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DC.MT 307.

15 Heat Treatment
Objectives
• Metals and alloys are subjected to different kinds of heat
treatment processes to develop appropriate microstructure
with desired set of properties.

• Hence a thorough understanding of fundamentals of


microstructural developments by different heat treatment
processes is necessary for structure-property correlations.

• The syllabus is designed to meet both the requirements.


Course Topics
• Fundamentals
– Iron-carbon equilibrium diagram, Isothermal transformation diagrams,
continuous cooling transformation diagram. Austenisation and
austenite grain size. Hardenability, its measurement and control.

• Heat Treatment of ferrous alloys


– Homogenisation, quenching and quenching media, annealing,
normalizing, hardening and tempering of steels. Case hardening
treatments-case carburizing and post carburizing heat treatment,
nitriding, carbonitriding, boronising, chromising, Toyota diffusion
processes. Surface hardening treatments-induction hardening, flame
hardening, laser hardening and electron beam hardening processes.
Course Topics
• Heat treatment of nonferrous alloys (7 L)
– Recrystallisation annealing of cold worked metals, age
hardening. Temper designations for aluminum and
magnesium alloys. Heat treatment of aluminium, copper,
magnesium, titanium and nickel alloys
Readings
• TEXTBOOKS::
1. R.E. Reed-Hill and R. Abbaschian: Physical Metallurgy
Principles, PWS Publishing Company, Boston, Third Edition.
2. Vijendra Singh: Heat treatment of Metals, Standard
Publishers Distributors, Delhi.
3. R.C. Sharma: Principles of Heat Treatment of Steels, New Age
International (P) Ltd. Publisher.
4. G. Krauss.: Principles of Heat Treatment of steel, ASM, 1980
5. Yu. M. Lakhtin: Engineering Physical Metallurgy and Heat
Treatment, Mir publisher, 1979.
Readings
• REFERENCE BOOKS::
1. Anil Kumar Sinha: Physical Metallurgy Handbook, McGraw-
Hill Publication, 2003
2. R.W.K. Honeycomb and H.K.D.H. Bhadeshia, Steels:
Microstructure and Properties, 3rd Edition, Butterworth-
Heinemann, 2006.
3. Metals Handbook, Heat Treatment, Ninth Edition, Vol 4, ASM
Grading
• Mid Term Examination : 30
• End Semester Examination : 50
• Assignments, Quizzes, Term-Papers :20
Definition of heat treatment
• Heat treatment is an operation or combination of operations
involving heating at a specific rate, soaking at a temperature
for a period of time and cooling at some specified rate. The
aim is to obtain a desired microstructure to achieve certain
predetermined properties (physical, mechanical, magnetic or
electrical).
Objectives of Heat Treatment
• The major objectives are
– to increase strength, harness and wear resistance (bulk
hardening, surface hardening)
– to increase ductility and softness (tempering,
recrystallization annealing)
– to increase toughness (tempering, recrystallization
annealing)
– to obtain fine grain size (recrystallization annealing, full
annealing, normalising)
– to remove internal stresses induced by differential
deformation, non-uniform cooling (stress relief annealing)
Objectives of Heat Treatment
– to improve machineability (full annealing and normalising)
– to improve cutting properties of tool steels (hardening and
tempering)
– to improve surface properties (surface hardening,
corrosion resistance-stabilising treatment and high
temperature resistance-precipitation hardening, surface
treatment)
– to improve electrical properties (recrystallization,
tempering, age hardening)
– to improve magnetic properties (hardening, phase
transformation)
Objectives of Heat Treatment
Classification of Ferrous Alloys
• Three types of ferrous alloys:

– Iron: less than 0.008 wt % C in α−ferrite at room


temperature

– Steels: 0.008 - 2.14 wt % C (usually < 1 wt % ) α-ferrite +


Fe3C at room temperature

– Cast iron: 2.14 - 6.7 wt % (usually < 4.5 wt %)


Steels
• Steel can be processed to produce a great variety of
microstructures and properties.

• Desired results are accomplished by heating in


temperature ranges and/or heating or cooling between
temperature ranges.

• The iron-carbon equilibrium phase diagram is the


foundation on which all heat treatment of steel is based.
– Temperature-composition regions where the various
phases in steel are stable
– Equilibrium boundaries between phase fields
Metallurgical Phenomena
• Steel is such an important material because of its
– Tremendous flexibility in metal working and
– Heat treating to produce a wide variety of mechanical,
physical, and chemical properties.

