MME101 Materials Engineering Fundamentals

Lecture 24
Part D: Controlling Microstructures
A. K. M. Bazlur Rashid
Professor, Dept. of Materials and Metallurgical Eng.
and Properties
Bangladesh Univ. of Eng. and Tech., Dhaka-1000 4 – Kinetics of phase transformations

Lecture outcome (LO)

At the end of this lecture, students should be able to

1. explain the importance of phase transformations,
and describe the kinetics of solid-state phase transformations,
2. explain the methods of heat treatment to manipulate structure, and
3. understand the importance of surface hardening operations and
describe different surface hardening operations.

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 Part 1
Kinetics of Phase Transformations

1. The Phase Transformation

❑ Can we control the microstructure that is formed during cooling/heating

of an alloy of fixed composition?
• Yes, by controlling the transformation mechanism
by varying the temperature and time of transformation.

❑ Phase transformation is the formation of a new phase having a distinct

physical/chemical character and/or a different structure than the parent phase.
❑ Manipulation of phase transformation is a major tool for controlling
the properties of metals and alloys.

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 ❑ The speed of a structural change is important.
• Some changes occur in only fractions of a second;
others take years to complete; some may not even complete at all !!

❑ Predicting the speed of a structural change is rather like predicting

the speed of an automobile.
• The driving force alone tells us nothing about the speed – it is like knowing
the energy content of the petrol.
• To get at the speed we need to understand the details of how the petrol is
converted into movement by the engine, transmission and road gear.

❑ In other words, we need to know about the mechanism of the change.

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❑ So, the questions are:

• How does the rate of transformation depend on time and temperature?
• How can we slow down the transformation
so that we can engineer non-equilibrium structures?
• Are the mechanical properties of non-equilibrium structures better?

❑ All these questions can be answered if we understand the kinetics of phase

transformation i.e., the time dependence of the transformation.

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 Types of phase transformations

❑ Structural changes have two types of mechanisms: diffusive and displacive.

Diffusive transformation Displacive transformation

• require the diffusion of atoms (or molecules) through • involve only a minor “shuffling” of atoms
the material, and are of two types: about their original positions by cooperative
small displacements of all atoms at the
1. diffusion-controlled transformations with no change
speed of sound !! (e.g., martensitic
in either the number or composition of the phases
transformation in some steels)
present (e.g., solidification of pure metal, allotropic
transformations, etc.)
2. diffusion-controlled transformation with some
alteration in phase compositions and often in the
number of phases present (e.g., transformation due
to the eutectic reaction, L➔S1+S2)

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2. Solid-state Phase Transformations

❑ A variety of phase transformations are ❑ Most of the solid-state phase transformations

important in the processing of materials. are diffusion-controlled and involved the
• Examples includes: formation of at least one new phase that has
solidification (L➔S transformation), different structure and/or composition from that
evaporation (L➔V transformation), etc. of the parent one.
• some atomic rearrangements via diffusion are
❑ However, the most important of all are required, which is a time-dependent phenomenon.
solid-state phase transformations
(represented by ➔ transformation).

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 ❑ All diffusion-controlled transformation processes commonly proceed by
nucleation and thermally activated growth mechanism.
• Nucleation involves the appearance of very small particles or nuclei
of the new phase (often consisting of only a few hundred atoms), which can grow.

• During growth, these nuclei increase in size, which results in the disappearance
of some (or all) of the parent phase.

❑ The transformation reaches completion if the growth of these new-phase

particles is allowed to proceed until the equilibrium fraction is attained.

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❑ For solid-state transformations, the fraction of material transformed y

over a period t is given by the Avrami equation:
y = 1 - exp (-ktn)
where k and n are time-independent constants.

