Thermal Processing of Metals

Annealing: Heat to Tanneal, then cool slowly.

• Stress Relief: Reduce • Spheroidize (steels):

stress caused by: Make very soft steels for
-plastic deformation good machining. Heat just
-nonuniform cooling below TE & hold for
-phase transform. 15-25 h.

• Full Anneal (steels):

Types of Make soft steels for
good forming by heating
Annealing to get γ, then cool in
furnace to get coarse P.
• Process Anneal:
Negate effect of
• Normalize (steels):
cold working by
Deform steel with large
(recovery/
grains, then normalize
recrystallization)
to make grains small.

Based on discussion in Section 11.7, Callister 7e. 1

 Heat Treatments
800
Austenite (stable)

T(°C) TE
A
a) Annealing P
b) Quenching 600
c) Tempered
Martensite
B
400 A
Adapted from Fig. 10.22, Callister 7e.

0%
200 M+A
50%
M+A
90%
b) a)

-1 3 5 c)
10 10 10 10
time (s) 2
 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 thermo-elastic stresses within the or even
cracking the metal piece.

Purposes of annealing:
• Relieve internal stresses
• Increase ductility, toughness, softness
• Produce specific microstructure
 Examples of heat treatment

Process Annealing –
effects of work-hardening (recovery and recrystallization) and
increase ductility. Heating limited to avoid excessive grain
growth and oxidation

Stress Relief Annealing –

minimizes stresses due to
o Plastic deformation during machining
o Nonuniform cooling
o Phase transformations between phases with different
densities
Annealing temperatures relatively low so that useful effects of
cold working are not eliminated
 Annealing of Fe-C Alloys (I)

• Lower critical temperature A1

below which austenite does not exist

• Upper critical temperatures A3 and Acm above which all material is austenite
5
 Annealing of Fe-C Alloys (II)

Normalizing: annealing heat treatment just above upper critical

temperature to reduce grain sizes (of pearlite and proeutectoid phase)
and make more uniform size distributions.

Austenitizing
6 complete transformation to austenite
 Annealing of Fe-C Alloys (III)

Full annealing: austenizing + slow cooling (several hours) Produces

coarse pearlite (and possible proeutectoid phase) that is relatively soft
and ductile. Used to soften pieces which have been hardened by
plastic deformation, but need to undergo subsequent
machining/forming.
Spheroidizing: prolonged heating just below the eutectoid temperature, results in the soft
spheroidite
7 structure. This achieves maximum softness needed in subsequent forming
operations.
 Quenching and Tempering
• We have found that Martensite (M) is very hard, strong, and
brittle. It sees little use as an end product.
• But, if we reheat to below 727, (250-650) and leave the M
there for a while, it changes into something with real
usefulness. Tempered Martensite. (TM)
• TM is ferrite, with an extremely fine dispersion of roughly
spherical particles of Fe3C. Extremely strong, but has ductility
and toughness. This is the primo stuff, as far as steel goes.
 A Typical Q&T Steel
• We will use Matweb to look over a couple of steels.
• Note the differences in strength and ductility in a 1060 Steel.
The annealed steel with have very coarse pearlite. The Q&T
steel will have very finely distributed cementite.

Process UTS Yield %EL Hardness

Annealed 90.6 ksi 53.7 ksi 22 88
Q&T 148.7 ksi 98.2 15 99
 Spheroidizing
• Strangely, sometimes we would like the steel to be just as soft
and ductile as absolutely possible.
• Why, do you think?
• Pearlite is not the lowest energy arrangement possible
between ferrite and cementite. If heated to just below the
eutectoid temperature, and left for an extended time, the
pearlite layers break down, and spherical clumps of cementite
are found.
• These spherical clumps are hundreds or even thousands of
times larger that those in TM, and spaced much further apart.

Softest, most duct.
http://info.lu.farmingdale.edu/depts/met/met
205/ANNEALING.html
 More on Spheroidite
• You have to spend a lot of energy cooking steel. Spheroidizing
is not really used with low carbon steels, since they are
already soft and ductile enough.
• Spheroidizing is done with the higher carbon steels, so they
will be as ductile as possible for shaping.
• Spheroidizing is done to improve the machineability of high
carbon steels. Having the massive cementite regions
enhances chip formation.
 Full Anneal
• The idea is to get the soft metal and relieve stresses. We
contrast this anneal with the “process anneal” associated with
CW.
• In the full anneal, we must fully austenitize the steel. This is
followed by a furnace cool, the slowest cooling rate possible.
• The result is coarse Pearlite mixed with primary phase. This
steel will be close to spheroidite in its softness and ductility.
 Normalizing Steel
• Here we austenitize the steel and then air cool as opposed to
furnace cooling.
• The result is a uniform microstructure, very uniformly spaced
pearlite in equal sized grains throughout.
• It is stronger and somewhat less ductile than full anneal.
• Often done after forging to normalize the grain structure.
 Hardenability
• We have seen the advantage of getting martensite, M. We
can temper it, getting TM with the best combination of
ductility and strength.
• But the problem is this: getting M in depth, instead of just on
the surface. We want a steel where Pearlite formation is
relatively sluggish so we can get it to the cooler regions where
M forms.
• The ability to get M in depth for low cooling rates is called
hardenability.
• Plain carbon steels have poor hardenability.
 Heat Treatment of Steels
Martensite has strongest microstructure.
Can be made more ductile by tempering.

