Iron-Carbon Phase Diagrams

In their simplest form, steels are alloys of

Iron (Fe) and Carbon (C). The Fe-C phase
diagram is a fairly complex one, but we will
only consider the steel part of the diagram,
up to around 7% Carbon.
In their simplest form, steels are alloys of Iron (Fe) and Carbon (C).
 Eutectoid transformation in steels
Eutectoid: 0.8 wt% C, 727 °C

γ (0.8 wt% C) cooling α (0.022 wt% C) + Fe3C

Acm

A3  When alloy of eutectoid composition (0.76 wt % C) is cooled slowly it

forms perlite, a lamellar or layered structure of two phases: α-ferrite
A1 and cementite (Fe3C)
 The layers of alternating phases in pearlite are formed for the same
reason as layered structure of eutectic structures: redistribution C
Hypo-Eutectoid

Hyper-Eutectoid

atoms between ferrite (0.022 wt%) and cementite (6.7 wt%) by

atomic diffusion.
 Mechanically, pearlite has properties intermediate to soft, ductile
ferrite and hard, brittle cementite

0.8
Eutectoid Transformation of Steel

Above TE
All Austenite

Below TE
All Pearlite
 Eutectoid Transformation of Steel

The dark areas are Fe3C layers, the light

phase is α-ferrite
 Eutectoid Transformation of Steel

 At low temperatures, the transformation occurs sooner (it is controlled by the rate
of nucleation) and grain growth (that is controlled by diffusion) is reduced.

 Slow diffusion at low temperatures leads to fine-grained microstructure with thin-

layered structure of pearlite(fine pearlite).

 At higher temperatures, high diffusion rates allow for larger grain growth and
formation of thick layered structure of pearlite (coarse pearlite)
Hypo-eutectoid and Hyper-eutectoid transformation in steels

Hypo-eutectoid Steel

Hyper-eutectoid Steel
 Phase Transformation
 Phase transformation is an even of Nucleation and Growth
 Nucleation: Free energy should be minimum Heterogeneous Nucleation
 Homogeneous Nucleation  Nucleation occurs at a surface, interface, impurity, or other
heterogeneities in the system
 Heterogeneous Nucleation
 The energy required for nucleation is reduced by a factor related to
the contact angle of the nucleus on the foreign surface
Homogeneous Nucleation

 Growth: Assume that stable nuclei exist prior to growth

Add molecules to a stable cluster Driven by free energy
decrease of phase change Kinetically limited

free energy versus embryo/nucleus radius, on which is shown

the critical free energy change (G*) and the critical nucleus
radius (r*)
Phase Transformation

where k and n are time-

independent constants
for the particular reaction
 The Limitation of Equilibrium Phase Diagrams

• Unable to indicate the time period required for the attainment of equilibrium
• Equilibrium conditions are maintained only if heating or cooling is carried out at
extremely slow and unpractical rates.

Concept of Time-Temperature-Transformation (T-T-T) Diagrams

The eutectoid reaction is fundamental to the development of microstructures in steel alloys.

γ (0.76 wt% C) ⇌ α (0.022 wt% C) + Fe3C (6.70 wt% C)

Pearlite is the microstructural product of this transformation.

 Time-Temperature-Transformation (T-T-T) Diagrams

Interpretation of the TTT diagram

 Above eutectoid temperature: only austenite exists
 Below eutectoid temperature: nucleation + growth
The percentage of the transformation product is related to the holding temperature and
holding time.

