Phase

Diagrams
 Phase Diagram
Microstructure is specified by the number of phases, their proportions, and
their arrangement in space.

Cast Iron

Phase diagrams will help us to understand and predict the microstructures

Phase Diagrams

For any given point (x,T) the phase

diagram can answer the following:
1. What phases are present?
2. What are the phase compositions?
3. What are the relative amounts of
the phases (phase proportions or
phase fractions)?
 Equilibrium phase diagram
or
Equilibrium diagram
or
Phase diagram

A diagram in the space of relevant

thermodynamic variables (e.g., T
and x) indicating phases in
equilibrium is called a phase
diagram.
 Components
The independent chemical species (element or
compound) in terms of which the composition of
the system is described are called components.

System components phases

Water H2O liquid

Water +ice H2O Liquid+solid

Mild steel Fe + C α + Fe3C

 Components and Phases
• Components:
The elements or compounds that are mixed initially (Al and Cu).
• Phases:
A phase is a homogenous, physically distinct and mechanically
separable portion of the material with a given chemical
composition and structure (α and β).

Aluminum-
Copper
Alloy

6
A single component phase diagram:
Unary diagram

A two-component phase diagram:

Binary diagram

A three-component phase diagram:

Ternary diagram
 Binary Isomorphous Phase Diagrams
Cu-Ni system:

• The liquid L is a homogeneous liquid solution composed of Cu

and Ni.
• The α phase is a substitutional solid solution consisting of Cu and
Ni atoms with an FCC crystal structure.
• At temperatures below 1080 C, Cu and Ni are mutually soluble in
each other in the solid state for all compositions.
• The complete solubility is explained by their FCC structure,
nearly identical atomic radii and electro-negativities, and similar
valences.
• The Cu-Ni system is termed isomorphous because of this
complete liquid and solid solubility of the 2 components.

13
 Criteria for Solid Solubility

Simple system (e.g., Ni-Cu solution)

Crystal
Structure electroneg r (nm)

Ni FCC 1.9 0.1246

Cu FCC 1.8 0.1278

• Both have the same crystal structure (FCC) and have

similar electronegativities and atomic radii (W. Hume –
Rothery rules) suggesting high mutual solubility.

• Ni and Cu are totally soluble in one another for all proportions.

14
Binary Isomorphous Phase Diagrams
Number and Types of Phases
 Gibbs Phase Rule

F = Degrees of freedom
C = No. of components in the system
P = No. of phases in equlibrium

F=C–P+2
If pressure and temp both are variables

F=C–P+1
If pressure is held constant
Phase Diagrams

For any given point (x,T) the phase

diagram can answer the following:
1. What phases are present?
2. What are the phase compositions?
3. What are the relative amounts of
the phases (phase proportions or
phase fractions)?
 Point A:
60 wt% Ni at 1100ºC

Q: Phase present?

Ans: α

Q: Phase composition ?

Ans: 60 wt%Ni
α
Q: Phase amount ?

Ans: 100%
 Point B:
35 wt% Ni at 1250ºC

Q: Phases present?

Ans: α + L

Q: Phase compositions ?

Tie Line Rule

α
Q: Phase amounts ?

Lever Rule
Composition of phases in the two-phase region
Tie Line Rule
α
L

Tie Line

CL= 31.5 wt% Ni

Cα= 42.5 wt% Ni
 Amount of phases in the two-phase region
α Tie-Line: A lever
L Alloy composition C0: Fulcrum
fL: weight at liquidus point

fα: weight at solidus point

The lever is balanced

fα
fL f L (C0 − C L ) = fα (Cα − C0 )

f L + fα = 1
Cα − C0 opposite lever arm
Tie Lever Rule fL = =
Cα − C L total lever arm
 Eutectic

• The term comes from the Greek 'eutektos', meaning 'easily melted’.

• A eutectic or eutectic mixture is a mixture of two or more phases

at a composition that has the lowest melting point.

• It is where the phases simultaneously crystallize from molten

solution.

• The proper ratios of phases to obtain a eutectic is identified by the

eutectic point on a binary phase diagram.

28
 Eutectic

• The phase diagram displays a simple binary system composed of two components,
A and B, which has a eutectic point.
• The phase diagram plots relative concentrations of A and B along the X-axis, and
temperature along the Y-axis. The eutectic point is the point where the liquid
phase borders directly on the solid α + β phase; it represents the minimum
melting temperature of any possible A B alloy.
• The temperature that corresponds to this point is known as the eutectic
temperature.
• Not all binary system alloys have a eutectic point: those that form a solid solution
at all concentrations, such as the gold-silver system, have no eutectic. An alloy
system that has a eutectic is often referred to as a eutectic system, or eutectic
alloy. 29
Copper-Silver Phase Diagram
 Eutectic Relation

• Solvus – (solid solubility line) BC, GH

• Solidus – AB, FG, BEG (eutectic isotherm)
• Liquidus – AEF
• Maximum solubility: α = 8.0 wt% Ag, β = 8.8 wt %Cu
• Invariant point (where 3 phases are in equilibrium) is at E;
CE = 71.9 wt% Ag, TE = 779C (1434F).
• An isothermal, reversible reaction between two (or more)
solid phases during the heating of a system where a
single liquid phase is produced.
Eutectic reaction
L(CE) α(CαE) + β(CβE)

cooling
L(71.9 wt% Ag) α(8.0 wt% Ag) + β(91.2 wt% Ag)
heating 31
Solder alloy?

An alloy of Pb and Sn

What is best composition of the

solder alloy?

Requirements:
1. should melt easily
2. should give a strong joint
60 - 40 Solder
 Pb-Sn Phase Diagram

Liquidus
Solidus
Solidus

Solidus

Solvus Solvus
 Pb-Sn Phase Diagram

• For lead & tin the eutectic composition is 61.9 wt% tin and the
eutectic temperature is 183ºC -- which makes this mixture useful
as solder.

• At 183ºC, compositions of greater than 61.9 wt% tin result in

precipitation of a tin-rich solid in the liquid mixture, whereas
compositions of less than 61.9 wt% tin result in precipitation of
lead-rich solid.

