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PHASE DIAGRAM

PHASE DIAGRAM Phase Diagram?

● PHASE, SYSTEM & COMPONENT
● INTERPRETATION OF PHASE DIAGRAM
● BINARY PHASE DIAGRAM A graphical representation of the
● REACTIONS IN PHASE DIAGRAM
● DEVELOPMENT IN MICROSTRUCTURE
relationships between
● Fe-Fe3C PHASE DIAGRAM environmental constraints (e.g.,
temperature and sometimes
Presented by pressure), composition, and regions
Dr-Eng. Akhmad A. Korda
of phase stability, ordinarily under
conditions of equilibrium.
Department of Metallurgical Engineering
Faculty of Mining and Petroleum Engineering
Bandung Institute of Technology

PHASE DIAGRAM PHASE DIAGRAM

ALLOY PHASE DIAGRAMS are useful to metallurgists, materials Phase: a homogeneous portion of a system that has uniform
engineers, and materials scientists in four major areas: physical and chemical characteristics.
(1) development of new alloys for specific applications,
Simple example : water (H2O) which can be presented in
(2) fabrication of these alloys into useful configurations, three phases : solid, liquid, vapour/gaseous, depend on
temperature and pressure
(3) design and control of heat treatment procedures for specific
alloys that will produce the required mechanical, physical,
b
and chemical properties, and

pressure
(4) solving problems that arise with specific alloys in their solid liquid
c
performance in commercial applications, thus improving o
product predictability.
a gas

In all these areas, the use of phase diagrams allows research, development, temperature
and production to be done more efficiently and cost effectively.
From ASM Handbook
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PHASE DIAGRAM PHASE DIAGRAM

System: (1) a specific body of material that is being considered, & Solution: a phase with more than one component
(2) a series of possible alloys consisting of the same components.
Solution: liquid solution & solid solution
● One component system, example water
● Two components system (binary system), Exam.: Fe-C, Cu-Zn Solute : one component or element of a solution present in a
● Three components system (ternary system), Exam.: MgO-Al2O3-SiO2
minor concentration. It is dissolved in the solvent.
● Four components system (quaternary system)
Solvent : The component of a solution present in the greatest
amount. It is the component that dissolves a solute.
General system for metal alloys is binary system
Solubility limit : The maximum concentration of solute that may
Component: a chemical constituent (element or compound) of be added without forming a new phase.
an alloy, which may be used to specify its composition.
Solubility limit: unlimited solubility and limited solubility
Example: for brass, its component: Cu and Zn

PHASE DIAGRAM PHASE DIAGRAM

The solubility of sugar (C12H22O11) in a sugar–water syrup.

Unlimited solubility: if the components can dissolve
without second phase formation
Example: Water and alcohol

Limited solubility: if the solute component has limit

solubility
Example: Water and sugar/salt

The solubility influences by temperature and pressure

How about water & oil ? No solubility

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PHASE DIAGRAM PHASE DIAGRAM

Solid solution
The present of subtitutional and interstitial atoms
Solid solution : A homogeneous crystalline phase that contains result in crystal lattice distortion
two or more chemical species.

substitutional solid solution

Solid solid solution strengthening mechanism
solution interstitial solid solutions

interstitial solid solutions

substitutional solid solution

PHASE DIAGRAM PHASE DIAGRAM

Subtitutional solubility & Hume-Rothery rule

William Hume-Rothery
William Hume-Rothery died on 27 September 1968 (b.
1899). He was a British metalurgist, internationally known for For substitutional, solute or impurity atoms replace or substitute for the
his work on the formation of alloys and intermetallic host atoms. There are several features of the solute and solvent atoms
compounds. During WW II, he supervised many government that determine the degree to which the former dissolves in the latter;
contracts for work on complex aluminium and magnesium
these are as follows:
alloys. He established that the microstructure of an alloy
depends on the different sizes of the component atoms, the
valency electron concentration, and electrochemical 1. Atomic size factor. Appreciable quantities of a solute may be accommodated
differences. in this type of solid solution only when the difference in atomic radii between
the two atom types is less than about 15%. Otherwise the solute atoms will
Hume-Rothery rules are an empirical guide to create substantial lattice distortions and a new phase will form.
when two metals are sufficiently similar to be 2. Crystal structure. For appreciable solid solubility the crystal structures for
completely miscible (form a single phase at all metals of both atom types must be the same (FCC with FCC, BCC with BCC).
relative concentrations). They are:
3. Electronegativity. The more electropositive one element and the more
1) Atomic radii no more than about 15% electronegative the other, the greater is the likelihood that they will form an
different. intermetallic compound instead of a substitutional solid solution.
2) Pure metals have the same crystal structure.
3) Atoms have similar electronegativities. 4. Valences. Other factors being equal, a metal will have more of a tendency to
dissolve another metal of higher valency than one of a lower valency.
4) Atoms have the same valence.
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PHASE DIAGRAM PHASE DIAGRAM

