MM-207 LECTURE SET-3

By Group 3
Autumn Semester 2014
Submitted to :
Prof. B.P. Kashyap

Solvus Line

Precipitation Hardening

Microstructure of precipitate
hardened 7150 Al

Age Hardening

Solvus
curve

Solvus curve

AGE-HARDENING PROCESS

STAGES OF PRECIPITATES

Al-Cu ppt structures

Stages of Precipitation Hardening

and their contributions
1. GP Zone

At room temperature, copper atoms segregate by diffusion to form

copper-rich zones called Guinier-Preston or GP zones. These are only
one atom thick and around 5 nm to 10 nm in diameter.
Hardening is therefore due to the increased work required to move
dislocations through the strained lattice (coherency stress) and work
required for dislocations to pass though the GP zones (cutting stress)

Stages of Precipitation Hardening

and their contributions
2. Zone

Above around 100C, further copper segregation produces theta"

phase which is a few atoms thick and up to 15 nm in diameter.
Hardening occurs by the same mechanisms as the GP zones, though
theta" zones have a stronger effect due to coherent lattice structure.

Stages of Precipitation Hardening

and their contributions
3. Zone

Further growth of the GP(2) zones leads to the formation of the

theta' phase, which is not fully coherent with the lattice.

Strengthening is due to a combination of lattice coherency strain

(coherency stress), precipitate cutting by dislocations (cutting
stress) and dislocation bowing between precipitates (bowing
stress).

Stages of Precipitation Hardening

and their contributions
4. Zone

With further ageing, the precipitate distribution changes as large,

widely dispersed precipitates grow at the expense of finely
dispersed small precipitates. Dislocation bowing between
precipitates becomes easy and the strengthening contribution
from coherency strain and precipitate cutting is lost. This is called
overaging.

DISLOCATION-PRECIPITATE INTERACTION

Al rich end of the Al-Cu phase diagram

T (C)

600

400

200

Al

Sloping Solvus line

high T high solubility
low T low solubility
of Cu in Al

15

30
% Cu

45

60

+
Slow equilibrium cooling gives rise to
coarse precipitates which is not good
in impeding dislocation motion.*

4 % Cu

( FCC )
( FCC ) CuAl2 (Tetragonal)

slow cool

0.5 % Cu
52 % Cu
4 % Cu

550o C
RT

RT

To obtain a fine distribution of precipitates the cycle A B C is used

Note: Treatments A, B, C are for the same

composition

C
+

4 % Cu
A

Heat (to 550oC) solid solution

supersaturated solution
B
C

Quench (to RT)

Increased vacancy concentration

Age (reheat to 200oC) fine precipitates

Hardness

100oC

180oC
20oC

Log(t)
Higher temperature less time of aging to obtain peak hardness
Lower temperature

increased peak hardness

optimization between time and hardness required

Hardness

180oC

Peak-aged

Dispersion of
fine precipitates
(closely spaced)

Coarsening
of precipitates
with increased
interparticle spacing
Overaged

Underaged

Log(t)
Region of solid solution
strengthening
(no precipitation hardening)

Region of precipitation
hardening
(but little solid solution
strengthening)

Peak-aged

CRSS Increase

Hardness

180oC

Log(t)
Particle
shearing

Particle
By-pass

1
r
r
Particle radius (r)
1
2

r f (t )

Age Hardening Curves

The most quoted age hardening curve
is that for Al-Cu alloys performed in
the late 40s. Keep in mind that age
hardening was known empirically
(Alfred Wilm) as a technologically
useful treatment from the early days
of aluminum alloys.
Higher Cu contents result in higher
maximum hardnesses because larger
volume fractions of precipitate are
possible.