35
 Solidification of Eutectic Mixture
• Mixtures of some metals, such as copper & nickel, are completely
soluble in both liquid and solid states for all concentrations of both
metals. Copper & nickel have the same crystal structure (FCC) and
have nearly the same atomic radii. The solid formed by cooling can
have any proportion of copper & nickel. Such completely miscible
mixtures of metals are called isomorphous.
• By contrast, a mixture of lead & tin that is eutectic is only partially
soluble when in the solid state. Lead & tin have different crystal
structures (FCC versus BCT) and lead atoms are much larger. No
more than 18.3 weight % solid tin can dissolve in solid lead and no
more than 2.2% of solid lead can dissolve in solid tin (according to
previous phase diagram).
• The solid lead-tin alloy consists of a mixture of two solid phases,
one consisting of a maximum of 18.3 wt% tin (the alpha phase)
and one consisting of a maximum of 2.2 wt% lead (the beta phase). 36
 Ex:1 Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 150°C, determine:
-- the phases present Pb-Sn
T(°C)
Answer: α + β system
-- the phase compositions
300
Answer: Cα = 11 wt% Sn L (liquid)
Cβ = 99 wt% Sn
α L+ α
-- the relative amount 200 183°C L+β β
of each phase 18.3 61.9 97.8
Answer: 150
C - C0 100
W = β α + β
α Cβ - Cα
99 - 40 59
= = = 0.67
99 - 11 88 0 11 20 40 60 80 99100
Cα C0 Cβ
Wβ = C0 - Cα C, wt% Sn
Cβ - Cα
40 - 11 29
= = = 0.33 37
99 - 11 88
 Ex:2 Pb-Sn Eutectic System
• For a 40 wt% Sn-60 wt% Pb alloy at 220°C, determine:
-- the phases present:
T(°C)
Answer: α + L
-- the phase compositions
300
Answer: Cα = 17 wt% Sn L (liquid)
CL = 46 wt% Sn L+α
-- the relative amount 220 α
200 L+β β
of each phase 183°C
Answer:
CL - C0 100
46 - 40 α + β
Wα = =
CL - Cα 46 - 17
6 0 17 20 40 46 60 80 100
= = 0.21 Cα C0 CL C, wt% Sn
29
C0 - Cα 23
WL = = = 0.79
CL - Cα 29 38
I. Microstructural Developments Pb-Sn System

• For alloys where

C0 < 2 wt% Sn T(°C) L: C0 wt% Sn
400
L
α
300 L

L+ α
200
α
TE α: C0 wt% Sn

Pb-Sn 100
α+ β
system

0 10 20 30
C0 C, wt% Sn
2
(room T solubility limit)

39
II. Microstructural Developments Pb-Sn System

2 wt% Sn < C0 < 18.3 wt% Sn

L: C0 wt% Sn
T(°C)
400
L
L
300 α
L+α
α: C0 wt% Sn
α
200
TE
α
β
Pb-Sn 100
α+ β
system

0 10 20 30
2 C0 C, wt% Sn
(sol. limit at T room ) 18.3
(sol. limit at TE) 40
III. Microstructural Developments Pb-Sn System

• Co = CE
• Results in a
eutectic
microstructure
with alternating
layers of a and b
crystals.

Pb-Sn
system

cooling
L(61.9 wt% Sn) α (18.3 wt% Sn) + β (97.8 wt% Sn)
heating
 Lamellar Eutectic Structure
• A 2-phase microstructure
resulting from the
solidification of a liquid
having the eutectic
composition where the phases
exist as a lamellae that Pb-rich
alternate with one another.

Sn-rich
• Formation of eutectic layered
microstructure in the Pb-Sn
system during solidification at
the eutectic composition.
Compositions of α and β
phases are very different.
Solidification involves
redistribution of Pb and Sn
atoms by atomic diffusion.
42
Hypoeutectic and Hypereutectic
 Iron Carbon System

• Pure iron when heated experiences 2

changes in crystal structure before it
melts.
• At room temperature the stable form,
ferrite (α iron) has a BCC crystal
structure.
• Ferrite experiences a polymorphic
transformation to FCC austenite (γ iron)
at 912 ˚C (1674 ˚F).
• At 1394˚C (2541˚F) austenite reverts
back to BCC phase δ ferrite and melts at
1538 ˚C (2800 ˚F).
• Iron carbide (cementite or Fe3C) an
intermediate compound is formed at 6.7
wt% C.
• Typically, all steels and cast irons have
carbon contents less than 6.7 wt% C.
• Carbon is an interstitial impurity in iron
and forms a solid solution with the α, γ, δ
phases. 44
 Phases in Iron Carbon System

Phase Symbol Description

Liquid L Liquid solution of Fe and C
δ-Ferrite δ Interstitial solid solution of C in
δ-Fe (high temperature bcc phase)
Austenite γ Interstitial solid solution of C in
γ-Fe (FCC phase of Fe)
Ferrite α Interstitial solid solution of C in
α-Fe (room temperature bcc phase)
Soft and Ductile
Cementite Fe3C Intermetallic compound of Fe and C
(orthorhombic system)
Hard and Brittle
Phases in Iron Carbon System
Phases in Iron Carbon System
Iron- Iron Carbide Phase Diagram
 Invariant Reactions in Fe-C System
A horizontal line always indicates an invariant reaction in
binary phase diagrams
 Invariant Reactions in Fe-C System

Peritectic Reaction
1493o C
α (0.1 wt % C ) + L (0.5 wt % C ) → δ (0.18 wt % C )

Eutectic Reaction
1150 o C
L (4.3 wt % C ) → γ (2.1 wt % C ) + Fe3C (6.67 wt % C )

Eutectoid Reaction
725o C
γ (0.8 wt % C ) → α (0.02 wt % C ) + Fe3C (6.67 wt % C )
Eutectoid Reactions in Fe-C System
Eutectoid Reaction
725o C
γ → α + Fe3C
cool
0.8 0.02 6.67

Pearlite
 Fe-C System: Eutectoid Reaction
Eutectoid Reaction
725o C
γ → α + Fe3C
cool
0.8 0.02 6.67

Pearlite

Ammount of Fe3C in Pearlite

Red Tie Line below eutectoid temp

pearlite 0.8 − 0.02 0.78

f F3C = = = 0.117
6.67 − 0.02 6.65
Microstructural Development in Fe-C System

Development of
Microstructure in a
hypoeutectoid steel
 Microstructural Development in Fe-C System

Proeutectoid
Ferrite

Pearlite

Microsructure of a hypoeutectoid steel, 0.38 wt% C

Microstructural Development in Fe-C System
Development of
Microstructure
in a
hypereutectoid
steel
Microstructural Development in Fe-C System
Pearlite

Proeutectoid
cementite on
prior
austenite
grain
boundaries

Microsructure of a hypereutectoid steel, 1.4 wt% C

 Microstructural Development in Fe-C System

Eutectoid Hypoutectoid Hypereutectoid

steel steel steel
α+Fe3C α+Fe3C α+Fe3C
Pearlite Pearlite + Pearlite +
proeutectoid ferrite proeutectoid
cementite
 TTT and CCT Diagrams

• There are two main types of transformation diagram that

are helpful in selecting the optimum steel and
processing route to achieve a given set of properties.

• These are time-temperature transformation (TTT)

and continuous cooling transformation (CCT)
diagrams.

• CCT diagrams are generally more appropriate for

engineering applications as components are cooled (air
cooled, furnace cooled, quenched etc.) from a
processing temperature as this is more economic than
transferring to a separate furnace for an isothermal
treatment.
 TTT and CCT Diagrams
• Time-temperature transformation (TTT) diagrams
– measure the rate of transformation at a constant temperature.

– In other words a sample is austenitised and then cooled rapidly

to a lower temperature and held at that temperature whilst the
rate of transformation is measured.
– Obviously a large number of experiments is required to build up
a complete TTT diagram.