Subtitutional solid solution Interstitial solid solution

● An example of a substitutional solid solution is found ● Impurity atoms fill the voids or interstices among the host atoms.
for copper and nickel. ● The higher atomic packing factors, the smaller interstitial positions.
● These two elements are completely soluble in one ● Normally, the maximum allowable concentration of interstitial impurity
another at all proportions. atoms is low (less than 10%).
● With regard to the aforementioned rules that govern ● Even very small impurity atoms are ordinarily larger than the interstitial
degree of solubility: sites, and as a consequence they introduce some lattice strains on the
adjacent host atoms.
 the atomic radii for copper and nickel are 0.128 and 0.125
nm, respectively,
 both have the FCC crystal structure, Carbon forms an interstitial solid solution when added to iron;
 their electronegativities are 1.9 and 1.8 the maximum concentration of carbon is about 2%. The
 the most common valences are +1 for copper (although it atomic radius of the carbon atom is much less than that for
sometimes can be +2) and +2 for nickel. iron: 0.071 nm versus 0.124 nm.

PHASE DIAGRAM PHASE DIAGRAM

Phase Diagram BINARY ISOMORPHOUS SYSTEMS

● Phase diagram : A graphical representation of the relationships between Isomorphous. Having the same crystal
environmental constraints (e.g., temperature and structure or complete solid solubility for
sometimes pressure), composition, and regions of phase all compositions (miscible).
stability, ordinarily under conditions of equilibrium. Example: Cu-Ni binary system

● Equilibrium : if its free energy is at a minimum under some specified Liquidus line. Line or
combination of temperature, pressure, and composition boundary separating liquid and
liquid solid phase regions. The
● Phase equilibrium : The state of a system where the phase liquidus temperature is that
characteristics remain constant over indefinite time temperature at which a solid
periods. At equilibrium the free energy is a minimum. phase first forms under
conditions of equilibrium
● Metastable: Nonequilibrium state that may persist for a very long time cooling.
Solidus line. The locus of points
● Phase diagrams are helpful in predicting phase transformations and the
at which solidification is complete
resulting microstructures, which may have equilibrium or nonequilibrium
upon equilibrium cooling, or at
character.
which melting begins upon
equilibrium heating.
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PHASE DIAGRAM PHASE DIAGRAM

INTERPRETATION OF Cu-Ni Phase Diagram

PHASE DIAGRAMS
1. Determination of present
phases
2. Determination of phase
composition
3. Determination of phase
amount
Schematic binary phase
diagram with a minimum in
the liquidus and a miscibility
1. Determination of
Schematic binary gap in the solid state present phases
phase diagram
showing miscibility in A point :
both the liquid and
solid states Ketercampuran atau 1100°C, 60 wt% Ni
misibilitas adalah sifat
kemampuan dua zat untuk
Phase:  (solid)
bercampur dalam semua
perbandingan (yaitu, saling
Schematic binary phase diagrams with mensolvasi sempurna satu B point :
solid-state miscibility where the liquidus sama lain pada konsentrasi
berapapun), membentuk 1250°C, 35 wt% Ni
shows a maximum (a) and a minimum (b) larutan homogen.
Phase:  (solid) & liquid

PHASE DIAGRAM PHASE DIAGRAM

INTERPRETATION OF PHASE DIAGRAMS INTERPRETATION OF PHASE DIAGRAMS

2. Determination of phase composition 3. Determination of phase amount

Cu-Ni Phase Diagram Cu-Ni Phase Diagram

at A point: at B point:
 (solid), compose of 60 Determine amount of the  solid
wt% Ni & 40 wt% Cu and liquid phase!

Use lever rule method!

at B point:
Phase:  (solid) & liquid

Use tie line (isotherm) method!