• The broad possibilities provided by the use of steel are


attributed mainly to two all-important metallurgical
phenomena:
1. Iron is an allotropic element; that is, it can exist in more than
one crystalline form; and
2. Carbon atom is only 1⁄30 the size of the iron atom.
Constitution of Iron

• 1538 C: Pure iron solidifies


from the liquid to ferrite, or
delta iron (bcc)

• 1395 C: Transformation from


delta iron gamma iron (fcc)

• 910 C : the structure reverts to


alpha iron

• 770 C : merely denotes a


change from nonmagnetic to
magnetic iron and does not
represent a phase change
Effect of Carbon on the Constitution of Iron
• Carbon is the main alloying
addition that capitalizes on the
allotropic phenomenon and lifts
iron from mediocrity into the
position of a unique structural
material, broadly known as
steel.

• Carbon more soluble in gamma


iron

• carbon is said to be an
austenitizing element
The Iron-Carbon Equilibrium Diagram
• Phases present are molten
alloy, austenite (gamma
phase), ferrite (alpha phase),
cementite, and graphite

• Carbon more soluble in gamma


iron

• carbon is said to be an
austenitizing element
The Iron-Carbon Equilibrium Diagram
• The iron-carbon diagram should be considered only a guide
– Alloying elements: The effects of alloying elements on
phase diagram
– Nonequilibrium structures : some heat treatments are
specifically intended to produce nonequilibrium structures
– Metastable Phases : It does not give any information
about other metastable phases. i.e. bainite, martensite
– Many heat treatments barely approach equilibrium
– No information about kinetics, grain size, and properties
δ ferrite
• Interstitial solid solution of carbon in iron of body centred
cubic crystal structure (Fig .2(a)) (δ iron ) of higher lattice
parameter (2.89Å) having solubility limit of 0.09 wt% at
1495°C with respect to austenite. The stability of the phase
ranges between 1394-1539°C.
γ phase (austenite)
• Interstitial solid solution of carbon in iron of face centred
cubic crystal structure having solubility limit of 2.11 wt% at
1147°C with respect to cementite. The stability of the phase
ranges between 727-1495°C and solubility ranges 0-0.77
wt%C with respect to alpha ferrite and 0.77-2.11 wt% C with
respect to cementite, at 0 wt%C the stability ranges from 910-
1394°C.
α-ferrite
• Interstitial solid solution of carbon in iron of body centred
cubic crystal structure (α iron) having solubility limit of 0.0218
wt % C at 727°C with respect to austenite.

• The stability of the phase ranges between low temperatures


to 910°C, and solubility ranges 0.00005 wt % C at room
temperature to 0.0218 wt% C at 727°C with respect to
cementite.
Fe3C or Cementite:
• Interstitial intermetallic compound of C & Fe with a carbon content of
6.67 wt% and orthorhombic structure consisting of 12 iron atoms and 4
carbon atoms in the unit cell.
• Stability of the phase ranges from low temperatures to 1227°C

Fig.9(a): Orthorhombic crystal structure of cementite. The purple atoms


represent carbon. Each carbon atom is surrounded by eight iron atoms. Each
iron atom is connected to three carbon atoms.
Critical Temperatures
• A0 = a subcritical temperature (<A1) = Curie temperature of
cementite=210°C
• A1 = Lower critical temperature=eutectoid temperature=727°C
• A2 = Curie temperature of ferrite=770°C
• A3 = upper critical temperature=γ+α /γ phase field boundary =
composition dependent=912-727°C
• A4 = Eutectic temperature=1148°C
• A5 = Peritectic temperature=1495°C
• Acm=γ/γ+cementite phase field boundary=composition dependent =727-
1148°C
• In addition the subscripts c or r are used to indicate that the temperature
is measured during heating or cooling respectively.
– c=chaffauge means heating, Ac
– r=refroidissement means cooling, Ar
Critical Temperature Lines
Types/morphologies of phases in Fe-Fe3C system

• Cementite=primary (CmI), eutectic (Cmeu), secondary


(CmII)(grain boundary allotriomophs, idiomorphs), eutectoid
(Cmed) and tertiary(CmIII).

• Austenite= austenite(γ)(equiaxed), primary (γI), eutectic


(γeu), secondary (γII) (proeutectoid),

• α-ferrite=ferrite (α) (equiaxed), proeutectoid or primary


(grain boundary allotriomorphs and idiomorphs)(αI),
eutectoid(αeu) and ferrite (lean in carbon) (α’).