• Continuous cooling transformation (CCT) diagrams

– measure the extent of transformation as a function of time for a
continuously decreasing temperature.
– In other words a sample is austenitised and then cooled at a
predetermined rate and the degree of transformation is
measured, for example by dilatometry.
– Obviously a large number of experiments is required to build up
a complete CCT diagram.
TTT Diagram
TTT Diagram
TTT Diagram
CCT Diagram
Different Cooling Curve in TTT Diagram
Summary: Processing Options
 Steel
• It wasn’t possible to make steel until about 1850
• Steel is an alloy of iron with up to 2% carbon and other elements
• Extremely wide range of strengths is available (100MPa to
2000MPa)
– Allotropy of iron is the key to producing high strength
• Strength depends mostly on carbon content and heat treatment
– Other alloy elements determine hardenability
Metal Classification
 Standard Steels
• Compositions of steels have been standardized by the American Iron
and Steel Institute (AISI) and the Society of Automotive Engineers
(SAE).
uses code
• First two digits constitute describe the chief alloying elements
• Last two or three digits are the carbon content in units of 0.01 %
e.g. 1040 is a plain carbon steel with 0.40% carbon (used for
structural purposes)

Alloying Carbon
Elements Content

XXXX(X)
• 52100 is a medium chromium steel with 1.00% carbon
(used in ball and roller bearings).
Different Classes of Steels
Different Classes of Steels
 Alloy Designations for AISI/SAE Steels

Alloy Type No. Alloy Type Number

Carbon Steels 1xxx Chromium Steels 5xxx
Plain Carbon Steels 10xx Low Chromium 51xx
Free Cutting Carbon Steel 11xx Medium Chromium 52xxx
Manganese Steels 13xx Corrosion & heat resisting 51xxx
Nickel Steels 2xxx Chromium-vanadium Steels 6xxx
3.5 % Ni. 23xx 1.0% Cr. 61xx
5.0 % Ni 25xx Chromium-nickel-moly. 86xx *
Nickel-chromium Steels 3xxx Chromium-nickel- moly 87xx *
1.25% Ni, 0.60% Cr 31xx Silicon-manganese Steels 9xxx
1.75% Ni, 1.00% Cr 32xx 2.00% Si. 92xx
3.50% Ni, 1.50% Cr 33xx
Corrosion & heat resisting 30xxx
Molybdenum Steels 4xxx * AISI Designations
Carbon-molybdenum 40xx
Chromium-molybdenum 41xx
Chromium-nickel- moly. 43xx
Nickel- moly. 1.75% Ni. 46xx
Nickel- moly. 3.5% Ni. 48xx
 Alloy Designations for AISI/SAE Steels

AISI designations add a letter prefix to the four

or five number designation to describe the
method of manufacturing.

AISI Prefix for Method of Manufacturing

Letter Method of Manufacturing

A Basic open-hearth alloy steel

B Acid Bessemer carbon steel
C Basic open-hearth carbon steel
D Acid open-hearth carbon steel
E Electric furnace alloy steel

Standard designations are also available for

cast irons.
Alloys Favorably Affecting Properties
 Effect of Elements in Steels

• Different elements are added to steels to given the steel different

properties.

• The elements pass on properties such as hardenability, strength,

hardness, toughness, wear resistance, etc.

• Some properties are beneficial while others are detrimental.

 Effect of Elements in Steels
• Boron: Improves hardenability without the loss of (or even with
some improvement in) machinability and formability.

• Calcium: Deoxidizes steels, improves toughness, and may improve

formability and machinability.

• Carbon: improves hardenability, strength, hardness, and wear

resistance; it reduces ductility, weldability, and toughness.

• Cerium: controls the shape of inclusions and improves toughness in

high-strength low alloy steels; it deoxidizes steels.

• Chromium: improves toughness, hardenability, wear and corrosion

resistance, and high-temperature strength; it increases the depth of
the hardness penetration resulting from heat treatment by promoting
carburization.
• Cobalt: improves strength and hardness at elevated temperatures.
 Effect of Elements in Steels
• Copper: improves resistance to atmospheric corrosion and, to a
lesser extent, increases strength with little loss in ductility; it
adversely affects the hot-working characteristics and surface quality.

• Lead: improves machinability; it causes liquid-metal embrittlement.

• Magnesium: has the same effects as cerium.

• Manganese: improves hardenability, strength, abrasion resistance,

and machinability; it deoxidizes the molten steel, reduce shot
shortness, and decreases weldability.

• Molybdenum: improves hardenability, wear resistance, toughness,

elevated-temperature strength, creep resistance, and hardness; it
minimizes temper embrittlement.
 Effect of Elements in Steels
• Nickel: improves strength, toughness, and corrosion resistance; it
improves hardenability.

• Niobium (columbium): imparts fineness of grain size and improves

strength and impact toughness; it lowers transition temperature and
may decrease hardenability.

• Phosphorus: improves strength, hardenability, corrosion resistance,

and machinability; it severely reduces ductility and toughness.

• Selenium: improves machinability.

• Silicon: improves strength, hardness, corrosion resistance, and

electrical conductivity; it decreases magnetic-hysteresis loss,
machinability, and cold formability.
 Effect of Elements in Steels
• Sulfur: Improves machinability when combined with manganese; it
lowers impact strength and ductility and impairs surface quality and
weldability.

• Tantalum: has effects similar to those of niobium.

• Tellurium: improves machinability, formability, and toughness.

• Titanium: improves hardenability; it deoxidizes steels.

• Tungsten: has the same effects as cobalt.

• Vanadium: improves strength, toughness, abrasion resistance, and
hardness at elevated temperatures; it inhibits grain growth during heat
treatment.
• Zirconium: has the same effects as cerium
 Carbon Steels
• Carbon steels are group by their
percentage of carbon content per
weight. The higher the carbon content
the greater the hardness, strength and
wear resistance after heat treatment.

• Low-carbon steel, also called mild

steels, has less than 0.30% carbon.
Used in everyday industrial products
like bolts, nuts, sheet, plate and tubes. High Carbon Steel Nails
•Medium-carbon steel has 0.30% to 0.60% carbon. Used for jobs
requiring higher strength such as machinery, automotive equipment parts,
and metalworking equipment.
• High-carbon steel has more than 0.60% carbon. Used parts that
require the highest strength, hardness, and wear resistance. Once
manufactured they are heat treated and tempered
 Alloy Steels
• Alloy steels are steels that contain significant amounts of alloying
elements.
 High strength low alloy steels
 Microalloyed steels
 Nanoalloyed steels

• High-strength, low-alloy steels (HSLA) steels were developed to

improve the ratio of strength to weight. Commonly used in automobile
bodies and in the transportation industry (the reduced weight makes
for better fuel economy ).
• Microalloyed steels Provide superior properties without the use of
heat treating. When cooled carefully these steels develop enhanced
and consistent strength.
• Nanoalloyed steels have extremely small grain size (10-100 nm).
Since their synthesis is done at an atomic level their properties can be
controlled specifically.
 Stainless Steels

• Stainless steels (200, 300, and 400 Of AISI designation)

- Corrosion resistance
- High strength and ductility
- High chromium content.

• In the presence of oxygen (air) they develop a thin, hard adherent

film of chromium oxide that protects the metal from corrosion.
The minimum chromium content should be 10% to 12% by weight.