ANTI-PHASE BOUNDARY

SUPERDISLOCATION

INTERFACES AND INTERPHASES

Mechanisms of Precipitate Hardening

1)Coherency Hardening: differences in density between the particle and the matrix
give rise to elastic stresses in the vicinity of the particle.
2)Chemical Hardening: creation of new surface when a particle is sheared increases
the area of the interphase boundary, which increases the energy associated with the
interface and hence an additional force must be exerted on the dislocation to force it
through the particle
3)Dispersion Hardening: As the incoherency increases, the dislocations tend to bow
around the particles and move which is termed as dispersion hardening

Chemical hardening

Cutting through a particle with a dislocation displaces one half relative to the other
by b, thereby creating new interfacial energy of 2rbg, where g is the interfacial
energy between the matrix and the particle. The distance over which this energy has
to be created occurs at the entry and exit points and so the characteristic distance is
of order b. Thus the force is dE/dx, or,
F = 2rbg/2b = rg

Coherency hardening
Differences in density between the particle and the matrix
give rise to elastic stresses in the vicinity of the particle.
This has been analyzed on the basis of the elastic stresses
that exist in the matrix adjacent to a particle that has a
different lattice parameter than the matrix.

This mechanism applies to the early stages of

precipitation, e.g. strengthening by GP zones.

Dispersion Hardening
In dispersion-hardening it is assumed that the precipitates do not deform with the
matrix and that the yield stress is the stress necessary to expand a loop of dislocation
between the precipitates. This will be given by the Orowan stress.
=b/L
The yield stress decreases as the distance between the obstacles increases in the
over-aged condition.

ISO-YIELD STRENGTH CURVES

Phase Transformation and Nucleation

Solidification

Nucleation

Nucleation

Growth

Homogenous

Nucleation
Heterogenous

Liquid solid
walls of container, inclusions
Solid solid
inclusions, grain boundaries,
dislocations, stacking faults

The probability of nucleation occurring at point in the parent phase is

same throughout the parent phase
In heterogeneous nucleation there are some preferred sites in the
parent phase where nucleation can occur

Bulk Gibbs free energy

Energies involved

Interfacial energy
Strain energy

Solid-solid transformation

New interface created

Volume of transforming material

The concepts are illustrated using solidification of a metal

Liquid Solid phase transformation

On cooling just below Tm solid becomes stable
But solidification does not start
E.g. liquid Ni can be undercooled 250 K below Tm
t
Solid stable

Liquid stable

Solid (GS)
G ve

G +ve
Tm

T - Undercooling

Liquid (GL)
For sufficient
Undercooling

Neglected in L S
transformations

Homogenous nucleation

Free energy change on nucleation

Reduction in bulk free energy increase in surface energy increase in strain energy

G (Volume).(G) (Surface).( )

4 3
G r .( Gv ) 4r 2 .( )
3

Gv f (T )

r3
r2

G r 3 .( Gv ) 4r 2 .( )
3

By setting dG/dr = 0 the critical values (corresponding to the maximum)

are obtained (denoted by superscript *)
Reduction in free energy is obtained only after r0 is obtained

dG
0
dr
2
r
Gv

As Gv is ve, r*is +ve

2
*
*
r1 0 r2
Gv
Trivial

dG
0
dr

G 0

3
r0
Gv

G 0

3
16

G *
3 Gv2

r*
Embryos

r0
Supercritical nuclei

Turnbulls approximation

h heat of fusion

Tm T
T
G h
h
Tm
Tm

Solid (GS)

Liquid (GL)
Tm

16 3 Tm

G
3
hT
*

dG
0
dr

*
hetero

*
hetero

Gv

G
G*hetero / G*homo

*
hetero

4
3

2

3
Cos

Cos

2
3 Gv

1 *
Ghomo 2 3Cos Cos 3
4

G*hetero (0o) = 0
no barrier to nucleation

G*hetero (180o) = G*homo

no benefit

0.75

G*hetero (90o) = G*homo/2

0.5

Cos

0.25
Complete wetting

No wetting

Partial wetting

0
0

30

60

90

120

(degrees)

150

180

Rate of nucleation =

dN
I
dt

No. of critical sized

particles

N Nt e
*

G*

kT

No. of particles/volume in L

Frequency with which they

become supercritical

' s e
*

H d

kT

lattice vibration frequency (~1013 /s)

s* atoms of the liquid facing the nucleus

Critical sized nucleus

Jump taking particle to supercriticality

nucleated (enthalpy of activation = Hd)
Critical sized nucleus

I Nt s e
*

G * H d

kT

G* I
T I

T = Tm G* = I = 0

T (K)

Increasing T

Tm

T=0I=0

Time Temperature Transformation (TTT) diagrams

A type of phase
diagram

Small driving
force for nucleation

Tm

T
Replot

T (rate sec1)

T (K)

T (K)