Optimum properties of quenched and tempered steel are realized with high content
of martensite

Problem: difficult to maintain same conditions throughout volume during cooling:

Surface cools more quickly than interior, producing range of microstructures in
volume
Martensitic content, and hardness, will drop from a high value at surface to a lower
value inside

Production of uniform martensitic structure depends on

• composition
• quenching conditions
16• size + shape of specimen
 Hardenability
Hardenability is the ability of Fe-C alloy to harden
by forming martensite

Hardenability (not “hardness”): Qualitative measure of rate at which

hardness decreases with distance from surface due to decreased
martensite content

High hardenability means the ability of the alloy to produce a high

martensite content throughout the volume of specimen

Hardenability measured by Jominy end-quench test performed for

standard cylindrical specimen, standard austenitization conditions,
and standard quenching conditions (jet of water at specific flow rate
and17temperature).
 Jominy end-quench test of Hardenability

Hardenability curve is the dependence of hardness on distance from

the quenched end.
18
 Hardenability Curve

Less Martensite

 Quenched end cools most rapidly, contains most martensite

 Cooling rate decreases with distance from quenched end: greater C
diffusion, more pearlite/bainite, lower hardness
 High hardenability means that the hardness curve is relatively flat.
19
 Influence of Quenching Medium, Specimen Size, and Geometry on
Hardenability
Quenching medium: Cools faster in water than air or oil. Fast cooling

warping and cracks, since it is accompanied by large thermal
gradients

Shape and size: Cooling rate depends upon extraction of heat to

surface. Greater the ratio of surface area to volume, deeper the
hardening effect

Spheres
Radial cool slowest, irregular objects fastest.
hardness
profiles of
cylindrical
steel bars

20
 Precipitation Hardening

• Inclusion of a phase
strengthens material

• Lattice distortion around secondary phase impedes dislocation

motion
• Precipitates form when solubility limit exceeded
• Precipitation hardening called age hardening
21
(Hardening over prolonged time)
 Heat Treatment for Precipitation Hardening (I)

• Solution heat treatment: To
solute atoms A dissolved to form a

single-phase (α
α) solution.
• Rapid cooling across solvus to exceed solubility limit. Leads to
metastable supersaturated solid solution at T1. Equilibrium
structure is α+β
β, but limited diffusion does not allow β to form.
• Precipitation
22 heat treatment: supersaturated solution heated to T2
where diffusion is appreciable - β phase starts to form finely
 Heat Treatment for Precipitation Hardening (II)

Discs of Cu atoms 1 or 2
monolayers thick

Lattice Distortions No Lattice Distortions

23
 Strength and ductility during precipitation hardening

24
 Jominy Test for Hardenability
• Hardenability not the same as hardness!
 Hardenability--Steels
• Ability to form martensite
• Jominy end quench test to measure hardenability.

Adapted from Fig. 11.11,

flat ground Callister 7e. (Fig. 11.11
specimen adapted from A.G. Guy,
Essentials of Materials
(heated to γ Science, McGraw-Hill Book
phase field) Rockwell C Company, New York,
1978.)
24°C water hardness tests

• Hardness versus distance from the quenched end.

Hardness, HRC

Adapted from Fig. 11.12,

Callister 7e.

Distance from quenched end

26
 Why Hardness Changes W/Position
• The cooling rate varies with position.

Hardness, HRC
60

40

20 distance from quenched end (in)

0 1 2 3
T(°C) 0%
600 100%
Adapted from Fig. 11.13, Callister 7e.
(Fig. 11.13 adapted from H. Boyer (Ed.)
400 Atlas of Isothermal Transformation and
Cooling Transformation Diagrams,
M(start) American Society for Metals, 1977, p.
200 376.)
A→M

0 M(finish)

0.1 1 10 100 1000

Time (s)
27
The Result is Presented in a Curve
Note:
1. Distance from quenched
end corresponds to a
cooling rate, and a bar
diameter
2. Notice that some steels
drop off more than others
at low cooling rates. Less
hardenability!

Rank steels in order of hardenability.