In addition to chromium, other alloying elements in stainless steels

typically are nickel, molybdenum, copper, titanium, silicon,
manganese, columbium, aluminum, nitrogen, and sulfur.
 Stainless Steels: Classification

» Austenitic stainless steels

» Ferritic stainless steels
» Martensitic stainless steels
– Ferritic stainless steels:
Chromium 12% ~ 25%
Carbon 0.1% ~ 0.35%
• They are ferritic in structure up to their melting temperature.
Therefore, austenite cannot form, and these steels cannot form
the hard martensitic structure.
• They are often used in applications not requiring high
strength, such as jewelry, decorations, utensils, and automotive
trim pieces.
 Stainless Steels: Classification
• Austenitic stainless steels
• Nonmagnetic, machinable and weldable,
• Not heat-treatable.

• Low-carbon steels
– Chromium 16% ~ 26%
– Carbon <0.15%
• Nickel 6% to 23%

• One particular austenitic stainless steel is 18/8 stainless, which

contains 18% chromium and 8% nickel.
• These stainless steels are used in the chemical processing
industry, for food utensils, for architectural products, and for other
generally low-strength applications.
 Stainless Steels: Classification

• Martensitic stainless steels

• Magnetic, lower machinability and weldability
• Heat-treatable (be hardened by rapid cooling
(quenching) the steel from the austenitic range).
•
• Chromium 6% ~ 18%
– Carbon 0.1% ~ 1.5%
• Can have up to 2% nickel, but most do not
contain

• An excellent material for knives and cutlery.

 Tool and Die Steels
• Tool and die steels are alloyed steels design for high strength,
impact toughness, and wear resistance at normal and elevated
temperatures.

– High-speed steels Maintain their hardness and strength at

elevated operating temperatures. There are two basic types the M-
series and T-series
 Tool and Die Steels

• M-series contain 10 %
molybdenum and have
higher abrasion resistance
than T- series

• T- Series contain 12 % to
18 % tungsten. They
undergo less distortion in
heat treatment and are less
expensive than the M-
series. M- series steel drill bits coated with
titanium
 Tool and Die Steels

• Dies are tools used for drawing wire, and for blanking, bending,
cutting, machine forging, and embossing.

– H-series (Hot-working steels) for use at elevated temperatures.

They have high toughness and high resistance to wear and
cracking.
– S-series (shock resisting steels) designed for impact toughness.
 Cast Iron

Cast iron:

A family of ferrous alloys composed of iron and

carbon 2 to about 4.5%
silicon up to about 3.5%

Cast irons are usually classified according to their solidification

morphology from the eutectic temperature:
- Gray cast iron, or gray iron
- Ductile cast iron, nodular cast iron
- White cast iron
- Malleable iron
 Cast Iron
Gray cast iron

- 3% to 3.5% carbon and more than 1% silicon.

- Graphite exists largely in the form of flakes. When it is broken,
the fracture path is along the graphite flakes and has, therefore a
gray, sooty appearance.
- Grey cast iron has almost no ductility and will break if heated or
cooled too rapidly.
- Grey cast iron is used in furnace doors, machine bases, and
crankshafts due to its compression strength, machinability, and
vibration-damping qualities.

o Silicon in gray cast iron improves strength.

o Graphite in gray cast iron promotes machinability and lubricity.
o Gray cast iron is the least expensive of all metallic materials.
 Grey cast Iron

Spheroidal graphite cast Malleable cast iron

 Cast Iron
• Ductile Iron (Nodular Iron)
- Ductility is increased.
- Graphite is in a nodular or spheroid form. It can be heat
treated to obtain a structure of tempered martensite.
- Ductile cast iron is often used for engine blocks, pistons,
crankshafts, machine parts, and similar pieces.
• White Cast Iron
- The structure is very hard, wear-resistant, and brittle because
of the presence of large amounts of iron carbide. - to be
used in rolling and crunching equipment where wear resistance
is necessary.
 Cast Iron

Malleable cast iron

• Heat-treated versions of white cast iron, similar to ductile cast
iron.
• Promotes ductility, strength, and shork resistance.
• Light cementite regions are surrounded by pearlite
• Malleable iron
• Dark graphite rsettes (tempered carbon) in an α Ferrite matrix
GRAIN SIZE DETERMINATION
The grain size is often determined when the properties of
a polycrystalline material are under consideration. The
grain size has a significant impact of strength and
response to further processing

Linear Intercept method

• Straight lines are drawn through several
photomicrographs that show the grain
structure.
• The grains intersected by each line segment are
counted
• The line length is then divided by an average
number of grains intersected.
•The average grain diameter is found by dividing this
result by the linear magnification of the
photomicrographs.
ASTM (American Society for testing and Materials)

ASTM has prepared several standard comparison charts, all having different
average grain sizes. To each is assigned a number from 1 to 10, which is termed
the grain size number; the larger this number, the smaller the grains.

Grain size no.

No. of grains/square inch

N = 2 n-1

NOTE: The ASTM grain size is related (or relates)

a grain area AT 100x MAGNIFICATION
Page 104: Callister
 Solidification

Solidification is a comprehensive process of transformation of the melt of an alloy

into a solid piece of the alloy which involves

• Crystallization of the liquid phase

• Segregation of impurities and alloying elements
• Liberation of the gases dissolved in the melt
• Shrinkage Cavities and
• Porosity formation.

Crystallization is transformation of liquid phase to solid Crystalline phase.

There are two general stages of phase transformation (crystallization) process –

• Nucleation
• Growth
http://www.substech.com/dokuwiki/doku.php?id=solidification
Solidification
Grain Structure for Pure Metals

• Two types of grains are formed for a pure metal

– Fine equiaxed grains
– Columnar

• Rapid cooling at the walls produces fine equiaxed grains

• Columnar grains grow opposite of the heat transfer throughout

the mold following the chill zone

Equiaxed Grains
• If crystals can grow approximately equally in all directions –
equiaxed grains will grow.

• Large amounts of under cooling is needed near the wall of the

mold.
 Nucleation

• Nucleation is a process of formation of stable crystallization centers of a new phase.

• Nucleation may occur by either homogeneous or heterogeneous mechanism,
depending on the value of undercooling of the liquid phase (cooling below the
equilibrium freezing point).

Supercooling, also known as undercooling, is the process of lowering the

Temperature of a liquid or a gas below its freezing point without it becoming a solid.

Undercooling value determines quantity of nuclei, forming in the crystallizing alloy.

When a liquid comes into a contact with cold and massive mold wall (chill zone),
it cools fast below the freezing point, resulting in formation of a large quantity of stable
nuclei crystals.
 Nucleation

Presence of foreign particles or other foreign substance in the liquid alloy (walls of the
casting mold) allows to initiate crystallization at minor value of undercooling (few degrees
below the freezing point). This is heterogeneous nucleation.

If there is no solid substance present, undercooling of a hundred degrees is required in

order to form stable nuclei or “seeds” crystals, providing following crystal
growth (homogeneous nucleation)
Solidification
 Solidification of Metals
 Involves liquid metal turning back in to solid metal
 The process is different for Pure metals and alloys
 Can be divided into two steps:
 Formation of stable nuclei
 Growth of crystals

Pure Metals
• Have a clearly defined melting point
• Temperature remains constant during freezing
• Solidifies from the walls of the mold toward the center of
the part
Microstructural Changes during Solidification

Alloy
L
T

TL
L+S
TS
S
S

t
Page 313 Callister
 Homogeneous nucleation
• No preferred nucleation sites

Heterogeneous nucleation
• Nucleation site
– Mold walls
– Inclusion
– Interface
– Surface
– Impurity
 Heterogeneous nucleation
• Nucleation site
– Mold walls
– Inclusion
– Interface
– Surface
– Impurity
Two Contribution to the total free energy change that accompany a solidification
transformation.