• Progress in transformation is usually ascertained by

either microscopic examination or measurement of some
physical property (such as electrical conductivity) whose
magnitude is distinctive of the new phase.
• Data are plotted as the fraction of transformed material
versus the logarithm of time; an S-shaped curve
represents the typical kinetic behavior for most solid-
state reactions.

plot of fraction reacted versus the logarithm of time

❑ By convention, the rate of transformation Nሶ is taken typical of many solid-state transformations in which
as the reciprocal of time required for 50% completion temperature is held constant
of the transformation: 𝑁ሶ = 1Τ𝑡0.5
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 ❑ Temperatures have profound influence on kinetics
and, thus, on the rate of transformation.

percent recrystallization as a function of time and at constant temperature for pure copper

❑ For most reactions, rate of transformation increases according to the following

Arrhenius equation:
A = temperature independent constant
R = A exp (-Q/RT) Q = activation energy for the reaction
T = temperature of transformation
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The overall transformation rate

❑ In practice, a phase transformation does not ❑ During nucleation, the clustering of atoms by
always take place exactly at the transition short-range diffusion takes place during the
temperature. formation of nuclei.
• For example, liquids may need to undercool
before solidification commences ❑ This diffusion-controlled effect is related to the
frequency at which atoms from the liquid attach
❑ With a lowering of temperature below the themselves to the solid nucleus, d.
equilibrium solidification temperature (Tm),
nucleation occurs more readily. ❑ The dependence of d on temperature is,
❑ Furthermore, the number of stable nuclei n* 𝑄𝑑
𝑣𝑑 = 𝐾2 𝑒𝑥𝑝 −
formed is a function of temperature 𝑘𝑇
Qd= a temperature-independent parameter
∗
∆𝐺 ∗ G* = activation free energy, which —the activation energy for diffusion.
𝑛 = 𝐾1 𝑒𝑥𝑝 − is the free energy required for the
𝑘𝑇 formation of a stable nucleus.
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 As G* is negative, a decrease As Qd is positive, a decrease
of temperature results in an of temperature results in a
increase in n* reduction in vd

❑ With a reduction of temperature from below Tm, the nucleation rate Nሶ first increases
(G* > Qd), achieves a maximum, and subsequently diminishes (G* < Qd).

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❑ The growth step in a phase transformation

begins once an embryo has exceeded the
critical size and becomes a stable nucleus.

❑ Particle growth occurs by long-range atomic

diffusion, which normally involves several
steps—for example, diffusion through the
ሶ growth
schematic plot showing curves for nucleation rate (𝐍),
parent phase, across a phase boundary, and ሶ and overall transformation rate versus temperature
rate (𝐆),
then into the nucleus.
❑ Near Tt, overall transformation rate is slow.
❑ Consequently, the growth rate Gሶ is • faster growth rate, slower nucleation rate
• few nucleus formed, grow rapidly to form coarser grains
determined by the rate of diffusion—namely,
❑ At much lower temperature than Tt,
𝑄 overall transformation rate is slow again
𝐺ሶ = 𝐶 𝑒𝑥𝑝 − • faster nucleation rate, slower growth rate
𝑘𝑇 • many nuclei formed; finer grains resulted due to slower growth rate
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 3. Time-Temperature-Transformation (TTT) diagram
❑ If, instead plotting the rate against temperature, un-transformed
we plot the start and finish times for a structure end of
transformation
transformation at various temperature, we obtain

Temperature
a graph which is a mirror image of the overall
transformation curve. transformed
start of
structure
transformation

log (time)

❑ This plot is known as Time-Temperature-

Transformation (TTT) diagram.

transformation rate time of transformation ❑ Commonly used to present the temperature

versus temperature versus temperature dependence of a transformation.
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Diffusional vs. martensitic transformation

untransformed structure Some background study about 0.8% C steel

Austenite Tt = 723 °C • Above 723 °C, the steel has a single-phase structure, called
austenite (), which is FCC.
Temperature

Pearlite
transformed • During cooling at 723 °C, austenite experiences a diffusional
nose
structure isothermal transformation to a mixture two new phases,
ferrite () and cementite (Fe3C), and this new structure is
start of Bainite called pearlite (P).
transformation
• This pearlite has a fingerprint-like structure.
end of
transformation • As cooling rate of this  ➔ P transformation is increased,
Martensite the fineness of the fingerprint increases, and the steel
becomes harder and stronger due to the formation of new
log (time) structure called bainite.
• For much faster cooling, an entirely new structure, called
TTT Diagram of 0.8% Carbon Steel
martensite, is formed by a diffusionless process.
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 Diffusional transformations
• occur relatively slowly
untransformed structure
• usually result in the formation of equilibrium phases
Austenite (pearlite/bainite)
Tt = 723 °C
• transformation occurs only when the time is increased
Temperature

