METALLURGY:

Phase Diagram

Dr. Suwaree Chankitmunkong

 PHASE DIAGRAM
01 Introduction

02 Types of phase diagram

03 Definition of basic term

04 Gibb’s phase rule

05 Binary phase diagram

06 Interpretation of phase diagram

07 Solidification
 t.TV WIVMW cpiogoyg phase diagram
Introduction I kinda )

Ø What is phase diagram ?

Phasenioriaoismsiaai
A phase diagram is a graphical representation of various phase present in the
alloy system at equilibrium at different temperature, pressure and composition

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• It shows the various types of phases present at different composition and
temperature
• It indicate solid solubility of an element in other
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:

• It show temperature range (melting or freezing temperature) over which

solidification or liquidification of material system occurs phase formation
• Information of the composition and amount of each phase in the system
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Ø Metallurgical applications
Compositions (alloying element addition)
i.e. adding Cr, P, S in Fe base metal
i.e adding Si, Mg, Cu in Al base metal
Steel
Aluminum
Phase diagram can use to predict the relationship among
microstructure, composition, conditions (temperature, press
ure, time), and mechanical properties 3
Thermal Equilibrium Diagram

• A chart that shows relationship between composition, temperat

ure and structures (phases) of alloys
– Phase diagram

• The phases are mostly in equilibrium.

– State of lowest thermodynamics energy
• Lowest Gibbs’ energy under constant T and P.
– Final structures that never changes

• Some phases aren’t actually in equilibrium.

– For example, Fe3C > coeinsooioo

Or
=
– D
Cementite will eventually turn into graphite.
– But we still have Fe3C in the phase diagram for practical purposes.

4
 Construction of Phase Diagram

Isomorphous

5
Types of phase diagram
• One component -> Unary phase diagram
• Two components -> Binary phase diagram or
Eutectic phase diagram
• Three components -> Ternary phase diagram

2 components: Cu-Ni equilibrium 3 components: Fe-Ni-Cr (Stainless steel) phase

1 component: Water phase diagram
phase diagram diagram at 900 degrees Celsius (ASM 1-27)

6
Definitions of Basic Term
• Component is element or chemical compound whose presence is necessary and
sufficient to make a system. A pure metal is one component system whereas and
alloy of metals is a two-component(binary) system etc.
• Phase (solid, gas, liquid) is a homogenous portion of system that has uniform
physical and chemical characteristics.
• Different phases are given different names or symbols like α (alpha), ß (Beta), γ (Gamm
a), etc. such as Fe solid-(α) and Fe solid (γ)

Example of pure Fe
• 1 components is Fe
• It can form different phases in
Fe solid-austenite phase (γ)
the system upon temperature
such as phase ferrite and
phase austenite

Picture are modified by refs [1,2] Fe solid-ferrite phase (α)

[1] A Controlled Carburization Process to Obtain Graphene-Fe 3 C-Fe Composites

[2] Tikalon Contact Page 7
Solubility limit
Solubility limit: maximum concentration of solute atoms that may dissolve in
the solvent to form a solid solution (i.e. water-sugar solution)
90 %wt of sugar at 100 ℃ (2 phase)
● ●

<80 %wt of sugar at 100 ℃ (1 phase)

65 %wt of sugar at 20 ℃ (1 phase)
8
Gibb’s Phase Rule
Ø Gibb’s Phase Rule

P+F = C+2
P = number of phases
F = number of degrees of freedom- number of variables that can be changed
independently of all other variables in the system
C = number of components
The number two indicates the ability to change temperature and pressure, the
se are non-compositional variables that affects the phases.

Ø How to use Gibb’s phase rule ?

• Phase rule helps to determine maximum number of phase present in an alloy s
ystem under equilibrium conditions at any point in phase diagram.
• The phase rule can also be used to determine the degree of freedom that can b
e changed

9
Ø Gibb’s Phase Rule
of freedom
degree
P+F = C+2
:
F

l phase Area: 1+ F = 1 + 2
1 Component F=2
• 2 variables can be changed (Temp & Pres
( ●
A
●
B sure)

V Line: 2+F = 1+2

T decrease, P decease
F=1
• 1 variable can be changed
●
C
Point: 3 + F = 1 + 2

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F = 0 Bisono
• No variables can be changed
• Triple point or Invariant point

"

T blog : ppg of

10
Example of Gibb’s Phase Rule

• How skier can move on the ice? Wnondefgvo9vgfp =

pressure bald
wingsuit origin Didio brush
✓
●

Pressure

!
°

( iwi . → o
'