• The first is the free energy difference between the solid and liquid phases, or the
volume free energy, ΔGv

• Second energy contribution results from the formation of the solid–liquid phase
boundary during the solidification transformation. Associated with this boundary is
a surface free energy, γ
Finally, the total free energy change is equal to the sum of these two contributions-
that is
Heat Treatment
Heat treating furnace at 1,800 °F (980 °C)
Steel castings after under going 12 hour 1,200 °C (2,190 °F) heat treatment
at Goodwin Steel Castings Ltd
Annealing Processing
 Heat Treatment

Steels are heat treated for one of the following reasons

1. Softening
Softening is done to reduce strength or hardness, remove residual stresses,
improve toughness, restore ductility, refine grain size

2. Hardening
Hardening of steels is done to increase the strength and wear properties. One of
the prerequisites for hardening is sufficient carbon and alloy content.
- Diffusion treatment hardening

3. Material Modification
Stress relieving, or strength properties, e.g., cryogenic treatment

Heat Treatment is the controlled heating and cooling of metals to alter their

physical and mechanical properties without changing the product shape

 Softening

 Annealing — Full Annealing, Process Annealing, Spheroidizing Annealing,

Stress-Relief Annealing

 Normalizing

 Tempering — Austempering and Martempering

Heat Treatment
 Heat Treatment

The critical temperatures (A1, A6, and Acm) are “arrests” in heating or cooling and
have been symbolized with the letter A, from the French word arret meaning arrest
or a delay point

The “c” is from the French word chauffage, meaning heating.

Thus, Ac1 is a few degrees above the ideal A1 temperature.

Ar, or Ar3, the “r” originating from the French word refroidissement, meaning
cooling.
 Process Annealing

Process annealing, also called "intermediate annealing", "subcritical annealing",

or "in-process annealing", is a heat treatment cycle that restores some of the
ductility to a work piece allowing it be worked further without breaking.

The piece is heated to a temperature typically below the austenizing temperature,

and held there long enough to relieve stresses in the metal. The piece is finally
cooled slowly to room temperature. It is then ready again for additional cold working.

The temperature range for process annealing ranges from 260°C(500 °F) to 760
°C (1400 °F), depending on the alloy
 Full Annealing
Full annealing is the process of slowly raising the temperature about 50 ºC (90 ºF)
above the Austenitic temperature line A3 in the case of Hypoeutectoid steels (steels
with < 0.77% Carbon) and 50 ºC (90 ºF) into the Austenite-Cementite region in the
case of Hypereutectoid steels (steels with > 0.77% Carbon).

Held for sufficient time to allow the material to fully austenitize, to form austenite or
austenite-cementite grain structure.

The material is then allowed to cool slowly so that the equilibrium microstructure is
obtained.
 Spheroidizing Annealing
Annealed hypereutectoid steel with a microstructure of pearlite and cementite network
generally gives poor machinability. Since cementite is hard and brittle, the cutting tool
cannot cut through these plates.

A heat-treating process which will improve the machinability is known as spheroidize

annealing.

Hypereutectoid steel is held for a long time at a temperature just below the lower
critical temperature line or is heated and cooled alternatively between temperatures
that are just above and just below the lower critical line.

Prolonged time at the elevated temperature will completely break up the pearlitic
Structure and cementite network. The cementite will become spheres. The cementite
Particles and the entire structure is called spheroidite.

This structure is desirable when minimum hardness, maximum ductility and

maximum machinability are required.
Spheroidizing Annealing
 Normalizing
The normalizing of steel is carried out by heating approximately 100°F above the
upper critical temperature line (A3 or Acm) followed by cooling in still air to room
temperature.
For hypereutectoid steels, it is necessary to heat it above the Acm line in order to
dissolve the cementite network.

The purpose of normalizing is to produce harder and stronger steel than full
annealing, so that for some applications normalizing may be a final heat treatment.

Normalizing is also carried out to improve machinability.

Normalizing
 Stress-Relief Annealing

Stress Relief Anneal is used to reduce residual stresses in large castings, welded
parts and cold-formed parts. Such parts tend to have stresses due to thermal cycling.

Parts are heated to temperatures of up to 600 - 650ºC (1112 - 1202ºF), and held for
an extended time (about 1 hour or more) and then slowly cooled in still air.
 Tempering
Untempered martensitic steel, while very hard, is too brittle to be useful for most
applications. A method for alleviating this problem is called tempering.

Most applications require that quenched parts be tempered.

Tempering consists of heating a steel below the lower critical temperature, (often
from 400 to 1105 ˚F or 205 to 595 ˚C, depending on the desired results), to impart
some toughness.

Higher tempering temperatures, (may be up to 1,300 ˚F or 700˚C, depending on

the alloy and application), are sometimes used to impart further ductility,

Tempering may also be performed on normalized steels. Other methods of tempering

consist of quenching to a specific temperature, which is above the martensite
start temperature, and then holding it there until pure bainite can form or internal
stresses can be relieved.

These include Austempering and Martempering.

 Austempering
Austempering is a quenching technique. The part is NOT quenched through the
Martensite transformation. Instead the material is quenched above the temperature
when Martensite forms MS, around 315 ºC (600 ºF). It is held till at this temperature
till the entire part reaches this temperature. As the part is held longer at this
temperature, the Austenite transforms into Bainite. Bainite is tough enough so
that further tempering is not necessary, and the tendency to crack is severely
reduced.
 Martempering
Martempering is similar to Austempering except that the part is slowly cooled through
The martensite transformation. The structure is martensite, which needs to tempered
just as much as martensite that is formed through rapid quenching.
 Case Hardening

• Case hardening or surface hardening is the process of hardening

the surface of a metal, often a low carbon steel, by infusing elements
into the material's surface, forming a thin layer of a harder alloy.

• Case hardening is usually done after the part in question has been
formed into its final shape.
 Case-Hardening - Processes

• Flame/Induction Hardening
• Carburizing
• Nitriding
• Cyaniding
• Carbonitriding
Case-Hardening - Processes

Case Hardened Steel

 Flame and Induction Hardening

• Flame or induction hardening are processes in which the surface of the

steel is heated to high temperatures (by direct application of a flame,
or by induction heating) then cooled rapidly, generally using water.

• This creates a case of martensite on the surface.

• A carbon content of 0.4–0.6 wt% C is needed for this type of

hardening.

• Application Examples -> Gears

 Carburizing

• Carburizing is a process used to case harden steel with a carbon

content between 0.1 and 0.3 wt% C.

• Steel is introduced to a carbon rich environment and elevated

temperatures (900 C) for a certain amount of time, and then
quenched so that the carbon is locked in the structure.

• Example -> Heat a part with an acetylene torch set with a fuel-rich
flame and quench it in a carbon-rich fluid such as oil
 Carburizing

• Carburization is a diffusion-controlled process, so the longer the steel

is held in the carbon-rich environment the greater the carbon
penetration will be and the higher the carbon content.

