Kinetics - Heat Treatment

Nonequilibrium Cooling
All of the discussion up till now has been for

slow cooling
Many times, this is TOO slow, and unnecessary
Nonequilibrium effects
Phase changes at T other than predicted
The existence of nonequilibrium phases at room
temperature

MSE 271

Unit 7

Time, the third dimension

Phase

diagrams only represent what should

happen in equilibrium (e.g. slow cooling)
Most materials are not processed under such
conditions
Time constraints
Desirable characteristics of nonequilibrium
microstructures

Heat treatment
Time

- temperature history required to generate

a certain microstructure
Kinetics - the science of time-dependent phase
transformations
Time - temperature - transformation (TTT)
diagrams are used to indicate the microstructure

MSE 271

Unit 7

Solid State Reactions

Most transformations do not take place

instantaneously
e.g. to change crystal structures, atoms must diffuse
- Which takes time
Energy is required to form phase boundaries
between parent and product phases

Phase Transformations
Metallic

Materials are extremely versatile

They possess a wide range of mechanical properties

Microstructure development occurs by phase

transformations
Properties can be tailored by changing
microstructure

MSE 271

Unit 7

Stages of Solid State Reactions

Nucleation
The formation of very small particles of the new
phase
Often begins at imperfection sites - especially
grain boundaries*

Growth
The nuclei increase in size
Some or all of the parent phase disappears
Complete when system reaches equilibrium
(may never be complete)

Rate of Transformation
The fraction of reaction that has occurred is

measured as a function of time

Usually at a constant T
Progress is usually determined by microscopy or
other physical property
Data is plotted as fraction transformed vs. log

time

MSE 271

Unit 7

Plot of solid state reactions

1.0
G=Cexp(-Q/RT)

At constant T

no i t c a r F

0.5

t0.5
Nucleation

Log of Heating Time, t

Growth

Multiphase Transformations
Phase

transformations occur when

Temperature changes or
Composition changes or
External pressure changes
Temperature is most common method to induce

phase transformations

Phase boundaries are crossed during heating or

cooling

MSE 271

Unit 7

Phase diagrams
When

a phase boundary is crossed, the alloy

proceeds towards equilibrium according to the
phase diagram
Most phase transformations require a finite time
Phase diagrams cannot indicate how long it
takes to achieve equilibrium
Many times the preferred microstructure is
metastable

Property changes in Fe-C alloys

Examples of kinetic principles can be found in the

Fe-C system
Pearlite transformation
Martensitic transformation

MSE 271

Unit 7

Pearlite transformation
Consider

the eutectoid reaction

(0.77 wt% C) (0.22% C) + Fe3C(6.70% C)

Austenite

transforms to ferrite and cementite changing iron content

Carbon diffuses away from ferrite to cementite
Temperature affects the rate:
Construct isothermal transformation diagrams from
% transformation diagrams

Pearlite transformation
Austenite Grain
Boundary

Austenite ()

Ferrite,

Growth of
Direction of
Pearlite

Austenite ()

Cementite Fe3 C

MSE 271

Unit 7

Pearlite
transformation

Interpretation of Isothermal
Diagrams
Eutectoid T is a

horizontal line
The start and finish curves are nearly parallel
Austenite exists to the left (not stable)
Pearlite exists to the right

MSE 271

Unit 7

Isothermal Diagrams
727C, Eutectoid Temperature- Austenite (stable)

Temperature, T, C

700
Coarse Pearlite
600
Fine Pearlite

500

AustenitePearlite
Transformation

10

102

103

104

105

106

Time, t, s

Validity of Isothermal Diagrams

Only valid for a particular composition for a

particular system
Other compositions will have different curves
Only valid when the temperature is constant

throughout the transformation

MSE 271

Unit 7

Martensite formation
Other microstructures form if there is a

temperature profile other than isothermal

Martensite (fast quenching - prevents C diffusion plate or needle like) Since it is diffusionless - it is almost instantaneous
Only dependent on T to which it is quenched