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nonbinding → Tino 's
ninoigroisriatm
Pressure increase > 1 atm, ice will be melted to water at zero-degree celsius

11
 Gibb’s Phase Rule for metallurgical application Temp

66009819 Ptt
=
C ( pressure
Ø Modified Gibb’s Phase Rule
P + F = C +0
1 at 1 atm of pressure

The number one indicates the ability to change temperature, these are non-compositional v
ariables that affects the phases.
quieting 88918
Ø Degrees of freedom cannot be less than zero
component phase
( ,
C + 1 – P => 0 or P <= C+1

The binary system have 2 component (C value = 2)

¥p 0
-

p =
2+1
P=2+1=3
p =3
A
Therefore, maximum 3 phases can be found in binary system at t
he equilibrium
12
Example of Cu-Ag phase diagram (F=1)
F=C+1-P
F = 2 + 1- 2 =1
Therefore, F = 1, which mean only one parameter
(T or C) needs to be specified to completely defin
a+L e the system

i.e. for a + L region,

If T is specified to be 1000 ℃, composition are
already determined as Ca and CL (fixed).

Cu(a) + Ag(β)

100 %wt Ag

13
 Invariant point

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*

2bWd
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, p)
*

tic :

I -76188 809118921Not -70911991W ON:3

told : 80911897 Voguls T

14
Binary Systems
Ø There are three main types of binary phase diagrams :
• Binary isomorphous system: Two metals have complete solubility in the li
quid and solid stage i.e. Cu-Ni phase diagram

• Binary eutectic system: Two metals have complete miscibility in liquid sta
ge and partial solubility in solid stage i.e. Sn-Pb phase diagram

• Binary peritectic system: Sometimes a solid solution phase, which has already been
formed, and the residual liquid phase react and form another solid solution phase or i
ntermetallic compound, having a composition between the compositions of the liquid
and the first solid ( L+S1 --> S2)

Ø Interpretation of binary phase diagrams:

For a given temperature and composition we can use phase diagram to determi
ne:
1) The presence of phases
2) The compositions of the phases
3) The relative fractions of the phases
15
Binary Systems (Binary isomorphous system)
• Binary isomorphous system: Two metals have complete solubility in the li
quid and solid stage i.e. Cu-Ni phase diagram

Liquidus line:
1455 ℃
separates liquid from liquid (L) + solid (a)
line Solidus line:
us
u id separates solid from liquid (L) + solid (a)
L iq
1,270 ℃ line i.e. at 100 %wt Cu
s
1,230 ℃ lidu Melting temperature is at 1,085 ℃
So
i.e. at 100 %wt Ni
Melting temperature at 1,455 ℃

1085 ℃ i.e. at Cu-40 %wt Ni

Liquidus temperature or melting t
emp. at 1,270 ℃
Solidus temperature or freezing te
mp. at 1,230 ℃
Picture was adapted by ref [1,2]
[1] M. Hansen & K. Anderko, Constitution of Binary Alloys, McGraw-Hill, 1958
[2] ASM International, ASM Handbook Volume 3: Alloy Phase Diagrams, 1992 16
 Example of phase diagram interpretation (types of phases p
rediction)
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no Umg in all for Migros fan :
add

• If you know T and C0 , then you can d

etermine number and type of phases
88 .
b ID : 8W agog b WI

1. Mark the constitution for a Cu–40 wt% Ni

alloy at temperature of 1300°C.
What does it consist of ? How many phases?
Answer: 1 phase of liquid

2. Mark the point for a Cu–35 wt% Ni at te

mperature of 1,250°C.
1250 ℃ What does it consist of ? How many phases?
Answer: 2 phases (liquid + solid a).

35%wt Ni

Picture was adapted by ref [1,2]

[1] M. Hansen & K. Anderko, Constitution of Binary Alloys, McGraw-Hill, 1958 17

[2] ASM International, ASM Handbook Volume 3: Alloy Phase Diagrams, 1992
 Interpretation of composition of each phase
(at given in %wt given)

• If we know T and C0, then we can defi

ne the composition of each phase 1. The constitution point for a Cu–35 wt% Ni
alloy at 1,350°C.
Answer:
• There is only liquid (L) phase
• The composition of liquid phase = the com
position of system that is 35% in the liquid

1,350 ℃
Point A
●
2. The constitution point for a Cu–35 wt% Ni alloy at 1,
250°C.
Tie line
Point B Answer:
1,250 ℃ ● • There is 2 phase of Liquid (L) phase and solid
• The composition of liquid phase is 32%Ni in the liq
uid
1,190 ℃ ● • The composition of solid phase is 43%Ni in the sol
Point C id