Pearlite
transformed
nose
structure Martensitic / diffusionless / displacive
transformations
Bainite
MARTENSITIC • very rapid, no diffusion involved
DIFFUSIONAL • systematic coordinated shearing of the lattice
• produce a metastable phase a.k.a. martensite
cooling
Martensite curve • transformation occurs only when the temperature is
decreased
log (time)
Can you design a cooling procedure
TTT Diagram of 0.8% Carbon Steel
to obtain 100% bainite structure?
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Part 2
Heat Treatment of Steels

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 4. Heat Treatment Fundamentals

❑ It is an operation or combination of operations involving

Temperature
• heating a metal or an alloy in its solid state holding
to a certain temperature,

• holding it there for some times, and cooling

• cooling it to the room temperature heating

at a predetermined rate to obtain desired properties.
Time

❑ All basic heat-treating processes for steels involve the transformation of austenite.
• the nature and appearance of these transformation products
determine the physical and mechanical properties of heat-treated steels.

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Heating Period
• Heating steel (at about 800 – 930 C) to form single-phase austenite.
• Rate of heating is usually less important, except for
[1] highly stressed materials, or [2] thick-sectioned materials.
Temperature

holding
Holding / Soaking Period
• Holding at the austenitising temperature cooling
for complete homogenisation of structure.
heating
• Usually, 1 hour per 1 inch section is enough for holding.
Time
Cooling Period
• Very important period of heat treatment operation.
• Cooling rate that determines the nature of transformation products of austenite.

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 ❑ Based on cooling conditions, heat treatment processes are classified as :
1. Annealing – very slow (equilibrium) cooling of sample to soften the structure
2. Normalising – moderate cooling to refine the grain structure
3. Hardening – very fast cooling to harden the structure
Temperature

HARDENING
Very fast cooling ANNEALING
NORMALISING Very slow cooling
Moderate cooling

Time
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Annealing of Steels

❑ Annealing is a treatment that consists of heating to the austenite zone,

followed by equilibrium cooling through the transformation range,
primarily for softening the steel.
❑ Since an equilibrium cooling is not practically possible, the sample is normally cooled
by keeping the sample inside the furnace and then stopped the furnace.

❑ Generally, in plain carbon steels, annealing produces a ferrite-pearlite structures.

❑ The general purposes of annealing include

1. inducing ductility, toughness, softness, and
2. relieve residual stresses

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 ❑ A careful estimation of the proportions of pearlite and/or ferrite present in an annealed
steel can be used to determine the approximate carbon content of the steel:

Wt.% C = 0.80 (% Pearlite area) + 0.008 (% Ferrite area)

(for steels containing <0.8 wt.% C)

Wt.% C = 0.80 (% Pearlite area) + 6.67 (% Cementite area)

(for steels containing >0.8 wt.% C)

Steel containing C < 0.8% have ferrite Steel containing C > 0.8% have pearlite (black)
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(white) and pearlite (black) grains grains surrounded by cementite (white) network
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❑ An approximate tensile strength of a hypoeutectoid steel can also be determined

in a similar manner:
Approx. Tensile Strength, psi = 120,000 (%Pearlite area) + 40,000 (%Ferrite area)

Tensile strength of steels containing more than 0.8% C can not be estimated
similarly, since their strengths are determined by the cementite network only.

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 Problem
Microstructure of an annealed steel sample is found to contain 25% ferrite area and
75% pearlite area. Identify the steel and determine its approximate tensile strength.

Wt.% C in steel = (0.80) (0.75) + (0.008) (0.25) = 0.602 %

So, the sample is a high carbon steel (C = 0.60 – 1.00 wt.%).

Also, since the carbon content is less than the eutectoid composition (C = 0.80 wt.%),
the sample is a hypoeutectoid steel.

Approx. Tensile Strength = (120,000) (0.75) + (40,000) (0.25) psi = 100,000 psi

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Normalizing of Steels
❑ Normalizing is done by heating the steel to the austenite zone,
followed by slow cooling to room temperature in still air. Cementite
Ferrite
❑ Normalising produces a harder and stronger steel
than annealing (due to a faster cooling rate).