 Nature of transformation-isothermal or athermal (time independent) or mixed

 Type of transformation-reconstructive, or displacive
 Rate of transformation
 Stability of phases under isothermal transformation conditions
 Temperature or time required to start or finish transformation
 Qualitative information about size scale of product
 Hardness of transformed products
 At T1, incubation period for pearlite=t2,
Pearlite finish time =t4

Minimum incubation period t0 at the nose of the

TTT diagram,

Log time
Schematic TTT diagram for plain carbon hypoeutectoid steel

γ=austenite
α=ferrite
CP=coarse pearlite
P=pearlite
FP=fine pearlite
UB=upper Bainite
LB=lower Bainite
M=martensite
MS=Martensite start temperature
M50=temperature for 50% martensite
formation
MF= martensite finish temperature
 Time-Temperature-Transformation (T-T-T) Diagrams
Pearlite
• The thickness of the ferrite/cementite layers in pearlite depends on the
temperature. With decreasing temperature, the layers become progressively
thinner.
• At temperatures just below eutectoid  relatively thick layers  coarse
pearlite
• In the vicinity of 540C  relatively thin layers  fine pearlite

- Smaller T: - Larger T:

colonies are colonies are
larger smaller
Bainite
 Bainite is formed at cooling rates slower than that for
martensite formation and faster than that for ferrite and
pearlite formation. There are two forms of bainite, known as
upper and lower bainite.
 Upper bainite generally forms at temperatures between
550 and 400°C.
 Low carbon steels exhibit fine bainitic laths, nucleated by a
shear mechanism at the austenite grain boundaries.
 Several proposed formation mechanisms, based on the carbon
content and transformation temperature of the steel, resulting
in slightly different morphologies.
 Lower bainite generally forms at temperatures between 400
and 250°C
 The appearance of lower bainite strongly resembles that of mechanism of the bainite transformation
martensite, but lower bainite is formed by a mixture of shear
and diffusional processes rather than just shear.
 In case of high carbon content, the cementite filaments become more continuous, and at high carbon contents, the bainitic
ferrite laths are finer with the cementite stringers more numerous and more continuous. The structure can appear more like
pearlite, and is termed 'feathery' bainite.
 In case of low carbon content: Carbon solubility in bainitic ferrite is Within the bainitic transformation temperature range,
much lower than in austenite, so carbon is rejected into the austenite austenite of large grain size with high inclusion density
surrounding the bainitic ferrite laths. When the carbon concentration promotes acicular ferrite formation under isothermal
in the austenite is high enough, cementite nucleates as discrete transformation condition. The morphology is shown
particles or discontinuous stringers at the ferrite/austenite interfaces schematically
 (c)

(a) Coarse Pearlite (b) Fine Pearlite

Micrograph of (a) coarse pearlite and (b) fine pearlite (c) full bainite.
Martensite
• Martensite is formed when austenitized Fe-C alloys are rapidly cooled (or quenched) to a
relatively low temperature (in the vicinity of the ambient).
• Non-equilibrium single phase
• A transformation product that is competitive with pearlite
• Transformation of FCC to BCT (body-centered tetragonal)
• Occurs instantaneously  time-independent
• The martensite grains nucleate and grow at a very rapid rate — the velocity of
sound within the austenite matrix. BCT Martensite
FCC Austenite (g phase)
(body-centered tetragonal)

The body-centered tetragonal unit cell for martensitic

steel showing iron atoms (circles) and sites that may be
occupied by carbon atoms (crosses). For this tetragonal
unit cell, c > a.
 Lenticular or plate
martensitic microstructure

Micrograph showing the lenticular or plate martensitic microstructure. The needle-shaped grains are the
martensite phase, and the white regions are austenite that failed to transform during the rapid quench. 1220X.
 Mechanical Behavior of Iron-Carbon Alloys
Pearlite
• Cementite (Fe3C) is much harder but more brittle
than ferrite (a). Hypo Hyper
• % Fe3C   strength, ductility

Brinell hardness
600
Martensite martensite
• Hardest and strongest, and most brittle 400

• Volume change  crack formation during

quenching 200
fine pearlite
0
0 0.5 1
wt%C
Hardness: fine pearlite << martensite.
Iron-Carbon Alloy system
 Types of steel and its applications
 Steel can be broadly categorized into four groups based on their chemical compositions:
1. Carbon Steels; 2. Alloy Steels; 3. Stainless Steels; 4. Tool Steels