Composition at liquid → CL
31.5 wt% Ni and 68.5 wt% Cu

Composition  (solid) → C
42.5 wt% Ni and 57.5 wt% Cu
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PHASE DIAGRAM PHASE DIAGRAM

INTERPRETATION OF PHASE DIAGRAMS Cu-Ni Phase Diagram Microstructural Evolution for Isomorph Alloys

Summary of phases present, phase 1. Equilibrium cooling

composition and phase amount! 2. Nonequilibrium cooling

 Very slow cooling

Equilibrium  Atoms are diffused perfectly
cooling
 In casting generally,
Phases-amount-composition table equilibrium cooling is never
obtained
Phase Phase composition Casting product shows
Phases amount dendritic structure
wt% Cu wt% Ni  Fast enough cooling
(%)
Non-
Liquid 68 0.68 x 68.5 0.68 x 31.5 equilibrium  Atoms are not diffused perfectly
B point
 solid 32 0.32 x 57.5 0.32 x 42.5 cooling  Generally in casting
Total 100 65 35

PHASE DIAGRAM PHASE DIAGRAM

Microstructural Microstructural
Evolution for Isomorph Evolution for Isomorph
Alloys Alloys

Equilibrium cooling for Non-Equilibrium cooling for

Cu – 35% Ni case Cu – 35% Ni case

In nonequlibrium cooling
segregation takes place

Segregation : non uniform

composition in a metallic
object due to nonequilibrium
cooling
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PHASE DIAGRAM PHASE DIAGRAM

Microstructural Evolution for

Microstructural
Isomorph Alloys
Evolution for Isomorph
Alloys Interdendritik microsegregation can be
reduced by homogenization heat
Segregation : non uniform treatment
composition in a metallic
object due to nonequilibrium
cooling Heat treatment is carried out below
nonequilibrium solidus temperature,
Poor quality of cast product then hold for few hours to allow
(different composition, diffusion
different properties)

(a) Interdendritic/micro segregation evolution during

solidification
(b) Segregation photo of Cu – Ni alloy Dendritic microstructure

PHASE DIAGRAM
a) b
) Solidification process
as-
as-cast homog
Cu-Ti enized
1% Cu-Ti
1%

c) d)
as-
as-cast homog
Cu-Ti enized
3% Cu-Ti
3%

Microstructure of (a) as-cast Cu-Ti 1%; (b) as-homogenized Cu-Ti 1%: (c) as-cast Cu-Ti
3% and (d) as homogenized Cu-Ti 3%. The as-cast microstructure is dendritic and the as
homogenized is polycrystalline grain.
After A.A. Korda & D. Nurhayani
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PHASE DIAGRAM PHASE DIAGRAM

Solidification process Solidification process

PHASE DIAGRAM BINARY EUTECTIC SYSTEMS

3 regions of single phase:

Cu – Ag phase diagram
,  & liquid
3 regions of two phases:
+L, +L & + 
 phase:
a solid solution rich in Cu;
it has Ag as the solute
component and an FCC
crystal structure.
 phase :
a solid solution rich in
Ag; it has Cu as the
solute component and
an FCC crystal
structure.
 and  phases are
considered to include pure
copper and pure silver,
respectively

 and   terminal solid

solution
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BINARY EUTECTIC SYSTEMS BINARY EUTECTIC SYSTEMS

Cu – Ag phase diagram Cu – Ag phase diagram

Max solubility of Ag
in Cu: B point
Composition at E:
Max solubility of Cu CE (71.9 wt% Ag)
in Ag: G point
Temp at E:
CBA : TE (779C)
Solubility limit of Ag
in  phase according at CE & TE :
temp change eutectic reaction
HGF :
Solubility limit of Cu Eutectic means easy
in  phase according to melt
temp change
BC & HG : solvus line
BA & GF : solidus line
BEG : solidus line
eutectic isotherm
AEF : liquidus line

E : invariant point

PHASE DIAGRAM BINARY EUTECTIC SYSTEMS

Exercise Pb – Sn phase diagram Cu – Ag phase diagram

Question:
For 40 wt% Sn-60 wt% Pb alloy at
150C.
(a) Phases present?
(b) Composition of phases?
(c) Mass fraction of the phase?

