PHASE DIAGRAMS

Assist. Prof. Dr. Gülhan Çakmak

[email protected]

All Materials Science Books

)

Introduction to Phase Equilibria in Ceramics

(Bergeron and Risbud

• 2 midterm,(20 % each)
• Pop quiz (10 %)
• 1 final exam(50 %)
It is obligatory to attend the classes
 Content
• Introduction •
Thermodynamics and Phase Equilibria Determinationof Phase Equilibria Diagrams
1.1 Systems. Phases. and Component 4.1 Experimental Methods
1.2 Equilibrium 4.2 Thermodynamic Calculations and Estimations
1.3 The Phase Rule
The One-Component System Hypothetical Binary Systems, Phase Analysis
2.1 Le Chatelier’s Principle 5.1 Hypothetical Binary Systems
2.2 The Water System 5.2 Phase Analysis Diagrams
2.3 Hypothetical Systems Problems
2.4 The Silica System
2.5 The Titania and Zirconia System TernarySystems
2.6 The Carbon System 6.1 Method of Determining Composition
The Two-Component System 6.2 Isoplethal Studiesin Ternary Systems
3.1 The Binary Eutectic 6.3 Alkemade Lines
3.2 Intermediate Compounds 6.4 Composition Triangles
3.3 SolidSolution 6.5 Isothermal Sections
3.4 Liquid Immiscibility 6.6 System with a Binary Compound Melting Incongruently
3.5 Structural Considerations of Liquid Immiscibility 6.7 Peritectic and Eutectic Reactions during Cooling
3.6 The System A1203-Si02 6.8 Resorption during Cooling
3.7 The System CaO-Si02. 6.9 Composition on an Alkemade Line
6.10 Phase Transformations
Aim of this course is TO UNDERSTAND PHASE
TRANSITIONS
AND
LEARN HOW TO READ and DRAW
PHASE DIAGRAMS
 Why Study Phase Diagrams

There is a strong correlation between microstructure and

mechanical properties, and the development of microstructure of
an alloy is related to the characteristics of its phase diagram.

Phase diagrams provide valuable information about melting,

casting, crystallization, and other phenomena.

4
Why Phase Diagrams Are IMPORTANT
 Why Phase Diagrams Are IMPORTANT
EXAMPLE -
Melting temperature of a mixture AB (solution) of two components A and B could be either lower or
higher than the melting point of each component (!). This could be a failure mechanism in electronic or
mechanical components. But could also be used to your advantage.
Chip-Solder-Joint-Failure

Some properties that might be difficult to predict using a “common sense” without the
knowledge of the phase diagrams
example 5: Tmelt (Au) = 1064 C, Tmelt (Si) = 2550
Tmelt (Sn) = 232 C, Tmelt (Pb) = 327 C…… but Tmelt C……but Tmelt (Au0.97 Si0.03 ) = 363 C, so thin layer
(Sn0.62 Pb0.38 ) = 183 C, so this is a common of gold is used to attach Si chip to a ceramic
soldering alloy substrate.
 Why Phase Diagrams Are IMPORTANT

EXAMPLE

Heart Stents

Shape memory alloys- thermally induced elastic recovery can be used to change a
small volume to a larger one.
Coronery artery disease is caused by plaque in-growth developing on and within an
artery’s inner Wall.
 Why Phase Diagrams Are IMPORTANT

There are lots of important reasons why you must care and try to understand phase
diagrams AS A MATERIAL SCIENTIST.

• To characterize compounds and phases

• To understand and tailor the reactions during the formation of any kind of
materials.

• Evaluate the thermal processes such as sintering and post sintering

processes

• Determine suitable process conditions,

• Produce desired materials

• Achieve service conditions of materials…

 Definition of Phase

Water + Ice Cubes Oil + Water

p:1 p:2

pure water (l) ice cube in water

sugar–water solution sugar–water solution
Air (N2, Ar, CO2, O2) (g) pyro-ceram
White gold (Au-Ag-Ni solution) fatty milk
In the physical sciences, a phase is a region of space
(a thermodynamic system), throughout which all
physical properties of a material are essentially
uniform. Examples of physical properties
include density, index of refraction, magnetization and
chemical composition. A simple description is that a
phase is a region of material that is chemically uniform,
physically distinct, and (often) mechanically separable
 Understanding the Basics of Phase Transitions
All Materials may in the state of;

Gas Liquid Solid

This state of material depends on the relative

magnitude of the attractive interatomic or
intermolecular forces.
How can you change the intensity of this magnitude?
 Understanding the Basics of Phase Transitions
So we have two basic variables that may cause a phase transition these are
pressure (P) and temperature (T).
TEMPERATURE (T)

Isobaric Process

Celcius (°C), Kelvin (K), Fahrenheit (F)