Carbon Steels Alloy Steels Stainless Steels Tool Steels

Contain trace amounts of Contain alloying elements Contain between 10-20% Tool steels contain tungsten,
alloying elements and e.g. manganese, silicon, chromium as the main alloying molybdenum, cobalt and
account for 90% of total steel nickel, titanium, copper, element and are valued for high vanadium in varying
production. chromium, and aluminum corrosion resistance quantities
Carbon steels can be further in order to influence the It can be divided into three groups Increase heat resistance and
categorized into three groups steel's properties, such as based on their crystalline durability, making them ideal
depending on their carbon its hardenability, corrosion structure: for cutting and drilling
content resistance, strength, • Austenitic steel equipment.
•Low Carbon Steels/Mild formability, weldability or • Ferritic steel
Steels contain up to 0.3% ductility. • Martensitic steel
carbon • Duplex steel
•Medium Carbon Steels
contain 0.3-0.6% carbon
•High Carbon Steels contain
more than 0.6% carbon
 Carbon Steels

Microstructure Properties Examples Applications

automobile body components,

Low hardness and cost. High structural shapes (I-beams, channel
Ferrite, AISI 304, ASTM
Low-carbon steel ductility, toughness, and angle iron), pipes, construction
pearlite A815, AISI 316L
machinability and weldability and bridge components, and food
cans.
Low hardenability, medium Railway tracks, train wheels,
Medium- AISI 409, ASTM
Martensite strength, ductility and crankshafts, and gears and machinery
carbon steel A29, SCM435
toughness parts

High- High hardness, strength, low AISI 440C, EN Cutting tools, springs high strength
Pearlite
carbon steel ductility 10088-3 wire and dies
 Alloy Steels
 Steel is essentially iron and carbon alloyed with certain additional elements.
 The process of alloying is used to change the chemical composition of steel and improve its properties over carbon
steel or adjust them to meet the requirements of a particular application.
 During the alloying process, metals are combined to create new structures that provide higher strength, less corrosion,
or other properties.
 Stainless steel is an example of alloyed steel that includes the addition of chromium.

Stabilizing austenite: Elements such as nickel, manganese, cobalt, and copper increase the temperatures range in which
austenite exists.
Stabilizing ferrite: Chromium, tungsten, molybdenum, vanadium, aluminum, and silicon can help lower carbon's solubility in
austenite. This results in an increase in the number of carbides in the steel and decreases the temperature range in which
austenite exists.
Carbide forming: Many minor metals, including chromium, tungsten, molybdenum, titanium, niobium, tantalum and
zirconium, create strong carbides that—in steel—increase hardness and strength. Such steels are often used to make high-
speed steel and hot work tool steel.
Graphitizing: Silicon, nickel, cobalt, and aluminum can decrease the stability of carbides in steel, promoting their breakdown
and the formation of free graphite.
Types of alloy steel
There are multiple subcategories of alloy steel. These include:
• Low-alloy steel
• High-strength low alloy (HSLA) steel
• High-alloy steel
• Stainless steel
• Microalloyed steel
• Advanced high-strength steel (AHSS)
• Maraging steel
• Tool steel

Applications:
• Low alloy steels are used in a wide range of industries due to their extreme strength, machinability, cost-
effectiveness and availability. They are found in military vehicles, construction equipment, ships, pipelines, pressure
vessels oil drilling platforms and in structural components.
• High-alloy steels can be expensive to manufacture and difficult to process. Nevertheless, their superior hardness,
toughness and corrosion resistance make them ideal for structural components, automotive applications, chemical
processing and power generating equipment
 Stainless steels
This term describes a group of steel alloys containing over 11% chromium. There are four main categories, which in turn
may be subdivided into many different proprietorial and generic grades.

 Austenitic — which contain 17 to 25% chromium combined with 8 to 20% nickel and/or magnesium and other trace
alloying elements. They are easily weldable due to the low carbon content and in their raw state are non-magnetic.
Magnetism can however, be induced by heavy working. Good strength is combined with high corrosion resistance.

 Ferritic — again have a high chromium content greater than 17% together with medium carbon content and small
quantities of molybdenum and silicon. Good corrosion resistance rather than high strength and generally non-
hardenable. Magnetic.