• Phase mixtures: Pearlite (P) and ledeburite(LB)


Important Reactions
• Peritectic reaction
Liquid+Solid1↔Solid2
L(0.53wt%C)+δ(0.09wt%C)↔γ(0.17wt%C) at 1495°C
Liquid-18.18wt% +δ-ferrite 81.82 wt%→100 wt% γ

• Eutectic reaction
Liquid↔Solid1+Solid2
Liquid (4.3wt%C) ↔ γ(2.11wt%C) + Fe3C (6.67wt%C) at 1147˚C
Liquid-100 wt% →51.97wt% γ +Fe3C (48.11wt%)
The phase mixture of austenite and cementite formed at
eutectic temperature is called ledeburite
Eutectoid Reaction
• Eutectoid Reaction
Solid1↔Solid2+Solid3
γ(0.77wt%C) ↔ α(0.0218wt%C) + Fe3C(6.67wt%C) at 727°C
γ (100 wt%) →α(89 wt% ) +Fe3C(11wt%)

• Typical density
α ferrite=7.87 gcm-3
Fe3C=7.7 gcm-3
volume ratio of α- ferrite:Fe3C=7.9:1
Development of Microstructure in Iron–Carbon Alloys

Photomicrograph of a eutectoid
steel showing the pearlite
microstructure consisting of
alternating layers of -ferrite (the
light phase) and Fe3C (thin layers
most of which appear
dark).
Fig.1: Fe-Cementite metastable phase diagram (microstructural)
L=liquid, Cm=cementite, LB=ledeburite, δ=delta ferrite, α=
1539˚C δ+L L alpha ferrite, α’= alpha ferrite(0.00005 wt%C) γ=austenite,
δ A5=1495˚C P=pearlite, eu=eutectic, ed=eutectoid, I=primary,
0.09 0.53 II=secondary, III=tertiary
δ+γ 0.17 1227˚C

1394˚C
L+γI 4.30 L+CmI
γ γI+LB LB+CmI A4=1147˚C
Temperature, °C

2.11
LB’ (γeu(γII
γI’(γII+CmII)+LB’ (γ’eu(γII
+CmII)+Cmeu)
+CmII)+Cmeu)
+CmI
A B C

Ledeburite=LB(γeu+Ceu)
910˚C D E F
A2 A3
=668/ Cm
770˚C 0.77
αI+γ γII+CmII
0.0218 A1=727˚C
α αI+ (P(αed P(αed+Cmed) (P(αed+Cmed)+CmII)+ LB’ (P(αed+Cmed) LB’ (P(αed+Cmed)
Pearlite

+CmII +CmII+Cmeu) +CmII)+Cmeu)+CmI


+Cmed)

αI(α’+CmIII)+ P(α (α’


ed ed (P(αed(α’ed+CmIII)+Cmed) +CmII)+ LB’
(P(αed(α’ed+C +Cm )+Cm ed LB’ ((P(αed(α’ed+CmIII)+Cmed)
) ((P(αed(α’ed+CmIII)+Cmed)
mIII)+Cmed) +CmIII +CmII)+Cmeu) +CmII)+ Cmeu)+CmI
II
Ao=210˚C
α’+CmIII
6.67
0.00005
Weight percent carbon 29
Evolution of microstructure (equilibrium cooling)

• Sequence of evolution of microstructure can be


described by the projected cooling on compositions
A, B, C, D, E, F.
Evolution of microstructure (equilibrium cooling)
Evolution of microstructure (equilibrium cooling)
Effect of Alloying Elements on Phase Diagram
• Based on stabilizing Austenite
– Mn, Ni, Co, Cu, Zn increase the range in which γ-phase, or
austenite is stable [by raising Ae4 and lowering Ae3
temperature and also tend to retard the separation of
carbides.

– These elements have γ-phase FCC crystal structure (or


similar structure) in which these elements are more
soluble than ferrite, and that is why, in the (α+γ) two phase
equilibrium, these segregate in austenite in preference to
ferrite.

– Elements like carbon and nitrogen (interstitial solid


solution forming elements) are also austenite stabilizers.
Austenite Stablizer
Effect of Alloying Elements on Phase Diagram
• Based on stabilizing Ferrite
– Cr, W, Mo, V, Si, Al, Be, Nb, P, Sn, Ti, Zr increase the range of α-
phase (by lowering A4 and raising A3 temperatures).

– These elements have α phase BCC crystal structure (or similar


structure) and thus in (α+γ) two phase equilibrium , these
elements segregate in ferrite in preference to austenite. These
elements decrease the amount of carbon soluble in austenite,
and thus tend to increase the volume of the free carbide in the
steel for a given carbide content.