1. The constitution point for a Cu–35 wt% Ni

alloy at 1,190°C.
Answer:
35%wt Ni • There is only solid (a) phase
• The composition of solid phase = the comp
32%wt Ni 43%wt Ni osition of system that is 35% in the solid
Picture was adapted by ref [1,2]
[1] M. Hansen & K. Anderko, Constitution of Binary Alloys, McGraw-Hill, 1958
[2] ASM International, ASM Handbook Volume 3: Alloy Phase Diagrams, 1992 18
 Interpretation of amount of each phase

• If we know T and C0, then we can define proportions of each phases in two-
phase alloys
1. The constitution point for a Cu–35 w
t% Ni alloy at 1,250°C.

Step I: Draw the line at given T and C0

Step II: Draw tie line where it intersects the liquidu

s and solidus lines at given T and C0 (i.e.
where the tie line crosses the phase boundaries)

Step III: Read the composition of each phase

1,250 ℃
The composition of liquid phase = 32%
The composition of solid phase = 43%
R S
Step IV: Use the composition of each phase subst
itute in the formula of level rule
The weight fraction of liquid and solid in the al
loy are
! (%&'&()
Wliquid = = x 100 = 72.72 = 73 %wt
"#! (%&'&*)
" (&('&*)
Wsolid = = x 100 = 27 %wt
Picture was adapted by ref [1] 35 %wt Ni "#! (%&'&*)
[1] Adapted from Fig. 9.3(a), Callister 7e.(Fig. 9.3(a) is adapted from Phase
Diagrams of Binary Nickel Alloys, P. Nash(Ed.), ASM International, Materials Park, OH (1991). 19
Basic Rules : จํานวนและประเภทของเฟส

• ถ้ารู ้ T และ Total composition เราสามารถหา จํานวน และ ประเภท ของเฟสที9เกิดขึ>น

Total Composition

20
Basic Rules :องค์ประกอบของเฟส

• ถ้ารู ้ T และ Total composition เราสามารถหา Composition ของแต่ละเฟสที:

เกิดขึ>น

21
Basic Rules :สัดส่ วนโดยนํ*าหนัก

• ถ้ารู ้ T และ Total composition เราสามารถหา ปริ มาณของแต่ละเฟสทีAเกิดขึ*น (ใน

หน่วยของ wt%)

!
wt% α = "#!

" R S
wt% β = "#!

22
Example
• What is an approximated composition of the initial solid that
forms?

• What are the phases that are present at 1300oc?

• What is the amount of solid (in kg) just above 1185oc?

• What is the composition of the solid just above 1185oc?

• What is the composition of the second solid that appears just

below 1185oc?

• What is the approximated composition of liquid that last

solidifies?

23
Conclusions

Ø Phase diagrams are useful tools that can be use to determine

• The melting/freezing temperature of alloy at given composition
• Number and types of phase
• The composition of each phase at given temperature and composition
• The amount or fraction of each phase at given temperature and composit
ion

Ø Advantages of phase diagram

• Development of new alloys ( WasimIan 8809as Noi y
'
:

• Fabrication of these alloys into useful configurations

• Design and control of heat treatment procedures for specific alloys that w
ill produce the required mechanical and physical and chemical properties.

24
Phase Diagram: Case 1

Two metals which are only partially soluble in each other in the liquid state

25
Phase Diagram: Case 2

Two metals mutually soluble in all proportions in the liquid but completely in
soluble in the solid state

26
Phase Diagram: Case 2

• Cooling at eutectic composition

– Eutectic liquid solidifies to form a eutectic structure
• Constant temperature during this process

27
Phase Diagram: Case 2

• Cooling at X
– Pure Cd solidifies
– Liquid becomes Bi-rich until eutectic composition
– Eutectic liquid solidifies to form a eutectic structure.
• Constant temperature during this process

28
 Phase Diagram Case 2

• Cooling at Y
– Pure Bi solidifies
– Liquid becomes Cd-rich until eutectic
composition.
– Eutectic liquid solidifies to form a eut Y
ectic structure.
• Constant temperature during this
process

29
Phase Diagram Case 3

Two metals mutually soluble in all proportions in the liquid and solid states

30
Equilibrium Vs Non-Equilibrium Cooling

Eq. Cooling Non-Eq. Cooling

การลดอุณหภูมิลงอย่างช้าๆ การลดอุณหภูมิลงอย่างรวดเร็ ว
มีเวลาให้อะตอมแพร่ ไม่มีเวลาให้อะตอมแพร่
Uniform solid structure Cored structure
No evidence of dendritic growth Visible evidence of dendritic growth

31
Equilibrium Vs Non-Equilibrium Cooling

32
Phase Diagram: Case 3

• Normally, the lowest melting po

int is that of the pure metal.
• Consider the phase diagram of
Potassium and Rubidium
– The lowest melting point is that of the al
loy
– The two types of atoms in the alloy are s
o incompatible that the solid solution w
ants to melt.