• The carburized section will have a carbon content high enough that it
can be hardened again through flame or induction hardening
 Carburizing
• The carbon can come from a solid, liquid or gaseous source.

• Solid source -> pack carburizing. Packing low carbon steel parts
with a carbonaceous material and heating for some time diffuses
carbon into the outer layers.

• A heating period of a few hours might form a high-carbon layer about

one millimeter thick.

• Liquid Source -> involves placing parts in a bath of a molten carbon-

containing material, often a metal cyanide.

• Gaseous Source -> involves placing the parts in a furnace maintained

with a methane-rich interior
 Nitriding
• Nitriding heats the steel part to 482–621°C in an atmosphere of NH3
gas and broken NH3 for 10 to 40 hours.

• The time the part spends in this environment dictates the depth of the
case.

• The hardness is achieved by the formation of nitrides.

• Nitride forming elements must be present in the workpiece for this

method to work.

• Advantage -> it causes little distortion, so the part can be case

hardened after being quenched, tempered and machined
 Cyaniding

• Cyaniding is mainly used on low carbon steels.

• The part is heated to 870-950°C in a bath of sodium cyanide

(NaCN)and then is quenched and rinsed, in water or oil, to remove
any residual cyanide.

• The process produces a thin, hard shell (0.5-0.75mm) that is harder

than the one produced by carburizing, and can be completed in 20 to
30 minutes compared to several hours.

• It is typically used on small parts.

• The major drawback of cyaniding is that cyanide salts are poisonous

 Carbonitriding

• Carbonitriding is similar to cyaniding except a gaseous atmosphere of

ammonia and hydrocarbons (e.g. CH4)is used instead of sodium
cyanide.
760 - 870 ºC

It is then quenched in a natural gas (Oxygen free) atmosphere. This quench is less
drastic than water or oil-thus less distortion. However this process is not suitable for high
precision parts due to the distortions that are inherent. The hardness achieved is similar
to carburizing (60 - 65 RC) but not as high as Nitriding (70 RC). The case depth is from
0.1 to 0.75 mm (0.004 to 0.030 in). The case is rich in Nitrides as well as Martensite.
Tempering is necessary to reduce the brittleness.
 Precipitation Hardening

• Precipitation hardening (or age hardening), is a heat treatment

technique used to increase the yield strength of malleable materials.

• Malleable materials are those, which are capable of deforming under

compressive stress.

• It relies on changes in solid solubility with temperature to produce

fine particles of an impurity phase, which blocks the movement of
dislocations in a crystal's lattice.
 Precipitation Hardening
• Since dislocations are often the dominant carriers of plasticity, this
serves to harden the material.

• The impurities play the same role as the particle substances in

particle-reinforced composite materials.

• Alloys must be kept at elevated temperature for hours to allow

precipitation to take place. This time delay is called aging
Alloy Development

Non Ferrous Alloys

 Nonferrous Alloys
Structural metals and alloys are often divided into two major categories, ferrous and
nonferrous materials.
• Ferrous alloys are those based on iron as the principal metal and include steels,
stainless steels, cast iron, etc, as discussed in our last lecture.
• Approximately 90% of the world’s production of metals/alloys are ferrous because
of their good strength, toughness, ductility and relatively low cost.

Nonferrous alloys are those based on other metals with particular emphasis on Al, Cu,
Ti, Zn, Zr, and Mg.
Aluminum is an extremely useful engineering material as:
• they are light weight and strong; Al has a density of 2700 kg/m3, which is about 1/3
that of steel.
• their strength to weight ratio is excellent.
• Al is non-toxic.
• Al is one of the best metal electrical conductors
• Al has good corrosion resistance due to its natural oxide layer, which is thin and
passive once formed.
 Aluminum
(cont’d)
Aluminum is an extremely useful engineering material as:
• Al stays ductile at low temperatures
• Al has a relatively low price
• It is the third most plentiful element on earth (next to oxygen and silicon).
• Al is easily alloyed and many of its alloys are stronger than pure Al.
• Al alloys are non-magnetic.
• Al alloys have a stable or predictable microstructure.
• Al alloys have an excellent machining, forming, and forging characteristics.
• Al alloys have a relatively high thermal expansion.
• Al alloys have a relatively high thermal conduction.
- Al’s FCC crystal structure retains its strength, ductility and toughness at
cryogenic temperatures. This is why we see many cryogenic tanks made
from Al.
 Aluminum
(cont’d)
Disadvantages of Aluminum include:
• Al has a low melting temperature so can’t be used at high temperatures
(above ~ 400 C)
• Al has low hardness so it is not good for wear resistance.
• Because Al’s elastic modulus is 1/3 that of steel, it’s deflection as a
structural component may be too great for the application.
• Al’s FCC structure work hardens so it may become brittle after plastic
deform and fracture easily.
• Al’s high thermal expansion sometimes causes problems with its use as an
interconnect for electronic devices. Good electronics use Cu alloys and the
best use Au.
 Hall- Heroult Process

Aluminum Carbon
Cathode Anode

Bauxite
Alumina CO2
Al O
plus
Fluoride salts

Pxxyy
xx = % Si Impurity Typical Grade: P1020
yy = % Fe Impurity 0.10% Si & 0.20% Fe

Additional Electrolytic Grades Range From:

Refining Available to get P0202 to P1535
99.999% Purity
The aluminum is produced extracting it from the aluminum oxide
(Al2O3), called also alumina, through an electrolysis process driven by
electrical current. The process uses as electrolyte a molten salts called
Cryolite (Na3AlF6) capable of dissolve the alumina. Carbon anodes are
immersed into the electrolyte (usually referred as the "bath") carrying
electrical current which then flows into the molten cryolite containing
dissolved alumina. As a result, the chemical bond between aluminum and
oxygen in the alumina is broken, the aluminum is deposited in the
bottom of the cell, where a molten aluminum deposit is found, while the
oxygen reacts with the carbon of the anodes producing carbon dioxide
(CO2) bubbles. The alumina reduction process is described by the
following reaction:
Aluminum Reduction Reaction

Once passed through the bath, the electrical current flows into the molten
aluminum deposit and is then collected by the bottom of the pot, usually
called "cathode".
Facility for producing aluminum sheet re-rolled
directly from molten aluminum

Metals Handbook vol 2, ASM

 Some Applications of Aluminum Alloys
• Heat-Treatable Alloys • Non-Heat-Treatable Alloys
– 2014 Hydraulic fittings for – 1060 Chem Processing Tanks
aircraft and automotive – 1100 Architectural
– 2036 6009 Automotive Body – 3003 General Purpose, Tanks
– 2219 tanks – 5052 Sheet Applications
– 6061 Structural
– 6101 Electrical Conductors
– 7075 High Strength Aircraft
 Classification of Aluminum Alloys
• Heat-Treatable Alloys • Non-Heat-Treatable Alloys
– Can obtain increased – Strengthened by work-
strength levels through hardening and solid solution
precipitation hardening strengthening
– Typical hardening additions – Elements such as manganese,
include copper, magnesium, silicon, iron and magnesium
zinc and silicon are typical solid-solution
– These additions show hardening agents
increasing solid solubility – Alloys of this type include the
with increasing temperature 1000, 3000, 4000 and 5000
– Alloys of this type include the series
2000, 6000 and 7000 series
 Aluminum Alloys
Aluminum alloys can be subdivided into two major groups based on their method of
fabrication:

•Wrought alloys
•Cast alloys

Wrought alloys are shaped by plastic deformation and have microstructures and
compositions different from the casting alloys because of the differences in
manufacturing requirements.