 Martensitic — have a high carbon content up to 2% and a low chromium content generally around 11.2%. Difficult to
weld. Magnetic.

 Duplex — grades contain both austenitic and ferritic phases. High tensile strength at normal temperatures is combined
with good corrosion resistance due to the addition of trace elements. Weldable, but becomes brittle above 300 °C.
 Ferritic
 Ferritic stainless steels possess a body-centred cubic crystal structure, similar to that of pure iron.
 They generally have a high chromium content of between 10.5 wt.% and 18 wt.%.
 They have a low carbon content, which gives them a relatively low strength and contain little to no nickel.
 Ferritic stainless steels are not hardenable by heat treatment. After annealing, they have yield strengths in
the range of 275 MPa – 350 MPa.
 Ferritic stainless steels are known to have low ductility, resulting in reduced formability, are magnetic, have
limited toughness and often lower corrosion resistance compared to other stainless steels.
 Their absence of nickel, however, gives them a lower cost.
 One of the main advantages of ferritic stainless steels is their high resistance to stress corrosion cracking.

 Applications
 409, used in the automotive industry for parts such as exhaust systems and tailpipes.
 410S, used in the oil and gas industry, ore processing and thermal processing.
 430, used in dishwasher linings, refrigerator cabinet panels, element supports and fasteners, stove trim
rings and chimney liners and automotive trim and lashing wire
 Austenitic
 Austenitic stainless steels are the most common category of stainless steel.
 They possess a face-centred cubic crystal structure.
 In addition to the main alloying elements of iron and chromium, these steels also contain nickel, manganese and
nitrogen.
 They are not hardenable via heat treatment but only by cold working (also known as work hardening).
 These steels have relatively low strength compared to the other steels and lower resistance to corrosion

Applications:
 It is used for many applications including cutlery, kitchen equipment, food processing equipment, automotive and
aerospace structural components and marine fasteners.
 Food preparation equipment, chemical processing equipment, laboratory benches and equipment, boat fittings, heat
exchangers and pharmaceutical and textile equipment and surgical equipment
 Paper handling equipment, chemical and petrochemical processing equipment, condensers in power generation stations,
food processing equipment and textile equipment
Examples:
304, 316, 317 alloys
 Martensitic
 Martensitic stainless steels posses the body-centred tetragonal crystal system.
 They can range from having a low to high carbon content, up to 1.2 wt.%, contain 12 wt.% – 15 wt.% chromium and 0.2
wt.% to 1.0 wt.% molybdenum.
 They do not contain nickel. Due to the presence of carbon, they are hardenable via heat treatment, similarly to carbon
steels.
 Martensitic stainless steels are magnetic and possess relatively high ductility and toughness, making them easier to
form.
 They can be moderately hardened via cold working. After annealing, they typically have yield strengths of around 275
MPa.
This is dependant on carbon content: higher carbon content results in increased strength and hardness but decreased
ductility and toughness. They exhibit moderate corrosion resistance and poor weldability.

 Examples & applications

 403, used in compressor blades and turbine parts.
 410, used for highly stressed parts, for examples in turbine blades, kitchen utensils, bolts, nuts and screws, pump and
valve parts, dental and surgical instruments, nozzles and parts for oil well pumps.
 416, which has the highest machinability of any stainless steel, is used for electrical motors, nuts and bolts, pumps, valves,
automatic screw machine parts and gears.
 420, used for cutlery, knife blades, surgical instruments, needle valves, shear blades, scissors and hand tools.
  Duplex Steel
 Duplex stainless steels possess a mixed microstructure of ferrite and austenite.
 They contain a high chromium content of 22 wt.% – 25 wt.%, a molybdenum content of up to 5 wt.% and a low nickel
content.
 Duplex stainless steels exhibit roughly twice the strength of austenitic stainless steels and possess greater resistance to
chloride stress corrosion cracking compared to austenitic stainless steels, albeit less so than ferritic.
 They exhibit toughness between that of ferritic and austenitic.