Tm

Time for transformation

t (sec)
Growth
sluggish

TTT diagram phase transformation

T (K)

Increasing % transformation

99% = finish

1% = start

t (sec)

Time- Temperature-Transformation (TTT) Curves Isothermal Transformation

Eutectoid steel (0.8%C)

800
723

Eutectoid temperature

Austenite

Coarse

Pearlite

600

Pearlite + Bainite

500
400
300
Not an isothermal
transformation

200

100

Fine

Bainite

Ms

Austenite

Mf
Martensite

0.1

102
10
t (s)

103

104

105

Time- Temperature-Transformation (TTT) Curves Isothermal Transformation

Eutectoid steel (0.8%C)

800
723

Eutectoid temperature

Austenite
Pearlite

600
+ Fe3C

500

Pearlite + Bainite

400

Bainite

300
200

100

Ms
Mf
Martensite

0.1

102
10
t (s)

103

104

105

Pearlite

[1]

[1]

+ Fe3C

Nucleation and growth

Heterogeneous nucleation at grain boundaries
Interlamellar spacing is a function of the temperature of transformation
Lower temperature finer spacing higher hardness

Bainite

[1]

[1]
Bainite formed at 348oC

Bainite formed at 278oC

+ Fe3C**

Nucleation and growth

Acicular, accompanied by surface distortions
** Lower temperature
carbide could be carbide (hexagonal structure, 8.4% C)
Bainite plates have irrational habit planes
Ferrite in Bainite plates possess different orientation relationship
relative to the parent Austenite than does the Ferrite in Pearlite

Martensite

( FCC )
0.8 %C

Quench

' ( BCT )
0.8 %C

Possible positions of
Carbon atoms
Only a fraction of
the sites occupied

FCC
Austenite

C along the c-axis

obstructs the contraction
FCC
Austenite
Alternate choice of
Cell

20% contraction of c-axis

12% expansion of a-axis

Tetragonal
Martensite

Austenite to Martensite 4.3 % volume increase

In Pure Fe after
the Matensitic transformation
c=a

Martensite
The martensitic transformation occurs without composition change
The transformation occurs by shear without need for diffusion
The atomic movements required are only a fraction of the interatomic
spacing
The shear changes the shape of the transforming region
results in considerable amount of shear energy
plate-like shape of Martensite
The amount of martensite formed is a function of the temperature to
which the sample is quenched and not of time
Hardness of martensite is a function of the carbon content
but high hardness steel is very brittle as martensite is brittle
Steel is reheated to increase its ductility
this process is called TEMPERING

Hardness (Rc)

60
Harness of Martensite as a
function of Carbon content
40

20

% Carbon
0.2

0.4

0.6
Properties of 0.8% C steel
Hardness (Rc)

Tensile strength (MN / m2)

Coarse pearlite

16

710

Fine pearlite

30

990

Bainite

45

1470

Martensite

65

Martensite tempered at 250 oC

55

1990

Constituent

Kolmogorov-Johnson-Mehl-Avrami Equation
The kinetics of transformation are typically described by a standard equation known
as the Kolmogorov-Johnson-Mehl-Avrami equation, named after the individuals who
derived it.
The characteristic of the kinetics is that of the S-curve, i.e. slow at first, then
accelerating, then decelerating.

1 exp kt

KJMA Notation
The central idea in the derivation of the KJMA equation is to focus on the increment
in the (volume) fraction transformed and to relate it to the current value of the
fraction transformed.
Notation:
f
fraction transformed
t
time
t50% time required for 50% transformation
r
radius
V volume
v
growth rate (speed)
t
incubation/delay time
N rate of nucleation, or, density of nuclei per unit volume

KJMA solutions

In general, the k value contains all the temperature dependent terms because
thermal activation affects
the growth strongly through
boundary/interface mobility,
and because the nucleation
density depends very strongly
on driving force.
See P&E p269:
v = v(T) = v0 exp-(Q/RT)

In general, the exponent n in the equation is related to the geometry of the

transformation.