Within each of these two major groups, they are further subdivided into two
subgroups:

•Heat treatable alloys

•Non-heat treatable alloys

Heat treatable alloys are strengthened by “age hardening”, whereas nonheat treatable
alloys are strengthened by strain hardening.
AWS Welding Handbook
Chemical Composition of Aluminum Alloys

[Reference: Resistance Welding Manual, p.11-2, RWMA]

 Non-Heat Treatable Alloys
Temper Designations
Designation Description Application
O Annealed, Lowest Strength, High ductility
Recrystalized
F As Fabricated Fabrication with no special control over thermal or strain
hardening
H1 Strain Hardened Strain hardened without subsequent anneal
H2 Strain Hardened Strain hardened more than the desired amount and then
& Annealed partially annealed to strength
H3 Strain Hardened Strain hardened and low temp stabilization treatment to prevent
& Stabilized age softening
 Heat Treatable Alloys
Temper Designations
Designation Description Application
O Annealed, Lowest Strength, High ductility
Recrystalized
F As Fabricated Fabrication with no special control over thermal or strain
hardening
W Solution Heat Unstable temper application with subsequent period of natural
Treatment age
T1 Cooled and naturally aged
T2 Cooled, cold worked & Naturally aged
T3 Solution heat treated, cold worked & naturally aged
T4 Solution heat treated & naturally aged
T5 Cooled and artificially aged
T6 Solution heat treated and Stabilized
T7 Solution heat treated, stabilized to provide special property
T8 Solution heat treated, cold worked, artificially aged
T9 Solution heat treated, artificially aged, then cold worked
T10 Cooled, cold worked, then artificially aged
th
For a more extensive description see the table in AWS Welding Handbook, Vol 3, 8 Ed. Page 9
 Requirements for Age Hardening
Not all alloys are age hardenable. Four conditions must be satisfied for an alloy to have
an age-hardened response during heat treatment.

1)The alloy system must display a decreasing solid solubility with decreasing
temperature. In other words, the alloy must form a single phase on heating above the
solvus line, then enter a two-phase region on cooling.

2) The matrix should be relatively soft and ductile, and the precipitate should be hard
and brittle. In most age hardenable alloys, the precipitate is a hard, brittle
intermetallic compound.

3) The alloy must be quenchable. Some alloys cannot be cooled rapidly enough to
suppress the formation of the precipitate. Quenching may, however, introduce residual
stresses that cause distortion of the part. To minimize residual stresses aluminum
alloys are quenched in hot water, at about 80 oC, i.e., a hot quench.

4) A coherent precipitate must form. (see next slide)

Many important alloys are age-hardenable including stainless steels and alloys based
on aluminum, magnesium, titanium, nickel, chromium, iron, and copper.
 Noncoherent & Coherent Precipitates

a) b)

a) A noncoherent precipitate has no relationship with the

crystal structure of the surrounding matrix.
b) A coherent precipitate forms so that there is a definite
relationship between the precipitate and the matrix’s
crystal structure.
 Age Hardening
There are three steps to age harden materials such as Aluminum.

1. Solution Treatment – the alloy is heated above the solvus temperature into a
single phase region of the phase diagram to dissolve any secondary phases such
as precipitates. The material is held at this temperature until a homogeneous
solid solution is produced. Al is usually solution-treated between 500 oC and 548
oC.

2. Quench – the alloy is rapidly cooled so the atoms do not have enough time to
diffuse to potential nucleation sites. The alloy remains as a single phase material
that is supersaturated with alloying elements. If the material is work hardened,
the increase in dislocations density can be used as nucleation sites during aging.

3. Aged – The alloy is heated to a temperature below the solvus so the atoms can
diffuse to numerous nucleation sites to produce precipitates Ideally, uniformly
highly dispersed, ultrafine precipitates give the best effect in age hardening or
precipitate strengthening.
The key metallurgical feature of aluminium alloys that may be
hardened (strengthened) by heat treatment is complete solute solid
solubility at high temperature but only very limited solute solid
solubility at room temperature. Historically this was first recognised
with Al - Cu alloy
The strength and hardness of some metal alloys may be enhanced by the
formation of extremely small uniformly dispersed particles of a second
phase within the original phase matrix; this must be accomplished by
appropriate heat treatment. The process is called Precipitation Hardening
or Age Hardening which involves three distinct steps:

Solution Treatment to minimize segregation in the alloy, Quenching to

create a supersaturated solid solution and Aging to facilitate the
formation of coherent precipitates which strengthen the alloy by
interfering with dislocation movement.

The precipitate particles act as obstacles to dislocation movement and

thereby strengthen the heat-treated alloys.
The Al-Cu phase diagram shown in Figure 1 shows this type of decrease
along the solvus between the α and α + θ regions. Consider a 96wt%Al –
4wt%Cu alloy which is chosen since there is a large degrease in the solid
solubility of solid solution α in decreasing the temperature from 550°C
to 75°C. The precipitation-hardening process involves three basic steps:
Solution Treatment, Quenching and Aging.
Solution Treatment, or Solutionizing, is the first step in the
precipitation-hardening process where the alloy is heated above the
solvus temperature and soaked there until a homogeneous solid solution
(α) is produced. The θ precipitates are dissolved in this step and any
segregation present in the original alloy is reduced.

Quenching is the second step where the solid α is rapidly cooled

forming a supersaturated solid solution of αSS which contains excess
copper and is not an equilibrium structure. The atoms do not have time
to diffuse to potential nucleation sites and thus θ precipitates do not
form.
Aging is the third step where the supersaturated α , αSS, is heated below
the solvus temperature to produce a finely dispersed precipitate. Atoms
diffuse only short distances at this aging temperature. Because the
supersaturated α is not stable, the extra copper atoms diffuse to numerous
nucleation sites and precipitates grow. The formation of a finely
dispersed precipitate in the alloy is the objective of the precipitation-
hardening process. The fine precipitates in the alloy impede dislocation
movement by forcing the dislocations to either cut through the
precipitated particles or go around them. By restricting dislocation
movement during deformation, the alloy is strengthened.
In the age hardening of Al-Cu alloys, four structures of the precipitates
can be recognized: (1) GP-1 Zones, (2) GP-2 Zones (also called θ"), (3)
the θ’ Phase, and (4) the θ -(CuAl2) Phase. A large number of very small
solute-rich clusters form during the early stages of the aging process that
are completely coherent, that is they form on the FCC lattice of the
matrix (Figure 2). Since the atomic dimensions of the solute-rich regions
will differ somewhat from that of the lattice, strains occur in the lattice
regions around the clusters. These regions that are distorted by the
clusters are referred to as Guinier-Preston zones.
GP-1 zones grow rapidly up to a certain size, typical of the temperature
of aging, and then growth practically stops. At room temperature this size
is 3-7 nm thick and at 70-130°C the diameter is of the order of 10-15
nm.