– Chromium is a special case of these elements as at low


concentrations , chromium lowers A3 temperature and raises
A4, but at high concentrations raises A3 temperature. Overall,
the stability of austenite is continuously decreased.
Ferrite Stablizer
Effect of Alloying Elements on Phase Diagram
• Elements can also be classified based on their effect on the stability of
cementite and their interaction with Carbon:
– Carbide-forming elements: Attractive interaction with C, increases
thermodynamic stability of cementite, segregates in cementite in
preference to austenite/ferrite phases, Mn, Cr, Mo, W, V, Nb, Ti
– Non-Carbide forming elements: Si, Ni, Cu
Effect of Alloying Elements on Phase Diagram
Fe-C-Mn System
Fe-C-Ni System
Fe-C-Si System
Effect on Ae3 Temperature

Andrews

Grange
Effect on Eutectoid temperature
• Elements like Ni, Mn i.e., the austenite stabilizers lower the eutectoid
temperature (727°C). Ferrite stabilizers like Cr, V, W etc. raise the eutectoid
temperature.
Effect on Eutectoid composition
• All the elements lower the eutectoid carbon content. Titanium and
molybdenum are the most effective in lowering it.
• For example, a steel with 5% Cr has its eutectoid point at 0.5%C as
compared to 0.8% in carbon steels. High speed steel has eutectoid point at
0.25% carbon.
Phase Transformations: Morphology
(a) Grain boundary allotrimorphs

(b) Widmanstätten Side Plates

(c) Widmanstätten Sawteeth

(d) Idiomorphs

(e) Intergranular Widmanstätten Plates

(f) Massive Structure


Nucleation
Nucleation
Nucleation
Nucleation

• K(T) variation with temperature is


negligible
• ∆GD is essentially independent of
temperature
• ∆G* depends on ∆GV
• ∆GV depends on undercooling
(∆T= Ae3-T)
Growth of Grain Boundary Allotrimorphs
Growth of Grain Boundary Allotrimorphs
Growth of Grain Boundary Allotrimorphs

• Effect of undercooling

• Effect of temperature on
diffusivity

• Similar expression can be


written for cementite
grain boundary
allotriomorps growth
Growth of Widmanstatten Side Plates

• V is molar volume of ferrite


• k is a thermodynamic factor approximately equal to one.
• σαγ is interfacial energy of α/γ interface
• D is diffusion coefficient of C in γ phase
Pearlite Transformation
• Nucleation: pearlite nucleates heterogeneously on austenite grain
boundary.
– Hypo and hyper-eutectoid steels: from the already formed ferrite and
cementite
– Eutectoid steels: from the active nuclei of ferrite/cementite
– General theory of nucleation of ferrite holds good
Pearlite Transformation
Pearlite Transformation
Bainite Transformation
• Growth is controlled by the growth of ferrite plates.
• Equation of growth for Widmanstatten ferrite plate
will apply.
Martensite Transformation
• Martensite may be considered as supersaturated solution of C in ferrite.
• Transformation may be considered austenite to ferrite transformation of
the same composition.
Martensite Transformation
Isothermal Transformation(IT) Diagrams
IT Diagram of (a) AISI-1034 and (b) AISI-1080 Steels
Effect of Grain Size on the IT Diagram
Continuous Cooling Transformation diagrams
• In practical situations we follow heat treatments (T-t procedures/cycles) in
which (typically) there are steps involving cooling of the sample.

• Hence, in terms of practical utility TTT curves have a limitation and we need to
draw separate diagrams called Continuous Cooling Transformation diagrams
(CCT), wherein transformation times (also: products & microstructure) are
noted using constant rate cooling treatments.

• The cooling rate may or may not be constant. The rate of cooling may be slow
(as in a furnace which has been switch off) or rapid (like quenching in water).

• CCT diagrams are determined by measuring some physical properties during


continuous cooling. Normally these are specific volume and magnetic
permeability. However, the majority of the work has been done through
specific volume change by dilatometric method. This method is supplemented
by metallography and hardness measurement.
Different cooling rates for eutectoid steel
Determination of CCT diagram for eutectoid steel

• Cooling data are plotted as temperature versus time. Dilation is recorded


against temperature. Any slope change indicates phase transformation.
Determination of CCT diagram
Determination of CCT diagram
Presentation of CCT Diagrams
• Equivalent Cooling Curve: The two cooling curves are considered
equivalent if:

1. the times to cool from Ae3 to 500°C are same.

2. the times to cool from Ae3 to a temperature halfway between Ae3


and room temperature , are same.

3. the cooling rates are same.

4. the instant cooling rates at 700°C are same.

• Therefore to make it useful different types of CCT diagrams need to


be made following any one of the above schedule that matches
with heat treatment cooling schedule.
Presentation of CCT Diagrams

Time of cooling from 800 C to 500 C


Relation Between IT and CCT Diagrams
Relation Between IT and CCT Diagrams
Relation Between IT and CCT Diagrams
• Let τ(t) is time required to obtain a given percentage of
transformation, X, at a temperature T during isothermal
transformation.