❑ General purposes of normalizing include: ANNEALED NORMALISED

coarse lamellar medium lamellar
1. Refining the structure pearlite pearlite
2. Inducing toughness

❑ Normalizing produces a finer and more abundant pearlite structure

than is obtained by annealing, which results in a harder and stronger steel.
❑ Since the cooling rate is no longer under equilibrium conditions,
the equilibrium constituents can not be predicted after normalizing.
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 Hardening of Steels
❑ Hardening is done by heating the steel ❑ During hardening, since the cooling rate is fast:
to the austenite zone, followed by • Insufficient time for C atoms to diffuse out of austenite
drastic cooling (or quenching) to room
• C atoms remained trapped inside the FCC austenite
temperature.
• Austenite cannot transform into BCC ferrite.
❑ The purposes of hardening: • A new highly distorted structure called martensite,
which has a body-centred tetragonal (BCT) structure is
1. to improve hardness resulted, which causes high hardness and brittleness
2. to improve wear resistance in steel.

❑ This austenite – ferrite transformation is a ❑ Since hardening is not a diffusion-controlled

diffusion-controlled process so that during process, the FCC to BCT transformation cannot be
equilibrium cooling: suppressed during cooling.
• C atoms diffuse out of austenite as cementite
• Austenite (FCC) transforms into ferrite (BCC) 27/38

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Part geometry
❑ Thicker the sample, more variation in the cooling rate
between the centre and surface of the sample.
Centre  slow cooling rate  low hardness
Surface  faster cooling rate  high hardness

Quenching medium
Martensite needles (black) in
retained austenite (white background) ❑ Severity of cooling medium influences the cooling rate.
Air  slow cooling rate  low hardness
Oil  moderate cooling rate  moderate hardness
❑ The basic aim of most hardening operations
Water  fast cooling rate  high hardness
is to obtain 100% full martensitic structure
to have the maximum hardness. Carbon and Alloy Content
❑ But we can’t always produce full martensite ❑ A minimum C level (at least about 0.3%) is necessary
throughout an entire part. to obtain full hardness.
• part geometry, minimum C and alloy content, ❑ Addition of alloying elements slows down the diffusion
and quenching medium influence the formation process, thereby making it easier for the steel to form
of martensite. martensite.

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 Tempering of steels
❑ In the as-quenched condition, the steel is too brittle for most applications.
The formation of martensite also leaves high residual stresses in the steel.
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❑ Tempering is done almost immediately after hardening
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(1) to relieve residual stresses, and (2) to improve

Toughness (ft-lb)
Hardness (RC)
Hardness
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ductility and toughness. The increase in ductility is
attained at the sacrifice of some hardness or strength. 40

20 Toughness
❑ In tempering, the hardened steel is heated and held to a low 0
0 200 400 600 800
to medium high temperature (below the austenite zone),
Tempering Temperature (C)
and then cooled to room temperature.
• The excess carbon atoms, trapped in martensite, gradually come out as cementite particles
and the metastable BCT martensite transforms into stable BCC ferrite.
• The selection of heating temperature depends upon desired properties.
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Part 3
Surface Treatment of Steels

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 5. Surface Treatment of Steels

❑ Many industrial applications require a hard wear-

resistant surface called the case, and a relatively
soft, tough inside called the core. hardened case
(C > 0.8%)
❑ Surface treatments (also known as case hardening
soft core
or surface hardening) are processes of hardening (C < 0.25%)
steel so that the surface layer or case is made
substantially harder than the interior or core.
• uses where such surface hardening treatments
are needed include roller, gear teeth, etc. tooth of a gear

❑ After surface hardening treatment, hardening treatment of the sample is done.

• during this process, martensite is formed at the surface, while the centre remained ferrite-peralitic.
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❑ The most frequently used case-hardening processes are :

1. carburizing,
chemical composition is altered
2. nitriding,
by the addition of carbon, nitrogen, or both
3. cyaniding and carbonitriding
4. flame hardening, and chemical composition is not altered;
5. induction hardening steel must have C content 0.3% or higher

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 Carburising

❑ Introduces C into the surface of steel by • Since the primary object of carburizing is to develop
heating the steel in contact with a a hard case and a relatively soft, tough core, only
carbonaceous medium to austenite zone, low-carbon steels (up to a maximum of about 0.25%
holding at that temperature, and then cool it. of carbon) are normally used.

