Kinetics - Heat Treatment

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
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
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

Kinetics - Heat Treatment

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Kinetics - Heat Treatment

Time, the third dimension

diagrams only represent what should

- temperature history required to generate

Solid State Reactions

Materials are extremely versatile

They possess a wide range of mechanical properties

Stages of Solid State Reactions

measured as a function of time

Plot of solid state reactions

Log of Heating Time, t

transformations occur when

Phase boundaries are crossed during heating or

a phase boundary is crossed, the alloy

Property changes in Fe-C alloys

the eutectoid reaction

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

transforms to ferrite and cementite changing iron content

Validity of Isothermal Diagrams

throughout the transformation

temperature profile other than isothermal

Mechanical Behavior of Alloys

Cementite is harder but more brittle than ferrite

Layer thickness also has an effect

Martensite Mechanical Behavior

The ability of a steel alloy to transform to martensite is

There is a relationship between mechanical properties

hardness is measured with respect to the

Jominy End-Quench Results

quenched end is cooled most rapidly and

Cooling rate decreases away from end and the

ductile material can become harder and

Ao and Ad are the cross sectional areas before and

does this occur?

microstructure and properties

appropriate heat treatment

movement of dislocations at high T

energy state (they have been deformed)

Defined as the temperature at which recrystallization

recrystallization, grains will continue to

All grains cant grow

properties to coarse-grained materials

diagrams are not used for nonmetallic

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