Dijlah University College

Subject: Phase diagram

Assist.lecturer. Mahmood W.Faraj

2023-2024

lecture# 5

Definitions and basic concepts:

One reason that a knowledge and understanding of phase diagrams is important

to the engineer relates to the design and control of heat-treating procedures; some
properties of materials are functions of their microstructures, and, consequently, of
their thermal histories.

► Phase equilibrium diagram is a graphic relationship between temperature

and weight ratios of elements and alloys contribute to the built of the
diagram.
► Phase diagrams provide information on the following:
□ Melting point .
□ Casting condition .
□ Crystallization condition .
□ phase transformations (changes).
► Phase is a uniform portion (part) of an alloy, and a homogeneous
combination of mater having a certain chemical composition and structure,
and uniform physical and chemical and mechanical properties. and which is

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 separated from other alloy constituents by phase boundary.[example: H20
can exit as a gas, liquid and solid. These are three different phases of water].
► Component: the element or compound which is present in the mixture (e.g.,
Al and Cu).
► Solvent - host or major component in solution, solute - minor component in
solution.
► Solubility Limit - max. concentration of atoms to be dissolved in the
solvent to form a solid solution. [example solubility of sugar in water]
This solubility limit of sugar in water depends on the temperature of the
water and may be represented in graphical form on a plot of temperature
along the ordinate and composition.

200

80

150
� 60
Liquid solution (syrup) liquid
solution
8. 4

! I _________
0 solid 100
sugar .....

20 ___
50
0
Sugar o 20 40 60 80 100
Water 100 80 60 40 20 0
Composition (wt%)

Figure 1. The solubility of sugar in a sugar-water syrup.

Example: What is the solubility limit at 20 ° C?
Answer: 65 wt% sugar.
If C0 < 65 wt% sugar at 20 ° C : syrup (1 phase)
If C0 > 65 wt% sugar at 20 ° C : syrup + sugar (2 phases)
► Phases and solubility: [Water and alcohol have complete solubility], [Salt
and water have limited solubility], [Oil and water have no solubility].

ONE-COMPONENT (OR UNARY) PHASE DIAGRAMS

All curve from three curves in the figure 2. represent case equilibrium
of two phases.

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From Phase Diagram of Water:
• Triple point - the point on a phase diagram at which the three states of
matter: gas, liquid, and solid exist.
• Critical point - the point on a phase diagram at which the substance is
indistinguishable between liquid and gaseous states (i.e., no separate
interface between three phases).
• Fusion(melting) (or freezing) curve - the curve on a phase diagram which
represents the transition between liquid and solid states
• Vaporization (or condensation) curve - the curve on a phase diagram
which represents the transition between gaseous and liquid states
• Sublimation (or deposition) curve - the curve on a phase diagram which
represents the transition between gaseous and solid states

I
''
I

...
Q)

..
I
:I I
Ill I
Ill
Cl) solid phase \ I
I
I
compressible I supercritical fluid
I 1
liquid
critical pressure
P, o·itical point

gaseous phase

vapour
critical
1empera1ure
T,p Tcr
Temperature

Figure 2. Pressure-temperature phase diagram for H2 O.

Note: the hidden green curve applied on water only, because the water expanded
when transform to solid (ice), while all another materials converge when
densification.

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 Alloying systems

There are many types of alloying systems which they are:

1) Binary system: It means that alloying have two metals (2 components)only.
2) Ternary system: It means that alloying have three metals only.
3) Multi system: It means that alloying have three and more than that metals.

Binary Phase Diagrams

Binary Alloy: when two metals or a metal and a small amount of a nonmetal are
mixed in their molten states and allowed to cool, the result is a binary alloy.
In general, binary alloys can be classified into the following types:
1) Solid solution type: The two components are completely soluble in each
other both in the liquid state and in the solid state. [example of Solid
solution; gold- silver alloy, cupper- nickel alloy].
2) Simple eutectic type: The two components are soluble in each other in the
liquid state but not in the solid state. [example of eutectic are carbon steels].
3) Combination type: The two components are completely soluble in the liquid
state, but are only partially soluble in the solid state (e.g. Pb-Sn)..

1) Solid solution system (Full Solubility) - (Cigar shaped diagram)

► Solid solution is a phase, where two or more elements are completely soluble in each
other.Depending on the ratio of the solvent (matrix) metal atom size and solute element
atom size,two types of solid solutions may be formed: substitution or interstitial.
► Solid solution formation usually causes increase of electrical resistance and mechanical
strength and decrease of plasticity of the alloy.
Simple solution system (e.g., Ni-Cu solution), Ni and Cu are totally soluble in all
proportions (sub stitutional Solid solution); b ecause of b oth have the same crystal
structure (FCC) and have similar electronegativities and atomic radii.
Crystal electroneg r (nm)
Structure
Ni FCC 1.9 0.1246
Cu FCC 1.8 0.1278

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In Solid solution system (Full Solubility diagram) there are three different
regions:
1. Liquid (single phase)
2. Liquid+ solid (double phase; L+ a)
3. Solid solution (single phase a)
► Liquidus: the boundary line between the liquid region and the double phase
reg10n.
► Solidus: the boundary line between the solid solution region and the double
phase region.
Composition (at% i)