 Understanding the Basics of Phase Transitions

TEMPERATURE (T)
Melting Freezing Boiling

Sublimation
ways of changing state of matter

Melting: The transition from the solid to the liquid phase

Freezing: The transition from the liquid phase to the solid phase
Evaporating: The transition from the liquid phase to the gas phase
Condensing: The transition from the gas phase to the liquid phase
Sublimation: The transition from the solid phase to the gas phase
Deposition: The transition from the gas phase to the solid phase
Ar Ice (solid)

Ar Gas

Liquid Ar

Melting Point and −189.35 °C

 Understanding the Basics of Phase Transitions
PRESSURE (P)

atm, bar, pascal, kg/m2

Understanding the Basics of Phase Transitions
PRESSURE (P)

Is it possible to produce solid Hydrogen?

1935 Wigner & Huntington, 25 GPa

2011 Eremets and Troyan, 260 – 300 GPa

FUEL
An efficient fuel and also a clean one, with only water as
an end product

It would release about 20 times the energy of liquid

hydrogen burning with oxygen
Graphite is slippery, soft and easy to handle and find. Diamond is the
hardest material known by the mankind. They both made of carbon…

Graphite

Diamond

Q: Is it possible to transform graphite to Diamond.

at temperatures well above 1700K and at

pressures in excess of 12 GigaPascals
 Definition of the Diagram

A diagram is a two-dimensional geometric symbolic representation

of information according to some visualization technique. The word
graph is sometimes used as a synonym for diagram.
Y axis

X Axis
What is a Phase Diagram?
 DEFINITION
A phase diagram is a graphical representation that show the state of matter at a
given conditions. They show the boundaries between phases and the processes
that occur when the pressure and/or temperature is changed to cross these
boundaries.

Phase diagrams are one of the most important sources of information concerning
the behavior of elements, compounds and solutions. They provide us with the
knowledge of phase composition and phase stability as a function of temperature
(T), pressure (P) and composition (C).

Phase diagrams provide some fundamental knowledge of what the equilibrium

structure of a metallic (or ceramic) alloy is, as a function of temperature and
composition.

Express behavior of solids, liquids and gases under variable external conditions
(P,T, composition) according to equilibrium thermodynamics
• The phases present in a material can be varied by
altering the external conditions imposed upon the
system. Common external factors that are used to
control or modify the constitution of materials are
Temperature, pressure anc composition.
• Phase diagrams are sort of metallurgical maps
which display, the stability areas of various phases
of a material system in terms of externally
controllable factors.
 Examples for the Supercritical Water

Submarine (Underwater) Volcanos Planetary atmospheres

Depth : 3 km Pressure : 92 atm

Pressure : Above 300 atm Temperature : around 478°C
Temperature : around 375°C The atmosphere of Venus is 96.5% carbon
dioxide and 3.5% nitrogen.

above the critical points of both major constituents and

making the surface atmosphere a supercritical fluid.
 First Phase Diagram in History
Fe-C Diagram (Sir William Chandler Roberts-Austen)
❑ What is Equilibrium?

❑ Thermodynamic Equilibrium (Brief Intro)

❑ Gibbs Phase Rule and Examples

❑ Le Chatelier’s Principle

❑ One Component Systems – Examples

 EQUILIBRIUM
Condition in which the
properties of a system do not
change with the passage of time

Equlibrium: represents the lowest energy state

of a system. Properties are invariant with
time.The characteristics of the system do not
change with time
• Within this course our major interest will lie on the effects of
temperature, pressure and composition on phase equilibria.

• The phase diagrams that we are going to examine are generally

constructed to represent the equilibria that exist in a gives system
under equilibrium conditions.

• That means, the heating and cooling rates in the system are
maintained extremely slow so that the phases are always allowed
to equilibrate among themselves and with their environments in
terms of temperature, pressure and chemical potential.
 Phase Rule (Gibbs Rule)

• In order to describe the relationship between

number of phases, number of components, and the
degrees of freedom in a sytem.

• ‘for any system at equilibrium,provided the

equilibrium between any number of phases is not
influenced by gravity, by electrical or magnetic forces
or by surface action, but only by temperature,
pressure, and composition. the number of degrees
of freedom(F) is related to the number of
components (C) and the number of phases (P) by
the phase rule.
 Phase Rule (Gibbs Rule)

F=C–P+2

F: Degrees of Freedom
Sir Josiah Willard GIBBS C: Number of components
(1839-1903)(Yale University)
P: Number of phases

F is the number of degrees of freedom, which means

the number of intensive properties such as
temperature or pressure, which are independent of
other intensive variables.
Component: The components of a system are the chemical species
which make up the system. These may be elements or compounds.
Example:iron carbon system→ iron and carbon

In the slag system CaO-FeO-Fe2O3-SiO2→ the components can be

taken as the oxides CaO, FeO,Fe2O3, SiO2.