Answer:
(a)  and 
(b) With tie line.
  10 wt% Sn – 90 wt% Pb
  98 wt% Sn – 2 wt% Pb
(c) With lever rule. Eutectic reaction:
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TIME-TEMPERATURE COOLING CURVE TIME-TEMPERATURE COOLING CURVE

Natural freezing and melting Cooling curve for a pure metal

curves of a pure metal showing possible undercooling

Ideal cooling curve Ideal freezing curve of a On cooling a liquid metal or alloy the solidification does not take place even
with no phase change pure metal under the solidification point or under the liquidus. This circumstance is known
as undercooling or supercooling. It is a state of unstable equilibrium

TIME-TEMPERATURE COOLING CURVE TIME-TEMPERATURE COOLING CURVE

Ideal freezing curve of a solid-solution alloy

A A A

Liquid Liquid Liquid

C
B B B
Temperature

Liquid + Solid Liquid + Solid

C C D
Solid Solid Solid

(a) (b) (c) E

D
D
Time

Cooling curves for (a) pure metal (b) binary alloys or The continual freezing that occurs during cooling through a two-phase liquid-
solid solution (c) binary eutectic system plus-solid field results in a reduced slope to the curve between the liquidus
and solidus temperatures
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TIME-TEMPERATURE COOLING CURVE PHASE DIAGRAM

DEVELOPMENT OF MICROSTRUCTURE IN EUTECTIC BINARY PHASE ALLOYS

Ideal freezing curves of (1) a hypoeutectic alloy, (2) a eutectic alloy, and (3) a
hypereutectic alloy superimposed on a portion of a eutectic phase diagram.

PHASE DIAGRAM PHASE DIAGRAM

DEVELOPMENT OF MICROSTRUCTURE IN EUTECTIC BINARY PHASE ALLOYS DEVELOPMENT OF MICROSTRUCTURE IN EUTECTIC BINARY PHASE ALLOYS
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PHASE DIAGRAM PHASE DIAGRAM

EUTECTIC Sn-Pb BINARY PHASE ALLOYS DEVELOPMENT OF MICROSTRUCTURE IN EUTECTIC BINARY PHASE ALLOYS

By Nikon Tech.

PHASE DIAGRAM PHASE DIAGRAM

DEVELOPMENT OF MICROSTRUCTURE IN EUTECTIC BINARY PHASE ALLOYS Common eutectic structures in alloy systems
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PHASE DIAGRAM PHASE DIAGRAM

EQUILIBRIUM DIAGRAMS HAVING INTERMEDIATE PHASES  Intermediate EQUILIBRIUM DIAGRAMS HAVING INTERMEDIATE PHASES  Intermediate
solid solution solid solution

6 solid solution: Cu – Zn phase diagram Cartridge brass: Cu – Zn phase diagram

Terminal ss :  &  70% wt Cu – 30% wt Zn
Intermediate ss : , , , 

The ’ phase is
termed an ordered
solid solution, one in
which the copper and
zinc atoms are
situated in a specific
and ordered
arrangement within
each unit cell.)

their positions have not been exactly determined. At low temperatures, diffusion
rates are very slow for the attainment of equilibrium.

PHASE DIAGRAM PHASE DIAGRAM

EQUILIBRIUM DIAGRAMS HAVING INTERMEDIATE COMPOUNDS EUTECTOID and PERITECTIC REACTIONS

 Intermetallic compound

Intermetallic Cu – Zn phase diagram

compound. A
compound of two
metals that has a
distinct chemical
formula.

On a phase
diagram it appears
as an intermediate
phase that exists
over a very narrow
range of
compositions.

Mg2Pb at composition of
18 wt% Mg – 81 wt% Pb Mg – Pb phase diagram
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PHASE DIAGRAM PHASE DIAGRAM

Eutectoid reaction : SUMMARY OF PHASE DIAGRAM REACTIONS

Peritectic reaction:

Cu – Zn phase diagram

PHASE DIAGRAM Fe-C SYSTEM

EXERCISE : Identify the reactions in phase diagram below! PURE IRON

Answer: Iron is an allotropic

metal. Allotropic metals
2000°C
exhibit more than one
 + L →  (peritectic reaction)
type of crystal structure,
1400°C depending on their
L →  +  (eutectic reaction) temperature.

1100°C Iron undergoes three

L1 →  + L2 (monotectic reaction)
phase changes when
600°C
cooled from the melting
 →  +  (eutectoid reaction) point to the ambient
temperature
400°C
L2 →  +  (eutectic reaction)
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Fe-C SYSTEM Fe-C SYSTEM

PURE IRON ● The basis for carbon steel is carbon interstitially dissolved in iron.
The carbon atoms occupy the spaces between the iron atoms in the
iron crystal structure.
● Carbon dissolves in the BCC and FCC forms of iron. The result is
ferrite and austenite respectively

● Austenite is capable of
dissolving significantly
more carbon than ferrite.
● Although the BCC lattice
has more spaces than
the FCC lattice, the
spaces are not large
enough to accommodate
a large number of
carbon atoms.

