold for 20 s. (b) Rapidly cool to 250°C. and is completed at about 100 s. hold for 100 s. Therefore. (c) Rapidly cool to 650°C. At room temperature. 10-19 10-20 . which does not transform further upon cooling. beginning after about 4 s. which does not transform further upon cooling. only about 50% of the specimen has transformed to pearlite. Final microstructure: 50% pearlite + 50% bainite. austenite transforms to bainite. beginning after about 7 s. bainite transformation has not yet begun. and quench to room temperature. even eutectoid steel that has been heated to its austenite phase. more and more austenite transforms to martensite as temperature drops. rapidly cool to 400°C. austenite transforms to pearlite. by 104 s. After 20 s. so the specimen is still 100% austenite. hold for 103 s.

10. the amount • When hyporeutectoid and hypereutectoid steels are of proeutectoid phase that forms depends on the cooled. no proeutectoid phase is formed. Fig. 10.2-14 and 10. cementite.2. • When the undercooling is so large that bainite or martensite is obtained.2-14 TTT diagram for a hypoeutectoid steel (0. respectively. More proeutectoid phase is formed when and the isothermal transformation temperature is high. 10-21 10-22 . The formation of proeutectoid ferrite or cementite adds an extra curve to the TTT diagram above the pearlite “nose” (Figs 10. Fig.2-15). showing an extra curve due to proeutectoid ferrite formation.5 wt% C) and its corresponding portion of the Fe-Fe3C phase diagram.2 Hypoeutectoid and Hypereutectoid Steels • Since the transformation of austenite to the proeutectoid phases requires the diffusion of carbon atoms. austenite first transforms to proeutectoid ferrite undercooling. 10.13 wt% C).2-15 TTT diagram for a hypereutectoid steel (1. before the eutectoid transformation to pearlite.

10. 10-23 10-24 . Like the TTT diagrams. • CCT diagrams are derived from a series of experimental sigmoidal curves at different cooling rates. Fig. transformations occur during continuous cooling to room temperature.1 CONTINUOUS COOLING T R A N S F O R M A T I O N D I A G RA M S Continuous Cooling in Steels • Because the temperature is constantly decreasing when • Strictly speaking. • In practice.10. TTT diagrams are valid only for the steel is cooled continuously. • There is no longer any bainite formation when cooling continuously at any given constant cooling rate because all the austenite will have transformed to pearlite by the time bainite transformation becomes possible.3. in which the material is longer times and lower temperatures when compared to assumed to be instantaneously quenched from a single- TTT diagrams (Fig. 10. CCT curves are shifted to isothermal transformations.3-1 Comparison of TTT and CCT diagrams for eutectoid steel.3-1). phase field to a specific temperature and held isothermally for various times to produce different amounts of the transformed products. it is more accurate to use continuous-coolingtransformation (CCT) diagrams. • Therefore. in which the temperature is constantly changing as the transformation progresses. each CCT diagram is valid for one alloy composition only.3 10.

10. structure (if cooled below MF). 10-25 10-26 .3-3 Critical cooling rate for a fully martensitic structure. The remaining austenite that does not transform to pearlite at the higher temperatures will begin to transform to martensite when the Ms temperature is reached.3-2 Different cooling rates produces different microstructures. When cooling within this range. Fig. • Slow cooling produces coarse pearlite while moderately fast cooling produces fine pearlite (Fig. • There is a critical cooling rate (140°C in Fig. It represents the minimum cooling rate that will avoid pearlite formation and produce a fully martensitic Fig.3-2). 10. 10.• The transformation from austenite to pearlite occurs over a range of temperatures rather than at a single temperature. 10. there is insufficient time to complete the austenite-to-pearlite transformation (since the cooling curves does not reach the pearlite finish curve on the right). 10.3-3) that will just miss the “nose” at which the pearlite transformation begins.3-3) over which both pearlite and martensite are produced. • There is a range of cooling rates (between 35 to 140°C/s in Fig.

assuming MF (or at least M90) is reached. (a) From Fig. the final microstructure is likely to be coarse pearlite.3-3 1°C/s lies to the far right of the CCT diagram. where nucleation is slow. which is the fastest cooling rate possible in order to still obtain 100% pearlite. and (d) 175°C/s. 10-27 . but growth is slower. at which there is no time for diffusion to occur. so the final microstructure is approximately 100% martensite. (b) 20°C/s. (b) 20°C/s lies closer to the cooling curve of 35°C/s. because diffusion becomes too slow at lower temperatures. nucleation is faster. The remaining austenite transforms to martensite when cooled through the martensite region of the CCT diagram. Final microstructure is a mixture of fine pearlite and martensite. For a faster cooling rate. 10. (d) 175°C/s is faster than the critical cooling rate of 135°C/s. (c) 50°C/s.Worked Example Determine the final microstructure of a small specimen of eutectoid steel that has been cooled from its austenite phase to room temperature at the following rates: (a) 1°C/s. but growth is fast. but the rapid drop in temperature means that the transformation from austenite to pearlite cannot be completed. pearlite nucleation and growth occurs. the final microstructure is likely to be fine pearlite. (c) 50°/s lies in the region of split transformation on the CCT diagram – at high temperatures.