20 40 60 80 100
600r----.---.-----,---.--,--.--.....--

2800
1500
Liquid 1453-C

2600
1400

� �
2400
1300

1200 2200

100 2000
108s•c

000 ,..__,___....__.___..__.__.__..__,___....__,
20 40 60 80 100
(Cu) Composition ( t% i) ( i)
Figure 3. The copper-nickel phase diagram.
For a given temperature and composition we can use phase diagram to
determine:
1) Phase presents: just locate the Temperature-Composition point and
determine the phase(s)
2) Phase composition.
3) Phase amount (in the double phase region) -The Lever rule

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At the point B:
1300 t-----

1) Phases presents: 2 Phases

(double phase; L + a)
2) Phase composition:
The Ni composition of the
liquid phase is CL 1200

The Ni composition of the

solid (a) phase is Ca
20 30 40 50
CL o Ca
3) Phase amount: Composition (wt% Nil

For two phases region, use

the Lever Rule.
Amount ofthe liquid phase is:
s
WL = R + s
Amount ofthe Solid phase is:

► Rule 1: Ifwe know T and C0 , then we know: the numbers and type ofphases
present.
Example: Point A (1100° C, 60wt%Ni): 1 phase: a
Point B (1250° C, 35wt%Ni): 2 phases: L + a
► Rule 2: Ifwe know T and Co, then we know: the composition ofeach phase.
Example: from Figure 3.
Point A (1100° C, 60wt%Ni): Only Solid solution (a),
Ca = Co ( = 60wt% Ni).
Point B (1250° C, 35wt%Ni): 2 phases: L + a;
CL= Cliquidus ( = 32wt% Ni)
Ca= Csolidus ( = 43wt% Ni)

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 ► Rule 3: If we know T and Co, then we know the amount of each phase
(given in wt%).
Example: from Figure 3.
Point A (1100° C, 60wt%Ni): 1 phase: a (only solid phase)
WL= 0, W 0. = 100 wt%

The Lever Rule

Finding the composition in a two phase region:
1) Locate composition and temperature in diagram
2) In two phase region draw the tie line or isotherm.
3) Note intersection with phase boundaries. Read compositions at the
intersections.
All material must be in one phase:
Wa+WL = 1
Mass of a component that is present in both phases (Co):
WaCa+WLCL = Co
Solution of these equations gives us the lever rule:
WL = (Ca - Co)/ (Ca - CL)
Wa = (Co - CL) I (Ca - CL)
Or'
Tie line

I
I
I
I I
t--R-;,;...,__--s -----e-1
I I I
I I I

+ t
I
Example: at Point B Alloy (35wt%Ni) at I I

temperature 1250° C;
1
3 f 4
c.,.
- Phases present? 2 phases: L+a;
- Compositions of liquid and solid?
CL= Cliquidus ( = 31.5wt% Ni)
Ca= Csolidus ( = 42.5wt% Ni)

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 - Phase amount (wt%)?
Co = 35wt%Ni
CL = Cliquidus ( = 3 l .5wt% Ni)
Ca= Csolidus ( = 42.5wt% Ni)

WL = (Ca - Co) I (Ca - CL) = (42.5 - 35)/ (42.5- 31.5) = 0.68

Wa = (Co - CL)/ (Ca - CL) = (35 - 31.5)/ (42.5- 31.5) = 0.32
Or;
Wa+WL = 1; Wa+0.68 = 1; Wa = 0.32
Development of microstructure in isomorphous alloys
1) Equilibrium (very slow) cooling:
► Solidification in the solid+
liquid phase occurs
gradually upon cooling
from the Liquidus line.
► The composition of the
solid and the liquid change
gradually during cooling
1200
(as can be determined by
the tie-line method.)
► Nuclei of the solid phase
form and they grow to
consume all the liquid at 30 40 50

Composition (wt% Nil

the solidus line.

Figure 4. Schematic representation of the
development of microstructure during
the equilibrium solidification of a 35 wt% Ni-
65 wt% Cu alloy

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 2) Non-equilibrium Fast cooling: (Coring in Solid Solutions)
► Compositional changes
require diffusion in solid
and liquid phases.

► Diffusion in the solid is

very slow ⇒ new layers 1300
that formed on top of the
existing grains have the
equilibrium composition
at that temperature but
once they are solid their
composition does not ui!.,
change. ⇒ Formation of i
layered (cored) grains. f
1200
► Diffusion in the liquid
is very fast ⇒ tie-line
method works ⇒
a greater proportion of
liquid phase as compared
to the one for
equilibrium cooling at
same T ⇒ Solidus line is
shifted to the right
(higher Ni contents), 20 30 40 50 60
solidification is complete Composition M% flril
at lower T, the outer part Figure 5. Schematic representation of the
of the grains are richer development of microstructure during
in the low-melting the nonequilibrium solidification of a 35 wt% Ni-
component (Cu). 65 wt% Cu alloy
► As a casting having a cored structure, upon heating grain boundaries will
melt first. This can lead to premature mechanical failure.
► Coring may be eliminated by a homogenization (annealing) heat
treatment carried out at a temperature below the solidus point for the
particular alloy composition. During this process, atomic diffusion occurs,
which produces compositionally homogeneous grains.