33
Phase Diagram: Case 4
Two metals mutually soluble in all proportions in the liquid and but partially
soluble in solid states

34
Equilibrium Cooling

35
Equilibrium Cooling

36
Equilibrium Cooling

37
Equilibrium Cooling

38
Example of Interpretation
Primary α

α L
Eutectic Reaction

α α β
Eutectic α Eutectic β
Equilibrium Cooling

Total α phase

39
Non-equilibrium Cooling • Cored structure
• Evidence of dendritic growth

40
 Phase Diagram: Case 5
A system with peritectic transformation L+αàδ

41
 Equilibrium Cooling

• Liquid solidifies
• Dendrite of α phase forms
at composition a.

Overall composition
42
Equilibrium Cooling

• Just above the peritectic temperature

• A mixture
– α phase at composition P.
– Liquid at composition R.

43
Equilibrium Cooling

• Just below the peritectic temperature

• L+αàδ
– Not all α is used.
• A mixture
– α phase at composition P.
– δ at composition Q.

44
Example of Interpretation

α L
Peritectic Reaction

α δ

45
Example

α L α L

Peritectic Reaction
Peritectic Reaction

α δ δ L
46
Non-Equilibrium Cooling

α phase is still present.

47
 Phase Diagram: Case 6

A system containing intermediate phases

48
 Phase Diagram: Case 6

• Mg2Sn has a fixed composition

– The phase “field” becomes a line.

• This phase diagram consists of

two eutectic phase diagrams.
• Microstructures during cooling
are similar to those of the
eutectic diagram.

49
50
 Equilibrium Cooling
• At temperature T
• Pure Au starts to solidify.

Overall composition 51
 Equilibrium Cooling

• Just above 418 oC

• Mixture
– Pure Au
– Liquid at composition C

Overall composition 52
 Equilibrium Cooling

• Just below 418 oC

• Au + L à Au2Pb
– Peritectic reaction
– Not all liquid is used.
• Mixture C
– Au2Pb (fixed compositi
on)
– Liquid at composition C

Overall composition 53
 Equilibrium Cooling
• Just above 254 oC
• Mixture
– Au2Pb (fixed composition)
– Liquid at composition D

Overall composition 54
 Equilibrium Cooling

• Just below 254 oC

• L + Au2Pb à AuPb2
– Peritectic Reaction
– Not all Au2Pb is used.
• Mixture
– Au2Pb (fixed compositi
on)
– AuPb2 (fixed compositi
on)

Overall composition 55
Solidification

• Formation of nuclei
• Growth of nucleus grows
• Formation of dendrites
(trees)
– Forming primary, secondary, tertia
ry branches
– Heat dissipates fast at tips

Fe dendrite from Fe-Cu alloy 56

 Solidification

• Dendrite branches grow and thicken

• At some point, the dendrite branches meet
– No further growth is possible.
– Grain boundaries

57
Solidification

• If metal is pure
– We see no evidence of dendritic
solidification
• For alloys
– Impurities atoms tend to remain
the molten portion
– Impurities solidify last (between
dendrite branches)
– These portion leave traces that
are visible through microscope.

58
 Solidification

• If the metal is cooled too rapidly, inter-dendritic

cavities/porosities (รู พรุ น) can occur.
– Molten metal does not have time to fill in the space due to solidification
shrinkage.
• This is different from blow-holes (โพรงแก๊ส) from
dissolved gas
– are irregular in shape.
– occur at any points.

59
Iron-Carbon Phase Diagram
Iron-Carbon Phase Diagram

Metastable

61
Iron-Carbon Phase Diagram

• α-iron
– Ferrite
– BCC
– เหนียว ไม่แข็ง
• γ-iron
– Austenite
– FCC
– นิ/ม รี ดขึ3นรู ปได้ง่าย
• δ-iron
– BCC
– ไม่เสถียร จะปรากฏที/อุณหภูมิสูง
• Fe3C
– Cementite
– Interstitial compound
– แข็ง แต่เปราะ เพราะมี คาร์บอนอยู่ 6.67%

62
THANK YOU