Number of components ,C: the number of components ‘C’ in the

phase rule expression is the smallest number of species that are
needed to be specified in relative abundance in order to be able to
specify the composition of each phase present under equilibrium
condition
• Unary system C: 1
• Ternary system C:3

In some cases it may become quite difficult to ascribe a value to

C owing to various chemical reactions leading to complex
formation. In such cases

C= number of chemical species-Number of independent

chemical reactions.
• Example: in a gaseous sytem which contains S2,
O2,SO2, SO3, there are 4 chemical species; between
them two independent chemical reactions occur:
• S2+2O2→ 2SO2
• S2+3O2→ 2SO3

thus the number of component C would be C=4-2=2

Phase: A portion of a system which has homogenius
physical and chemical properties, e.g. Atomic
structure, composition

SINGLE
Diamond PHASE Ice+water
Fog in Bandırma
Pure copper coin Air+solid particles

MULTI PHASES
 EXERCISE
Find out the number of phases in given systems

?Single phase? Melt iron and slag

Brass repeller

?Multi phase?

Pure fruit juice Alumina seals

Component: Individual chemical substances (elements or compounds)

Two phases but one component -H2O-

Iced water One phase but two components -Cu&Sn-

One phase but four components

Bronze profile -Si3N4 & Al2O3 & AlN & SiO2-

Sialon thermocouple sheat

One Component System (C=1)
F=C–P+2
F=1–P+2
F=3-P
Solid
l

Pressure (atm)
For 1 phase condition
(s or l or v regions)
Liquid
F = 2 (2 degrees of freedom) s

So T, P are the variables. You g

can play around T and P at
the same time.

The Composition is not a

variable because you only have Vapour
one component !!!!!!
Temperature (°C)
One Component System (C=1)
D
F=1–P+2 E
F=3-P

Pressure (atm)
Liquid
For 2 phase condition
(boundary lines) Solid
AB (solid – vapor) B
BD (solid – liquid)
BE (liquid – vapor) Vapour
F = 1 (1 degree freedom)

So T or P are the variables. A

Temperature (°C)
On these boundary lines T and P are dependent on each other. If you increase or
decrease one of them the other one will be automatically fixed in the diagram
 Solid
Liquid
Pressure (atm)

Vapour

Solid melts at this temperature

Temperature (°C)
One Component System (C=1)

F=1–P+2
F=3-P

Pressure (atm)
Liquid

For 3 phase condition

(point I) Solid
F=0 I
You don’t have any Vapour
variables to play…

Temperature (°C)
On these boundary lines T and P are dependent on each other. If you increase or
decrease one of them the other one will be automatically fixed in the diagram
 Liquid
Solid
Pressure (atm)

Liquid boils at this point

Vapour

Temperature (°C)
 Phase Rule (Gibbs Rule) - HOMEWORK

CaCO3(s) CaO(s) + CO2(g)

F: Degrees of Freedom
F=C–P+2 C: Number of components
P: Number of phases

Calculate F for the given system

 One Component Phase Diagrams

• Some real example of stability maps. Simplest

form is when c:1→ pure materials
• P vs Tequilibrium; p=2
s+l co-existance curve

p=1 p=2
equilibrium;
evaporation l+v co-existance curve
condensation
p=1
ice cube in boiling water
p=1
sublimantion 4.58 mmHg
0.01 ̊C
equilibrium;
s+v co-existance curve
p=2 Adapted from Callister & Rethwisch 8e.
 POSITIVE OR NEGATIVE SLOPE

Pressure (atm)

Liquid

Solid

Vapour

Temperature (°C)
Le Chatelier’s Principle
If an attemp is made to change the pressure, temperature and the concentration of
a system in equilibrium, then the equilibrium will shift in such a manner as to
diminish the magnitude of alteration in the factor which is varied.

Constant Volume SYSTEM

Liquid
Liquid
SOLID PHASE
SOLID PHASE (MELTED)

Heating The System

Due to the constant volume, more of the solid phase will melt than expected. Because
melting absorbs heat which will lead to an endothermic reaction. Also the specific
volume of the melt will increase time by time and at the same time the pressure of the
system will increase too…
Le Chatelier’s Principle
<<< P

<P
Pressure (P)

Temp. Decreases
Temp. Decreases
Constant Heat Liquid
Liquid Liquid
SOLID PHASE SOLID PHASE SOLID PHASE

Initial Intermediate Final

Now lets assume that we have a system under constant heat at the initial. In other
words the temperature of the system is constant. Lets say 120 C. If you decrease the
pressure that you apply a reaction will occur which will tend to decrease the effect of
pressure change; that is the volume of the system would increase. At the same time
temperature of the system will decrease.
 D
E
Pressure (atm) Liquid

Solid

B
Vapour

A
Temperature (°C)
 Clausius – Clapeyron Equation
(Quantitative Representation of Le Chateliers Principles
The Slopes of the boundary lines are usually
positive because in going from low to a higher
dP ΔH temperature, the entalphy change is positive
= and the volume change is most often positive…
dT T.ΔV
On the other hand we have some exceptions.
For H2O, Bi and Sn materials the slopes of the
melting curve.

