Chapter One Engineering Materials

Ferrous Alloys Engineering Materials 4th. Year / 1st. Semester

Important things
Subject: Engineering Materials is highlighted

Stage :4th year \ Semester :1st \ Code: ME414

Lecturers:

Dr. Murtadha Abbas Almaliky & Mrs. Nagham Mohammed Altimime

Syllabus:

Chapter One: Ferrous Alloys

Chapter Two: Non- Ferrous Alloys

Chapter Three: Ceramics

Chapter Four: Polymers

Chapter Five: Composites

References:

1. The Science and Engineering of Materials, Sixth Edition by Donald R. Askeland,

Pradeep P. Fulay, and Wendelin J. Wright.

2. Materials Science and Engineering An Introduction ninth Edition by William D.

Callister, Jr. and David G. Rethwisch.

3. Heat Treatment of Metals Volume one, by J.L. Smith, G.M. Russel, and S.C.
Bhatia.
4. An Introduction to the Metallurgy of Steel and its Alloys by Robert A. Francis

5. ‫بيللي ترجمة حسين باقر رحمة للا‬. ‫مبادئ هندسة المعادن والمواد تأليف ف‬
Chapter One Engineering Materials
Ferrous Alloys Engineering Materials 4th. Year / 1st. Semester

CHAPTER ONE
FERROUS ALLOYS

1.1 Introduction
Ferrous alloys, which are based on iron-carbon alloys, include plain carbon steels, alloy and tool steels,
stainless steels, and cast irons. These are the most widely used materials in the world. In the history of
civilization, these materials made their mark by defining the Iron Age. Steels typically are produced in
two ways: by refining iron ore or by recycling scrap steel.
In producing primary steel, iron ore (processed to contain 50 to 70% iron oxide, Fe2O3 or Fe3O4)
is heated in a blast furnace in the presence of coke (a form of carbon) and oxygen. The coke reduces the
iron oxide into a crude molten iron known as hot metal or pig iron. At about ~1600°C, this material
contains about 95% iron; 4% carbon; 0.3 to 0.9% silicon; 0.5% manganese; and 0.025 to 0.05% of sulfur,
phosphorus, and titanium. Slag is a byproduct of the blast furnace process. It contains silica, CaO, and
other impurities in the form of a silicate melt.
Because the liquid pig iron contains a large amount of carbon, oxygen is blown into it in the basic
oxygen furnace (BOF) to eliminate the excess carbon and produce liquid steel. Steel has a carbon content
up to a maximum ~2% weight basis. In the second method, scrap is often melted in an electric arc furnace
in which the heat of the are melts the scrap. Many alloy and specialty steels, such as stainless steels, are
produced using electric melting. Molten steels (including stainless steels) often undergo further refining.
The goal here is to reduce the levels of impurities such as phosphorus, sulfur, etc. and to bring the carbon
to a desired level.
Molten steel is poured into molds to produce finished steel castings or cast into shapes that are later
processed through metal-forming techniques such as rolling or forging. In the latter case, the steel is either
poured into large ingot molds or is continuously cast into regular shapes.

1.2 Classification of Ferrous Alloys:

Nomenclature AISI (American Iron and Steel Institute) & SAE (Society of Automotive Engineers). The
AISI maintained a numbering system for wrought stainless steel in which the three digits indicate the
various compositions. The 200 and 300 series are generally austenitic stainless steels, whereas the 400
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Ferrous Alloys Engineering Materials 4th. Year / 1st. Semester

series are either ferritic or martensitic. Some of the grades have a one-letter or two-letter suffix that
indicates a particular modification of the composition.
The unified numbering system (UNS) is an alloy designation system widely accepted in North
America. Each UNS number relates to a specific metal or alloy and defines its specific chemical
composition, or in some cases a specific mechanical or physical property. A UNS number alone does not
constitute a full material specification because it establishes no requirements for material properties, heat
treatment, form, or quality.
• 10xx Plain Carbon Steels
• 11xx Plain Carbon Steels (desulfurized for machinability)
• 15xx Mn (10 ~ 20%)
• 40xx Mo (0.20 ~ 0.30%)
• 43xx Ni (1.65 - 2.00%), Cr (0.4 - 0.90%), Mo (0.2 - 0.3%)
• 44xx Mo (0.5%)
Where xx is wt% C x 100
Example: 1060 steel – plain carbon steel with 0.60 wt% C
Stainless Steel -- >11% Cr – AISI number e.g. 40
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Figure 1.1 Classification scheme for the various ferrous alloys.