• After carburizing, the steel will have a high carbon

❑ Depth of penetration of C depends on case graduating into the low-carbon core.
(1) heating temperature,
• Thus, the carburised steel becomes hardenable
(2) heating time, and (i.e., capable of forming martensite by hardening heat
(3) composition of carbonaceous medium treatment) at the surface, but not at the core since
(solid/liquid/gaseous). the C level is not altered there.

Carburising process raises the surface carbon level only.

Hardening heat treatment of the carburised steel must be done to form martensite at the surface.
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ferrite and pearlite pearlite only pearlite and cementite

Surface
structure of a carburized steel
Method of Carburising
1. Pack carburising – sample is packed with mixture of barium carbonate and coke or charcoal.
2. Liquid carburising – sample is heated inside a liquid salt bath consisting of cyanide (poisonous!),
chloride, and carbonate salts. The case contains both C and N, but principally C.
3. Gas carburising – sample is heated around hydrocarbon gas mixture comprising methane,
ethane, and natural gas. 34/38

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 Nitriding

• Introduces N at the surface. • The steel is heated inside a nitrogenous medium, usually
The absorbed atomic nitrogen forms ammonia gas, at a temperature (of about 510 - 565 °C),
iron nitrides, which is extremely hard. well bellow than that required for carburizing (925 °C).
• Since a heating temperature lower than that used in carburizing
• Post hardening heat treatment of steel is used, less distortion occurs in the nitrided steel.
is not necessary, which saves energy.
• The time required is relatively long, normally being 1 or 2 days.
• But to develop full hardness, presence The case, even after 2 days of nitriding, is generally less than
of certain alloying elements (Al, Cr, 0.50 mm and the highest hardness exists in the surface layers
Mo) in steel is necessary to form to a depth of only about 0.03 mm.
harder nitrides than iron nitride. • For a larger case depth, carburizing instead of nitriding is used.

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Cyaniding and Carbonitriding

❑ The case contains both C and N.

❑ Produced either in liquid salt bath (cyaniding) or by use of
gaseous atmosphere (carbonitriding).
❑ Heating temperatures are about 760 – 870 °C.
❑ Exposure time is short and a case depth up to 0.25 mm (in cyaniding)
and 0.75 mm (in carbonitriding) is developed.
❑ Post-hardening heat treatment is required for developing hardness.

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 Flame and Induction Hardening

❑ The chemical composition is not changed in these processes.

• Steel must have sufficient carbon to develop full hardness
(by forming martensite). Carbon levels up to 0.30 – 0.60 % are
necessary.

❑ During these processes, surface of steel is heated very

quickly to the austenite zone, either by oxy-acetylene torch
(in flame hardening) or by induction heating (in induction flame hardening
hardening).
❑ The core of steel remains cold.
❑ Then the sample is quenched to form martensite in the case.
The core remained un-altered (with a ferrite-pearlite structure).
induction hardening
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Summary of surface hardening methods

Post-Heat
Method Media Method Hardening Method
Treatment
Carburising Source of C (solid, Surface composition changed Necessary Hardness developed in high C case by
liquid or gas) by C addition hardening treatment (to form martensite).
Nitriding Source of N Surface composition changed Not N reacts with Fe and other alloys (Al, Cr,
(ammonia gas) by N addition necessary Mo, etc.) to form nitrides; Extremely hard
thin case developed.
Cyaniding Source of C and N Surface composition changed Necessary Hardness developed due to formation of
(liquid salt bath) by C & N addition martensite and nitrides.
Carbonitriding Source of N and C Surface composition changed Necessary Hardness developed due to formation of
(liquid salt bath) by N & C addition martensite and nitrides.
Flame Oxy-acetylene Surface composition NOT Not Surface is quickly heated and then
hardening torch changed; a minimum C level necessary hardened to form martensite. The core
(>0.30%) in steel required. remained un-altered.
Induction Induction Surface composition NOT Not Surface is quickly heated and then
hardening hardening changed; a minimum C level necessary hardened to form martensite. The core
(>0.30%) in steel required. remained un-altered.
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 Next Class
Lecture 25
Part E: Processing and Applications
1 – Introduction to processing

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