 Examples & applications

 2205, used in chemical processing, oil and gas processing equipment, marine and other high chloride environments,
effluent scrubbing systems, pulp and paper industry, cargo tanks for ships and trucks, food processing equipment,
biofuels plant.

 2304, used in chloride containing environments, welded pipe systems, transportation, heat exchanger tubes,
construction, pressure vessels, caustic solutions and the food industry.

 2507, used in oil and gas industry equipment, offshore platforms, chemical process industries, desalination plants,
mechanical and structural components and power industry FGD systems
 Heat treatment of steel

Majorly two types

• Bulk heat treatment and
• Surface treatments
Acm

Bulk heat treatment A3

Surface treatments
1. Annealing, 1. Carburizing
723C Full Annealing
2. Normalizing, 2. Nitriding
3. Hardening, 3. Carbo-nitriding A1
4. Tempering

Eutectoid steel
Annealing Stress Relief Annealing
1. Full Annealing 
T Recrystallization Annealing
2. Recrystallization Annealing
Spheroidization
3. Stress Relief Annealing
4. Spheroidization Annealing Hypo-eutectoid steel Hyper-eutectoid steel
Tempering
1. Martempering 0.8 %
2. Austempering Wt% C
 Full Annealing
 The purpose of this heat treatment is to obtain a material with high ductility. A microstructure with coarse pearlite (i.e.
pearlite having high interlamellar spacing) is endowed with such properties.
 The range of temperatures used is given in the figure below.
 The steel is heated above A3 (for hypo-eutectoid steels) & A1 (for hyper-eutectoid steels) → (hold) → then the steel is
furnace cooled to obtain Coarse Pearlite.
 Coarse Pearlite has low (↓) Hardness but high (↑) Duc lity.
 For hyper-eutectoid steels the heating is not done above Acm to avoid a continuous network of proeutectoid cementite
along prior Austenite grain boundaries (presence of cementite along grain boundaries provides easy path for crack
propagation).

Recrystallization Annealing
 During any cold working operation (say cold rolling), the material becomes harder (due to work hardening), but loses its
ductility. This implies that to continue deformation the material needs to be recrystallized (wherein strain free grains
replace the ‘cold worked grains’).
 Hence, recrystallization annealing is used as an intermediate step in (cold) deformation processing.
 To achieve this the sample is heated below A1 and held there for sufficient time for recrystallization to be completed.
Stress Relief Annealing
 Due to various processes like quenching (differential cooling of surface and interior), machining, phase transformations (like
martensitic transformation), welding, etc. the residual stresses develop in the sample. Residual stress can lead to undesirable
effects like warpage of the component.
 The annealing is carried out just below A1 , wherein ‘recovery*’ processes are active (Annihilation of dislocations,
polygonization).
Spheroidization Annealing
 This is a very specific heat treatment given to high carbon steel requiring extensive machining prior to final hardening &
tempering. The main purpose of the treatment is to increase the ductility of the sample.
 Like stress relief annealing the treatment is done just below A1.
 Long time heating leads cementite plates to form cementite spheroids. The driving force for this (microstructural)
transformation is the reduction in interfacial energy.

 NORMALIZING
 The sample is heat above A3 /Acm to complete Austenization. The sample is then air cooled to obtain Fine pearlite. Fine
pearlite has a reasonably good hardness and ductility.
 In hypo-eutectoid steels normalizing is done 50C above the annealing temperature.
 In hyper-eutectoid steels normalizing done above Acm → due to faster cooling cementite does not form a continuous film
along GB.
 The list of uses of normalizing are listed below.
 Purpose Normalizing
 Refine grain structure prior to hardening
 To harden the steel slightly
 To reduce segregation in casting or forgings