During solid liquid transformation the volume

P: Pressure on the System change upon heating is not positive

T: Temperature of the System

H: The enthalpy accompanying the phase change (calories / mol)

V: the change in the spesific volume accompanying the phase change

 What is the exact change in volume of the
water when it freezes as ice?

Liquid water Ice

Mass = 100 g Mass = 100 g

Volume = 100 mL Volume = 108.7 mL
Density = 1.0 g/mL Density = 0.92 g/mL

mice = mwater Vice > Vwater dice < dwater

The slope of solid-liquid boundary line is negative due to

the negative volume change
Negative or Positive Slope?

• The slope of the A-C line depends on the relative densities of

the solid and the liquid.

• A positive slope means that the solid is more dense than the
liquid, a negative slope means the opposite.

What we know is that ice is less dense than water and thus, for the same
mass ice occupies more volume than water and hence the ice will have
larger molar volume than the liquid
 One Dimensional Phase Diagram of a Pure Substance

Melting Point of Pure A

700

Liquid A
600
Solid A
500

400

300

Pure A
(ex.: Ni, Cu etc.)

In practical phase diagrams boiling is of little interest, so the diagram is usually limited to liquid and
solid states.
 Types of Phase Diagrams
❑ One Component(Unary) System

[ H2O, CO2, SiO2, Pure Metals, Pure Oxides etc…]

❑ Two Component (Binary) System

[(Metal Alloys; Ni-Cu, Fe-Fe3C, etc.), Ceramics; (Oxide-Oxide, Oxide-Nonoxide, etc.)

❑ Three Component (Ternary) System

❑ Four Component (Quaternary) System

One Component (Unary) System – (Quartz - SiO2)

≈ 2 % volume change occurs

during the inversion

This is a schematically drawn diagram. Due to the low vapor pressures it is not easy to
distinguish these type of diagrams…
One Component (Unary) System – (Zirconia - ZrO2)

Monoclinic

Tmelting

1170C

Tetragonal

Cubic
Tetragonal
Monoclinic

2370C

Cubic
 TEM Image of a Zirconia Based Material

Tetragonal
Grains

Monoclinic
Grain
TRANSFORMATIONS (In case of using Y2O3)
Temperature (C)
3000
Liquid (L) L+F

2500
Cubic (F)

2000 Transformable 1600 C Tie Line

Tetragonal (T)
1400 C Tie Line
1500

T+F
1000 M
+
T

500

Non-Transformable
0 Cubic
Monoclinic (M) Tetragonal (T')

5 10 15
Mol % Yttria
 TRANSFORMATION TOUGHENING IN ZIRCONIA
MICROCRACKING
This can be induced by the incorporation of ZrO2 particles in a ceramic
matrix (cubic ZrO2 or another ceramic such as Al2O3). On cooling through
the transformation temperature (Tt-m), the volume expansion of 3-5 %
occurring in the ZrO2 particles causes a crack to form.
One Component (Unary) System – (Carbon System)
Question 1: A one-component system consists of two solid
phases (S1 and S2), a liquid phase (L) and a vapor phase
(V). S1 and S2 can be melted and sublimed. S1 is more
denser than S2 which is more denser than liquid. The
transformation S1-S2 is endothermic. Construct the phase
diagram which describes the system?
2 COMPONENT (BINARY) PHASE DIAGRAMS

for materials phase

relations
are determined at
atmospheric pressure
2 COMPONENT (BINARY) PHASE DIAGRAMS
BINARY ISOMORPHOUS PHASE DIAGRAMS
2 COMPONENT (BINARY) PHASE DIAGRAMS
BINARY EUTECTIC SYSTEMS
 EQUILIBRIUM THERMODYNAMICS
a system at equilibrium has a minimum energy.
G = E + PV – TS = H - TS
G: Gibbs Free Energy

energy
E: The internal energy

Free
P: Pressure on the system

V: Volume of the system

T: The absolute
Temperature
Equilibrium
S: The Entropy of the Stable state
system
EQUILIBRIUM
The kinetic and the potential
E: The internal energy energies of all the atoms and
molecules in the system
ΔE : E2-E1 = q-w
E1: initial energy of the system q: initial energy of the system
E2: final energy of the system w: work done by the system