KJMA plots

A very useful way to analyze the kinetics of

transformation (e.g. recrystallization) is to plot the
quantity -ln(1-f) versus time on a double-logarithmic plot.
The slope of the line is then the exponent, n.

logln(1 f ) log(k) nlog(t)

Heat-Treatment
Heat treatment is a method used to alter the physical, and
sometimes chemical properties of a material. The most
common application is metallurgical
It involves the use of heating or chilling, normally to
extreme temperatures, to achieve a desired result such as
hardening or softening of a material
It applies only to processes where the heating and cooling
are done for the specific purpose of altering properties
intentionally

Heat Treatment of Steels for Strength:

Steel = 0.06% to 1.0% carbon
Must have a carbon content of at least .6% (ideally) to
heat treat.
Must heat to austenitic temperature range.
Must rapid quench to prevent formation of equilibrium
products.
Basically crystal structure changes from BCC to FCC at
high Temp.
Almost always followed by tempering.

Types of Heat-Treatment (Steel)

Annealing
Normalizing
Spheroidizing
Tempering and Quenching
Precipitate Hardening
Surface Heat Treatments

Time-TemperatureTransformation (TTT)Curve

The TTT diagram for AISI 1080 steel (0.79%C, 0.76%Mn) austenitised at
900C

Annealing

It is a heat treatment wherein a material is altered,

causing changes in its properties such as strength and
hardness

It the process of heating solid metal to high

temperatures and cooling it slowly so that its particles
arrange into a defined lattice

Advantages of Annealing

What does it do?

1. Reduce hardness
2. Remove residual stress (stress relief)
3. Improve toughness
4. Restore ductility
5. Refine grain size

Types of Annealing

1.
2.
3.
4.

Stress-Relief Annealing (or Stressrelieving)

Normalizing
Isothermal Annealing
Spheroidizing Annealing (or
Spheroidizing )

Stages of annealing:

Stages of annealing:
Heating to required temperature
Holding (soaking) at constant temperature
Cooling

Soaking time at the high temperature needs to be long enough to allow desired transformation
to occur.
Cooling is done slowly to avoid warping/cracking of due to the thermal gradients and thermoelastic stresses within the or even cracking the metal piece.

1. Stress-Relief Annealing

It is an annealing process below the

transformation temperature Ac1, with
subsequent slow cooling, the aim of
which is to reduce the internal
residual stresses in a workpiece
without intentionally changing its
structure and mechanical properties

Causes of Residual Stresses

1. Thermal factors (e.g., thermal stresses caused by
temperature gradients within the workpiece during
heating or cooling)
2. Mechanical factors (e.g., cold-working)
3. Metallurgical factors (e.g., transformation of the
microstructure)

How to Remove Residual Stresses?

R.S. can be reduced only by a plastic deformation in the
microstructure.
This requires that the yield strength of the material be lowered
below the value of the residual stresses.
The more the yield strength is lowered, the greater the plastic
deformation and correspondingly the greater the possibility or
reducing the residual stresses
The yield strength and the ultimate tensile strength of the steel
both decrease with increasing temperature

Stress-Relief Annealing Process

For plain carbon and low-alloy steels the temperature to
which the specimen is heated is usually between 450 and
650C, whereas for hot-working tool steels and high-speed
steels it is between 600 and 750C
This treatment will not cause any phase changes, but
recrystallization may take place.
Machining allowance sufficient to compensate for any
warping resulting from stress relieving should be provided

2. Normalizing
A heat treatment process consisting of
austenitizing at temperatures of 3080C
above the AC3 transformation temperature
followed by slow cooling (usually in air)
The aim of which is to obtain a finegrained, uniformly distributed, ferrite
pearlite structure
Normalizing is applied mainly to unalloyed
and low-alloy hypoeutectoid steels
For hypereutectoid steels the austenitizing
temperature is 3080C above the AC1 or
ACm transformation temperature

Normalizing Heating and

Cooling

Normalizing Austenitizing
Temperature Range

Effect of Normalizing on Grain Size

Normalizing refines the grain of a steel that

has become coarse-grained as a result of
heating to a high temperature, e.g., for
forging or welding

Carbon steel of 0.5% C. (a) As-rolled or

forged; (b) normalized. Magnification 500

Spheroidizing
Spheroidizing: prolonged heating just below the eutectoid temperature, results in
the soft spheroidite structure. This achieves maximum softness needed in
subsequent forming operations.
Spheroidite consists of small spherical structure of cementite in the matrix of -iron.
The spheroidite is the softest and weakest of all the carbon steels.