 HARDENING

 The sample is heated above A3 | Acm to cause Austenization. The

sample is then quenched at a cooling rate higher than the critical
cooling rate (i.e. to avoid the nose of the CCT diagram).
 The quenching process produces residual strains (thermal, phase
transformation).
 The transformation to Martensite is usually not complete and the
sample will have some retained Austenite.
 The Martensite produced is hard and brittle and tempering
operation usually follows hardening. This gives a good
combination of strength and toughness.
 Quenching and Tempering: quenching in a suitable medium from an austenitizing temperature, typically 845 to 925°C
(1550 to 1700°F), and reheating to achieve desired hardness.
 Carburizing: adding carbon to the surface of steel, in a controlled atmosphere furnace, to increase the ultimate
hardness, typically to a depth of 0.5 to 1.0 mm (0.020 to 0.040 in.). The process is followed by quenching and
tempering.
 Nitriding: adding nitrogen in a controlled atmosphere furnace to form nitrides in the steel, which develops very high
hardness and superior wear resistance. The case depth is normally several hundredths of a millimeter (a few
thousandths of an inch) thick. The process is followed by quenching and sometimes tempering.
Carbonitriding: adding both carbon and nitrogen in a controlled atmosphere furnace to optimize properties, to a
depth similar to carburizing. The process is followed by quenching and tempering.
 Austenitizing: Heating to an austenitizing temperature and cooling under controlled conditions to develop a
combination of ductility and hardness with maximum impact toughness. Generally applied to fairly high alloy steels.
 Marquenching: Heating to an austenitizing temperature and quenching in molten salt. The process results in
minimum transformation stress, and is applied only to fairly high alloy steels. The process is followed by tempering.
 MARTEMPERING & AUSTEMPERING

 These processes have been developed to avoid residual

stresses generated during quenching.
 In both these processes Austenized steel is quenched above
Ms (say to a temperature T1) for homogenization of
temperature across the sample.
 In Martempering the steel is then quenched and the entire
sample transforms simultaneously to martensite. This is
followed by tempering.
 In Austempering instead of quenching the sample, it is held at
T1 for it to transform to bainite.
Cast Iron
 Alloys of Fe and C (like steel) but contain
higher Carbon •
 Typically Carbon is 2.5 to 4%
 Very brittle, not amenable to deform
 Easy to cast (due to lower melting point) into
complicated shapes and cheap
 With alloying, good foundry practice and
heat treatment, properties can be varied
over wide range
 Carbon can occur in cast iron as: combined
carbon (Fe3C) or free carbon (graphite)
 Shape and distribution of free carbon also
important
  Parameters that influence are: Carbon content, Alloy and impurity content, Cooling rate during and after freezing,
Heat treatment after casting

 Classification of Cast Irons is based on metallographic structure

 White Cast Iron (combined carbon Fe3C)
 Malleable Cast Iron (free carbon as irregular particles)
 Chilled Cast Iron (white cast iron at the surface and gray cast iron at the interior)
 Grey Cast Iron (Flake Graphite)
 Spheroidal Graphite (SG) / Ductile Cast Iron / Nodular Cast Iron (free carbon as spheroids) 6. Alloy Cast
Iron

White Cast Iron ( Fast cooling rate)

Applications:
Ball-mills, pumps; wearing plates, drawing-dies, extrusion nozzles, grinding balls, parts of sand slingers.
 Malleable Cast Iron
Grey Cast Iron

Compressive strength
>> tensile strength

Application: Application:
Electrical fittings and equipment, hand tools, pipe fittings, Clutch plates, brake-drums, heavy
washers, brackets, farm equipment, mining hardware, and machine beds; counter weights in
machine parts. elevators, furnaces; guards and frames,
gear housings; pump housings; housing
for steam turbines, cylinders, pistons,
A high cooling rate and a low carbon equivalent favours the engine frames, etc
formation of white cast iron A low cooling rate or a high
carbon equivalent promotes grey cast iron
 Chilled Cast Iron
 Obtained by casting against a chiller
 Surface is White C.I. (faster cooling rates)
 Harder / wear resistant surface
 Depth depends on composition (C, Si decrease chill depth) Carbide forming elements like Cr, Mo increase chill
depth
 Applications: Railway car wheels, crushing rolls, heavy machinery