 Factors Which Improve Hardenability
• 1. Austenitic Grain size. The Pearlite will have an easier time
forming if there is a lot of g.b. area. Hence, having a large
austenitic grain size improves hardenability.
• 2. Adding alloys of various kinds. This impedes the γ
P
reaction.
TTT diagram of a
molybdenum steel 0.4C
0.2Mo

After Adding 2.0%

Mo
 Hardenability vs Alloy Composition
• Jominy end quench 100 10 3 2 Cooling rate (°C/s)
results, C = 0.4 wt% C 60

Hardness, HRC
100

4340 80 %M
50
40 4140

Adapted from Fig. 11.14, Callister 7e.

8640
(Fig. 11.14 adapted from figure furnished 5140
courtesy Republic Steel Corporation.) 20
0 10 20 30 40 50
Distance from quenched end (mm)
• "Alloy Steels" 800
(4140, 4340, 5140, 8640) T(°C) TE
--contain Ni, Cr, Mo 600 shift from
A B
(0.2 to 2wt%) A to B due
400 to alloying
--these elements shift
the "nose". 200 M(start)
--martensite is easier M(90%)
to form. 0 -1 3 5
10 10 10 10 Time (s)
30
 Quenching Medium
• Effect of quenching medium:
& Geometry
Medium Severity of Quench Hardness
air low low
oil moderate moderate
water high high
• Effect of geometry:
When surface-to-volume ratio increases:
--cooling rate increases
--hardness increases

Position Cooling rate Hardness

center low low
surface high high

31
 Heat Treatment of Steels
• 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.
• The FCC can hold more carbon in solution and on rapid
cooling the crystal structure wants to return to its BCC
structure. It cannot due to trapped carbon atoms. The net
result is a distorted crystal structure called body centered
tetragonal called martensite.
 10.4 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!
 10.4 Direct Hardening - Selective
Hardening :
• Same requirements as austenitizing:
– Must have sufficient carbon levels (>0.4%)
– Heat to austenite region and quench
• Why do?
– When only desire a select region to be hardened:
Knives, gears, etc.
– Object to big to heat in furnace! Large casting w/ wear
surface
• Types:
– Flame hardening, induction hardening, laser beam
hardening
Flame Hardening:
Induction Hardening
Diffusion Hardening (aka Case Hardening):
• Why do?
– Carbon content to low to through harden with previous
processes.
– Desire hardness only in select area
– More controlled versus flame hardening and induction
hardening.
– Can get VERY hard local areas (i.e. HRC of 60 or greater)
– Interstitial diffusion when tiny solute atoms diffuce into
spaces of host atoms
– Substitiutional diffusion when diffusion atoms to big to
occupy interstitial sites – then must occupy vacancies
 Diffusion Hardening:
• Requirements:
– High temp (> 900 F)
– Host metal must have low concentration of the
diffusing species
– Must be atomic suitability between diffusing
species and host metal
 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

 10.6 Softening and Conditioning -
• Recrystallization
• Annealing
– Process anneal
– Stress relief anneal
– Normalizing
• Tempering
 10.6 Softening and Conditioning -
Recrystallization
• Done often with cold working processes
• Limit to how much steel can be cold worked
before it becomes too brittle.
• This process heats steel up so grains return
to their original size prior to subsequent cold
working processes.
• Also done to refine coarse grains
 10.6 Softening and Conditioning -
Annealing
• Annealing – primary purpose is to soften the
steel and prepare it for additional processing
such as cold forming or machining.
• If already cold worked - allows
recrystallization.
 10.6 Softening and Conditioning -
Annealing
• What does it do?
1. Reduce hardness
2. Remove residual stress (stress relief)
3. Improve toughness
4. Restore ductility
5. Refine grain size
 10.6 Softening and Conditioning -
Annealing
• Process Steps:
1. Heat material into the asutenite region (i.e.
above 1600F) – rule of thumb: hold steel for one
hour for each one inch of thickness
2. Slowly furnace cool the steel – DO NOT QUENCH
3. Key slow cooling allows the C to precipitate out
so resulting structure is coarse pearlite with
excess ferrite
4. After annealing steel is quite soft and ductile
 Annealing versus Austenitizing:
• End result: One softens and the other hardens!
• Both involve heating steel to austenite region.
• Only difference is cooling time:
– If fast (quenched) C is looked into the structure =
martensite (BCT) = HARD
– If slow C precipates out leading to coarse pearlite (with
excess cementite of ferrite) = SOFT
 10.6 Softening and Conditioning –
Other forms of Annealing
• Normalizing – use when max softness not
required and cost savings desired (faster
than anneal). Air cooled vs. furnace cooled.
• Process Anneal – not heated as high as full
anneal.
• Stress Relief Anneal – lower temp (1,000F),
slow cooled. Large castings, weldments
 10.6 Softening and Conditioning -
Temper
• 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)
 10.6 Softening and Conditioning -
Temper
• Typical HT steps:
– 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
The Heat Treat Processes