Direct Hardening Austenitizing and quench

Austenitizing again taking a steel with .6% carbon or greater and heating to the
austenite region.
Rapid quench to trap the carbon in the crystal structure called martensite (BCT)
Quench requirements determined from isothermal transformation diagram (IT
diagram).
Get Through Hardness!!!

Austenitizing:

Heat to austenite
range. Want to be
close to
transformation
temperature to get
fine grain structure.

For this particular steel want to cool from about 1400 F to <400 F in about 1
second!

Quenching:

Depending on how fast steel must be quenched (from IT diagram), the

heat treater will determine type of quenching required:
Water (most severe)
Oil
Molten Salt
Gas/ Air (least severe)
Many phases in between!!! Ex: add water/polymer to water reduces
quench time! Adding 10% sodium hydroxide or salt will have twice
the cooling rate!

Softening and Conditioning - Tempering

Almost always done following heat treat as part of the austenitizing process!
Because of lack of adequate toughness and ductility after heat treat, high carbon
martensite is not a useful material despite its great strength (too brittle).
Tempering imparts a desired amount of toughness and ductility (at the expense of
strength)

Softening and Conditioning - Tempering

Typical HT steps (Summarized Again):

Austenize: Heat into stable single phase region and HOLD for
uniform chemistry single phase austenite.
Quench: Rapid cool crystal changes from Austenite FCC to
Martensite BCT which is hard but brittle.
Temper: A controlled reheat (BELOW AUSTENITE REGION).
The material moves toward the formation of a stable two phase
structure tougher but weaker.
Quench: The properties are then frozen in by dropping
temperature to stop further diffusion

TTT of Idealized Hot Quench Tempering

MARTEMPERING

To avoid residual stresses generated during quenching

Austenized steel is quenched above Ms for homogenization of temperature
across the sample
The steel is then quenched and the entire
sample transforms simultaneously
800
Eutectoid temperature
Tempering follows
723
Austenite
Pearlite
600
+ Fe3C

Pearlite + Bainite

400

Bainite

Martempering

500

300

Ms

200

AUSTEMPERING

Austempering

Mf
100

Martensite
0.1

10

102
t (s)

To avoid residual stresses generated during quenching

Austenized steel is quenched above Ms
Held long enough for transformation to Bainite

103

104

105

Phases During Quenching and Tempering

80-100 C- No detectable changes

100-250 C- Martensite decomposes with precipitation of Carbon as dispersed Iron
Carbide particle.
250 C- Martensite decomposition into tempered martensite is complete which is
supersaturated solution of C in -Fe
250-350 C- Additionally, retained austenite also decomposes.
350 C- After decomposition of martensite and austenite, elastically deformed
crystals of -Fe solid solution in which finely dispersed particles of cementite are
distributed

ROLE OF ALLOYING ELEMENTS

Interstitial
Segregation / phase separation

Solid solution

Substitutional

Element Added
Compound (new crystal structure)

Plain Carbon Steel

Alloying elements

+ Simplicity of heat treatment and lower cost

Low hardenability
Loss of hardness on tempering
Low corrosion and oxidation resistance
Low strength at high temperatures
hardenability
Provide a fine distribution of alloy carbides during tempering
resistance to softening on tempering
corrosion and oxidation resistance
strength at high temperatures
Strengthen steels that cannot be quenched
Make easier to obtain the properties throughout a larger section
Elastic limit (no increase in toughness)

Alter temperature at which the transformation occurs

Alter solubility of C in or Iron
Alter the rate of various reactions

Ausforming and TTT

Ausforming also known as Low and

High temperature thermomechanical
treatments is a method used to
increase the hardness and
stubbornness of an alloy by
simultaneously tempering, rapid
cooling, deforming and quenching to
change its shape and refine
the microstructure. This treatment is
an important part in the processing of
steel.

Diffusion Hardening

Most Common Types:

Carburizing
Nitriding
Carbonitriding
Cyaniding

Diffusion Hardening - Carburizing

Pack carburizing most common:

Part surrounded by charcoal treated with activating chemical then heated to
austenite temperature.
Charcoal forms CO2 gas which reacts with excess carbon in charcoal to form CO.
CO reacts with low-carbon steel surface to form atomic carbon
The atomic carbon diffuses into the surface
Must then be quenched to get hardness!