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 I Cored vs Equilibrium Phases

• c. changes as we solidify.
• Cu-NI case: First a to solidify has c. = 46 wt% Ni.
Last a to solidify has c. = 35 wt¾ NI.

• Fast rate of cooling: • Slow rate of cooling:

Cored structure Equilibrium structure

For large cooling rate there is

not enough time for diffusion!

Example - Equilibrium Cooling:

A copper-nickel alloy of composition 35wt% Ni - 65wt% Cu is slowly cooled
from 1300°C;
(a)At what temperature does the first solid phase L

form?
Answer: Around 1250 °C 1300

(b) What is the composition of this solid phase?

Answer: 46 wt% Ni
(c) At what temperature does complete
solidification of the alloy occur?
Answer: Around 1210 °C 1,00

(d) What is the composition of the last liquid

remaining prior to complete solidification?
• 24 wt% Ni
(e) What is the amount of the solid phase at point ____.so_-'
c?
110020'-----'-30__,___•.._o

Oimposllion (wt"I. Na

Wa = (Co - CL) / (Ca - CL) = (35 - 32) / (43 - 32) = 27%

Wa+WL = 1 ⇒ WL= 73%

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Cooling Curves

Pure Metal
Upon cooling from liquid state, the temperature of the pure metal (A or B)
drops continuously till melting point at which solidification starts. Solidification
happens at a constant temperature (line PQ) as a result from formation of crystals
and loss of latent heat. The temperature drops again on completion of
solidification.

Alloy
For any alloy (1, 2, 3) temp temperature drops till the Liquidus (Ll, L2, L3).
However, in this case, solidification proceeds over a range of temperature. Once
solidification completes at the solidus (SI, S2, S3) the temp temperature drops
agam.

t L l
L. L.
:::, :::,
(0
L.
I
I Q)

E 3:
Q)
I- I
I
I

A Wt.%8-+ B Time-+

Cooling Curves describe creation of Cu-Ni solid solution phase diagram

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 cr,yJ'ol� r-••'"!1
For,n cornplelo

I
y

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Single :
phase
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Cooling Curve of Pure Metal

.,_v,.,;f Ct:,y4f"o/s
t, - - - -- R,
•
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-Fe,rrr,

5;,,,a/e. :
Two
J
'
,

• F,..e%ing
� - - - - -�- - - - - - - - - -- -�◄•--- co,nplet◄
I Y:
0..:
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Pnot!le : Pha.:1es I
I I
�
� '.(.Mu�_y Stage) :
I I
t

L,' CJi d Solid• Li uid Solid .

TJMC
Cooling Curve of solid solution alloy.

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Sample question:
Metal A melts at 1400°C, Metal B melts at 600°C. Thermal arrest data is obtained
from cooling curves for the alloy of AB and is shown below.
%A 0 10 20 30 50 60 80 90 100
st
1 Arrest point 600 700 860 960 1140 1220 1320 1370 1400
2nd Arrest point 600 630 690 760 910 1000 1160 1280 1400
1st Arrest point: Freezing Start temperature °C.
2nd Arrest point: Freezing End temperature °C.
(i) plot and label the equilibrium diagram
(ii) for an alloy containing 40% of A and 60% B state
(a) solidification start temperature
(b) solidification ending temperature
(c) composition of phases at 900° C
(d) the amount of phases
(e) the ratio of phases
Solution:
(i) plot and label the equilibrium diagram

1500
1400
1300
1200
u 1100
0
1000
- 1�1, "Q

� 900
,a 800 - :�:-
e
a; 700
600
i! 500
�1st Arrest point
�2nd Arrest point
400
300
200
100
0
0 10 20 30 40 50 60 70 80 90 100
Composition wt% A

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 (ii)for an alloy containing 40% of A and 60% B state
(a) Solidification start at 1060°C.
(b) Solidification ending at 840°C
(c) Composition of phases at 900°C,
Liquid Point (CL) = 24% A 76% B
Solid point (C8)= 48% A and 52% B.
(d) Amount of the phases is determined by Law of Lever rule:

WL = (Cs - Co)/ (Cs - CL)= (48 - 40)/ (48- 24)= 0.33

Ws = (Co - CL)/ (Cs - CL)= (40 - 24)/ (48- 24)= 0.67
Or;
Ws + WL = 1; Ws + 0.33= 1; Wa = 0.67
(e) Ratio of the phases:

WL = 0.33, Ws = 0.67
Ratio = Ws/W L =0.67/0.33 = 2

Example: Nickel, Aluminum & Copper have face cantered cubic structure yet Ni
is soluble in copper whereas Al has only a limited solubility. Explain why it is so?
Answer: Both the metals must have same crystal structure, valence & nearly same
atomic diameter. Both Ni & Cu have the same crystal structure (FCC) and have
similar electronegativities and atomic radii as well as valence. Aluminum has
larger atomic radius, and higher valence. Therefore its solubility of Al in Cu is
limited.

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