Fe-C SYSTEM Fe-C SYSTEM

Fe-C SYSTEM  Fe – Fe3C PHASE DIAGRAM IMPORTANT REACTION IN Fe – Fe3C PHASE DIAGRAM

1. Peritectic reaction

cooling
 + L  (at 1495oC)

2. Eutectic reaction
cooling
L  + Fe3C (at 1148oC)

3. Eutectoid reaction
cooling
  + Fe3C (at 727oC)
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Fe-C SYSTEM Fe-C SYSTEM

PHASES IN Fe – Fe3C PHASE DIAGRAM

The phase diagram is used to
predict the steel
microstructure, especially Austenite : an interstitial solid solution of C in Fe-.
carbon steels Austenite can dissolve up to 2% C at 1129oC

Solid phases in carbon steel:

Ferrite : an interstitial solid solution of C in Fe-.
1. Ferrite (alpha, )
2. Austenite (gamma, ) Ferrite can dissolve up to 0.022% C at 723oC
3. Cementite (Fe3C)
4. Delta ferrite (delta, ) Cementite : a compound of Fe and C referred to as Fe3C. Cementite is
5. Pearlite (ferrite & cementite) an intermetallic compound and contains 6.67% C.

Pearlite : a lamellar aggregate of ferrite and cementite formed from the

eutectoid decomposition of austenite during slow cooling
(diffusion controlled phase transformation). The phase is
actually metastable, which can decompose to iron and
graphite at elevated temperature over prolonged time

Fe-C SYSTEM Fe-C SYSTEM

Figure shows two Figure shows two

diagrams; the stable diagrams; the stable
iron-graphite diagram iron-graphite diagram
(dashed lines) and the (dashed lines) and the
metastable Fe-Fe3C metastable Fe-Fe3C
diagram. The stable diagram.
condition usually takes a
very long time to develop, The stable condition
especially in the low- usually takes a very long
temperature and low- time to develop,
carbon range, and especially in the low-
therefore the metastable temperature and low-
diagram is of more carbon range, and
interest. therefore the metastable
diagram is of more
interest.
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Fe-C SYSTEM Fe-C SYSTEM

MICROSTRUCTURAL EVOLUTION IN Fe- C ALLOY

Ferrite Austenite

Fe-C SYSTEM Fe-C SYSTEM

PEARLITE FORMATION

0.022 wt% C

6.7 wt% C
0.76 wt% C Pearlite
(tough)

Ferrite, Fe-
(ductile)

Cementite, Fe3C
(hard)
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Fe-C SYSTEM Fe-C SYSTEM

HYPO-EUTECTOID COMPOSITION(wt% C < 0.76) HYPO-EUTECTOID COMPOSITION (0.38 wt% C)

Fe-C SYSTEM Fe-C SYSTEM

DETERMINATION OF  PROEUTECTOID AND PEARLITE AMOUNT HYPER-EUTECTOID COMPOSITION (wt% C > 0.76)

Pearlite fraction:

 proeutectoid fraction, W ’ :

 Total fraction (eutectoid & proeutectoid) =

Cementite fraction (Fe3C) =

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Fe-C SYSTEM Fe-C SYSTEM

HYPER-EUTECTOID COMPOSITION (1.4 wt% C) DETERMINATION OF PEARLITE AND PROEUTECTOID CEMENTITE AMOUNT

Pearlite fraction:

Proeutectoid cementite fraction:

Fe-C SYSTEM Fe-C SYSTEM

CARBON STEELS
MICROSTRUCTURE

(a) Austenite
(b) Ferrite
(c) Pearlite
(d) Magnified pearlite
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Fe-C SYSTEM CARBON STEELS

CARBON STEELS
MICROSTRUCTURE
(a) 0.20% C, slow cooling
(b) 0.20% C, magnified
(c) 0.40% C, slow cooling
(d) Eutectoid steel(0.8% C)
slow cooling

Note :
Etchant: Nital 2%
Dark region: pearlite
Light region: ferrite

CARBON STEELS CARBON STEELS

Mechanical Properties of Steels

 The mechanical properties of steel are largely

dictated by the phase transformations they
undergo upon cooling

 If we heat steel to the single phase austenite

region and vary the cooling rate, we can
control the microstructure

 Understanding phase transformations of

metallic alloys
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CARBON STEELS CARBON STEELS

Cooling rate affect pearlite interlaminar spacing

Cooling rate
affect
pearlite
interlaminar
spacing