Hardening and a decrease in ductility accompany the formation and

growth of the GP-1 zones; these effects have been attributed to the
distortion of the lattice which inhibits the movement of dislocations.

The GP-1 zones are eventually replaced by GP-2 zones during the aging
process. GP-2 zones (“θ" phase) are larger than the GP-1 zones and their
number is correspondingly smaller since the amount of solvent in the
zones does not change. The size range for the θ" phase is 10-100 nm
diameter, and 1-4 nm thick. Optimal mechanical properties are achieved
by growing the θ" phase as large as possible without beginning to from
the intermediate θ’ phase.
With continued aging, the intermediate ‘θ’ phase will begin to form
causing recrystallization, softening, and a decrease in strength; this is
known as over-aging. The θ’ phase has a tetragonal structure with a
different lattice parameter from the matrix; no coherency strains exist,
but each particle is surrounded by a ring of dislocations. The size of the
θ’ phase depends on time and temperature; size ranges from 10 to 600
nm diameter with a thickness of 10-15 nm.
Eventually the θ’ phase is replaced by θ-(CuAl2) which has the same
structure and composition as the θ phase found by solidification.
Not all structures form at all aging temperatures.

Below 80°C aging seldom progresses past the GP-1 stage; only above
220°C does the θ’ phase appear within a reasonable time interval, and
temperatures above 280°C are needed for the θ phase to appear.

Conversely, at higher temperatures the early stages do not appear and

the GP-1 zones do not appear above 180°C; the θ" phase will not form
above 230°C.
Maximum hardness is reached sooner at higher temperatures and the
maximum hardness reached generally decreases as the aging temperature
is raised for precipitation-hardening.
Consider an alloy of composition Al + 4wt% Cu.

At a temperature of 550°C (point A on the diagram) the equilibrium

microstructure is a complete, random solid solution of copper atoms in
the aluminium matrix; this is designated as α phase.

at room temperature and after extremely slow cooling the equilibrium

microstructure consists of an extremely dilute concentration of copper in
the α phase together with coarse particles of an equilibrium second phase
CuAl2, which are formed predominantly at high temperatures (say
between about 450°C and 300°C during cooling).

Rapid quenching from A to B freezes in the random solid solution that

existed at 550°C.
The characteristic phase diagram for Al - Cu is illustrated in
Figure
The copper atoms cluster in local groups (picture C in to form the
Guinier-Preston zones (GP zones) that were introduced at the start of
this section. The process is called precipitation; that is, the clusters of
solute atoms (the GP zones) precipitate out from solid solution.
the quenched alloy is said to be in a metastable state of supersaturated
solid solution. This means that the microstructure is thermodynamically
unstable, with a metallurgical driving force for the alloy to move towards
the equilibrium structure - the total free energy of the system is
progressively reduced as it moves towards equilibrium
Heat Treatment for Aluminum - 3
• Precipitation Hardening:
• Some times called age hardening, used on aluminum, copper, nickel, magnesium
and some stainless alloys

• Ageing:
• The ageing process can be divided into two main categories after the ageing
temperature

• Natural Ageing:
• The Heat treatable alloys changes properties when stored at room temperature after
solution heat treatment and quenching.

• Artificial Ageing: By heating the solution heat treated material to a temperature

above room temperature and holding it there the precipitation accelerates and the
strength is farther increased compare to natural ageing
Age Hardening
 Age Hardening

nuclei of the θ
precipitate, which
is eventually forms
in Al-Cu Alloys.

The yield strength hardens by the formation of precipitates,

which after longer times rippen (get large) and the strength falls
off. The strength does not fall off at low aging temperatures.
2. Solid solution hardening- the solute
distorts the lattice and drag the dislocation
movement
3. Precipitate hardening- fine particle
distributed within grain or at grain boundary
to prevent dislocation movement

42
The second digit indicates special purity controls
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 Nickel and Cobalt Alloys
Nickel and Cobalt alloys are used for corrosion protection and for high-temperature
resistance, taking advantage of their high melting points and high strengths.

Nickel is FCC and has good formability. Cu-Ni is the classic example of complete solid
solubility. Monel is the name given to commercial alloys with Ni-Cu ratios of roughly
2:1 by weight.

These alloys are good examples of solution hardening in which the alloys are
strengthened by the restriction of plastic deformation due to solid-solution formation.

Cobalt is FCC above 417 oC and HCP below this temperature.

Cobalt is used because of its exceptional wear resistance, and because of its resistance to
body fluids, as a biomedical material for prosthetic devices such as hip and knee socket
replacement.

Typical alloys and their uses are listed in the following table.
Superalloys: a broad class of materials with specially high
strength at elevated temperatures
Turbine blade design for active cooling by a gas shown in a) and the increase
in the high-temperature capability of Ni superalloys as a result of improved
manufacturing methods from producing a polycrystalline material to a single
crystal material.
 Titanium Alloys
While there are numerous other nonferrous alloys such as Mg, Zn, and Zr,
which can be considered for special applications, the alloys that has received
considerable attention is Titanium, Ti.

•Ti is relatively light weight (4505 kg/m3)

•Ti has excellent corrosion resistance, especially in sea water
•Ti has a high strength to weight ratio
•Some Ti alloys have a strength of over 150,000 psi (1000 MPa)
•It’s surface oxide (TiO2) breaks down at ~500 C, which limits the range of its
use, but surface coatings help to increase it’s range of use to much higher
temperatures (~1000 C).
•Ti has a HCP structure at room temperature and changes to BCC at 882 C –
alloying with niobium stabilizes the BCC phase to room temperature, which
enhances fabricability.
•Typically, other elements added to Ti increase its strength and machinability.
 Refractory Alloys
Refractory metals include tungsten (W), molybdenum (Mo), tantalum (Ta) and
niobium (Nb).

Their metallic bonds are weak resulting in low yield strengths.

They have exceptionally high melting temperature (>1925 C) and so have

high-temperature service.

They have a BCC structure so they display a ductile to brittle transition

temperature. Hot forming these materials aids their fabrication into useable
products.

Applications include filaments for light bulbs (tungsten), rocket nozzles,

nuclear power generators (niobium), electronic capacitors (tantalum and
niobium) and chemical processing equipment.
 Precious Metals
These include gold, silver, palladium and rhodium.

They are precious and expensive.

These materials resist corrosion and make very good conductors of electricity.
As a result alloys of these materials are often used as electrodes for devices.

Because of their corrosion resistance, they are used as nano-sized particles as

catalysts in automobile exhaust systems and in petroleum refining. In exhaust
gases, they facilitate the oxidation of CO to CO2 and NOx to N2 and O2.
Processing of Metals
 Materials may have harden by
1. Strain hardening- when ductile metals are
cold worked, this leads to increase of
dislocation density and distorted lattice. If
the cold working stops, the atom may
diffuse again into a more stable form. This
process called ‘Annealing’ and can be
speed up by controlled heat treating
procedure. (The effect of temperature on
grain structure includes Recovery,
Recrystallisation and Grain growth) 73