Martensite

Tempering of Steel

MSE 271

Unit 7

10

Mechanical Behavior of Alloys

Pearlite

Cementite is harder but more brittle than ferrite

Thus, the more Fe3C in an alloy the stronger and
harder the material
However, also makes it less ductile and not as tough (low
impact resistance)

Layer thickness also has an effect

Fine pearlite is harder and stronger than coarse

Martensite Mechanical Behavior

Strongest, hardest, and most brittle
Hardness

is dependent on C content
Martensite is not as dense - therefore when it
transforms it causes stress
Tempering (heat treatment) of martensite
relieves stress - makes it tougher and more
ductile

MSE 271

Unit 7

11

Hardenability

The ability of a steel alloy to transform to martensite is

its hardenability
Dependent on:
Composition
Quenching medium

There is a relationship between mechanical properties

and cooling rate
Hardenability refers to the degree to which is transforms
to martensite and to the depth an alloy may be
hardened

Hardenability
Jominy End-Quench
Cylindrical specimen is cooled from the end by a
spray or water
Specimen size, shape is specified
Water spray and time is specified
The

hardness is measured with respect to the

distance from the quenched end
Flat is ground along length
Rockwell hardness measured

MSE 271

Unit 7

12

Jominy End-Quench Results

The

quenched end is cooled most rapidly and

has highest hardness
100% martensite

Cooling rate decreases away from end and the

hardness decreases
A hardenable steel retains large hardness
values for long distances
Each steel has unique hardenability curves

Cold Working
A

ductile material can become harder and

stronger as it is plastically deformed
Strain hardening = work hardening = cold
working (meaning the strain is imposed at low
temperatures)
Most metals strain harden at room temperature.

MSE 271

Unit 7

13

Cold Working
The degree of plastic deformation is expressed as
% cold worked:
A Ad
x 100
%CW = o
Ao

Ao and Ad are the cross sectional areas before and

after plastic deformation occurs

Cold Working
Why

does this occur?

Dislocation-dislocation strain field interactions
Dislocation density increases with cold working so the average separation between dislocations
decreases
Strain hardening may be removed by annealing
(heating to higher T to allow dislocations to
move)

MSE 271

Unit 7

14

Recovery, Recrystallization
Plastic deformation results in changes in

microstructure and properties

Grain shape
Strain hardening
Increased dislocation density
Original properties can be regained by

appropriate heat treatment

Recovery, recrystallization, grain growth

Recovery
Some of the stored strain energy is relieved by

movement of dislocations at high T

Number of dislocations is reduced
Configuration of dislocation is altered
Properties return to their pre-cold-worked state

MSE 271

Unit 7

15

Recrystallization
Even after recovery, grains are still in a high

energy state (they have been deformed)

Recrystallization is the formation of a new set of
strain-free equiaxed grains.
New grains form by nucleation and growth
Short range diffusion

Recrystallization
Recrystallization depends on

Time
Temperature
Recrystallization temperature

Defined as the temperature at which recrystallization

reaches completion in 1 hr.

MSE 271

Unit 7

16

Stages of Recrystallization
Cold Worked
Initial Stage
Intermediate Stage
Complete Recrystallization
Grain Growth
Grain Growth, Higher Temperature

Grain Growth
After

recrystallization, grains will continue to

grow
Occurs in all crystalline materials - why?
Energy is associated with grain boundaries As grain size increases, total boundary area decreases

All grains cant grow

Large ones grow at the expense of small ones

MSE 271

Unit 7

17

Grain Growth
Fine grained materials usually have superior

properties to coarse-grained materials

If an alloy is coarser than desired, refinement
may be accomplished by physically deforming
and then recrystallizing.

Summary
TTT

diagrams are not used for nonmetallic

materials
Grain growth is especially important in ceramics
Heat treatment to bond powder particles and
reduce porosity is called sintering for ceramics

MSE 271

Unit 7

18