Diffusion Hardening - Nitriding

Nitrogen diffused into surface being treated. Nitrogen reacts with steel to form very
hard iron and alloy nitrogen compounds.
Process does not require quenching big advantage.
The case can include a white layer which can be brittle disadvantage
More expensive than carburizing

Source of nitrogen

Reduction process: 2NH3

2N + 3H2

Recovery, Recrystallization & Grain Growth

Plastic deformation in the temperature range (0.3 0.5) Tm COLD WORK

point defect density
Cold work

dislocation density

Point defects and dislocations have strain energy associated with them
(1 -10) % of the energy expended in plastic deformation is stored in the
form of strain energy

Annealed material
Stronger material
Cold work

6
9
dislocation ~ (10 10 )
dislocation ~ (1012 1014 )

 point defect density

Anneal

Cold work

Material tends to lose

the stored strain energy

dislocation density
Increase in strength
of the material

Low temperature
Cold work

Softening of the material

Recovery

Anneal
High temperature

Recrystallization

Cold work

Anneal

Recovery

Recrystallization

Grain growth

 Strength
Hardness
Cold work

Electrical resistance
Ductility
Changes occur to almost all physical and mechanical properties
X-Ray diffration
Laue patterns of single crystals show pronounced asterism
due to lattice curvatures
Debye-Scherrer photographs show line broadning
Residual stresses + deformations

Recovery
Recovery takes place at low temperatures of annealing
Apparently no change in microstructure

Excess point defects created during Cold work are absorbed:

at surface or grain boundaries
by dislocation climb
Random dislocations of opposite sign come together and annihilate each
other
Dislocations of same sign arrange into low energy configurations:
Edge Tilt boundaries
Screw Twist boundaries
POLYGONIZATION
Overall reduction in dislocation density is small

POLYGONIZATION

Bent crystal

Low angle grain boundaries

Recrystallization
Trecrystallization (0.3 0.5) Tm
Nucleation and growth of new, strain free crystals

Nucleation of new grains in the usual sense may not be present and
grain boundary migrates into a region of higher dislocation density
G (recrystallization) = G (deformed material) G (undeformed material)

TRecrystallization is the temperature at which 50 % of the material

recrystallizes in 1 hour

Region of higher
dislocation density

Direction of grain
boundary migration

Region of lower
dislocation density

Further points about recrystallization

Deformation recrystallization temperature (Trecrystallization)
Initial grain size recrystallization temperature
High cold work + low initial grain size finer recrystallized grains

cold work temperature lower strain energy stored

recrystallization temperature
Rate of recrystallization = exponential function of temperature

Trecrystallization = strong function of the purity of the material

Trecrystallization (very pure materials) ~ 0.3 Tm
Trecrystallization (impure) ~ (0.5 0.6) Tm
Trecrystallization (99.999% pure Al) ~ 75oC
Trecrystallization (commercial purity) ~ 275oC
The impurity atoms segregate to the grain boundary and retard their
motion Solute drag (can be used to retain strength of materials at
high temperatures)

 The impurity atoms seggregate to the grain boundary and retard their
motion Solute drag (can be used to retain strength of materials
at high temperatures)
Second phase particles also pin down the grain boundary during its
migration

Hot Work and Cold Work

Hot Work Plastic deformation above TRecrystallization

Hot Work

Cold Work Plastic deformation below TRecrystallization

Cold Work

Recrystallization temperature (~ 0.4 Tm)

Grain growth

Globally
Driven by reduction in grain boundary energy
Locally
Driven by bond maximization (coordination number maximization)

Electical conductivity
Internal stress

Ductility

Tensile strength

Cold work

Recovery

Recrystallization

Grain growth

Creep
Creep (sometimes called cold flow) is the tendency of a solid material to move slowly
or deform permanently under the influence of mechanical stresses. It can occur as a
result of long-term exposure to high levels of stress that are still below the yield
strength of the material. Creep is more severe in materials that are subjected to heat for
long periods, and generally increases as they near their melting point. The rate of
deformation is a function of the material properties, exposure time, exposure
temperature and the applied structural load.

Creep Equation

Where is strain, n is stress coefficient, Q is the activation energy and

other symbols have usual meaning.

Creep equation represented graphically