1.3 The Iron-Carbon Phase Diagram:

A portion of the iron–carbon phase diagram is presented in Figure (1.2) Pure iron , upon heating,
experiences two changes in crystal structure before it melts. At room temperature the stable form, called
ferrite, or (α) iron, has a BCC crystal structure. Ferrite experiences a polymorphic transformation to FCC
austenite, or (γ) iron, at (910OC). This austenite persists to (1390oC), at which temperature the FCC
austenite reverts back to a BCC phase known as δ ferrite, which finally melts at (1535oC). All these changes
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are apparent along the left vertical axis of the phase diagram. The composition axis in Figure (1.2) extends
only to 6.70 wt % C; at this concentration the intermediate compound iron carbide, or cementite (Fe 3C),
is formed, which is represented by a vertical line on the phase diagram. In practice, all steels and cast irons
have carbon contents less than 6.70 wt% C; therefore, we consider only the iron–iron carbide system.

Figure 1.2 The iron–iron carbide phase diagram.

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1. δ-phase (δ- ferrite): solid solution of C in BCC iron at high Temperature.

2. γ-phase (Austenite): solid solution of C in FCC iron with 1.7% solubility of C in Fe, formed by
peritectic reaction between liquid and δ- ferrite at high temperatures, large grains and straight grain
boundaries, stable at a temperatures above A1, high ductility.
3. α-phase (ferrite): A solid solution of C in BCC iron with 0.03% solubility of C in Fe, formed
from austenite through solid phase transformation, small grains and irregular grain boundaries,
stable at room temperature, ductile and soft, not so strong.
4. Iron carbide (Fe3C) or cementite, it is an intermetallic compound with carbon content of 6.67%.
Very hard and brittle. the more cementite the steel contains, the harder and more brittle
5. Pearlite (P): laminar structure of ferrite and cementite, formed as a product of eutectoid
transformation of austenite at A1and 0.8% C, good combined strength and toughness, ideal for
structural applications
6. Graphite (G): pure C; stable.

1.4 PLAIN CARBON STEELS

Steel theoretically is an alloy of iron and carbon. When produced commercially however, certain
other elements such as manganese, silicon, sulphur and phosphorus are inevitably present in small
quantities. When these four elements are present in their normal amounts, the product is referred to as
plain carbon steel. The proportion of carbon has a significant effect on properties and therefore uses of the
steel. Increasing carbon content increases strength, but decreases ductility, toughness and weldability.
Applications where ductility is important, such as sheet products, tend to be low carbon, while applications
where hardness and strength are important, such as tools and knives, tend to be high carbon.

Typical changes in strength and ductility of simple carbon steels with carbon content are shown in
Figure 1.3. In practice, the properties are usually improved with alloying elements or heat treatment. Plain
carbon steels are generally classed into three sub-groups according to their carbon content, although there
is little agreement as to the carbon limits. Low-carbon steels (sometimes called mild steels) have less than
about 0.30 per cent carbon and have good formability and weldability, but are not hardenable by heat
treatment and are of fairly low strength (a yield strength of less than about 300 MPa). The structure is
almost entirely ferritic up to about 0.15 per cent carbon with increasing proportions of pearlite from then
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on. Medium carbon steels have between 0.30 and 0.80 per cent carbon, have higher strengths and can heat
treated if the section size is small. High-carbon steels have more than 0.8 per cent carbon with low
toughness and formability, but high hardness and wear resistance. Table 1-1 indicates some typical
properties and applications of plain carbon steels. Plain carbon steels are the lowest cost materials and can
be considered for many simple applications. However, if improved properties are required, steel can be
upgraded by the addition of one or more alloying elements.

Figure 1.3: Typical mechanical properties of plain carbon steels

Table 1-1: Classification and applications of plain carbon steel

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Ferrous Alloys Engineering Materials 4th. Year / 1st. Semester

1.5 EFFECTS OF ALLOYING ELEMENTS

In general, alloying elements are added to steel in small percentages usually less than 5 per cent to improve
strength or other mechanical properties. Larger amounts, often up to 20 per cent, are required to produce
special properties such as stability at high temperatures or corrosion resistance. The additions may affect
the properties in a number of ways. Some, such as manganese, silicon and nickel, will go into the ferrite
and improve the strength by solid solution strengthening. Some, such as chromium, vanadium and
molybdenum, form precipitates which strengthen the steel by precipitation hardening. If stable at high
temperatures, such as those precipitates formed by vanadium, these may further strengthen the material
by preventing growth of the austenite grains. Certain elements, for example chromium and boron, increase
the time required for the austenite to change to martensite, enabling martensite to be obtained in larger
sections; i.e., they increase the hardenability. Some additions have effects on other properties as well
aluminum and silicon are used to remove dissolved oxygen from the melt. Machinability may be enhanced
by additions of sulphur, selenium or lead. Copper is added to low alloy steels to provide improved
corrosion resistance.
The individual effects of the major alloying elements are described below. The first six elements
are found in small amounts in plain carbon steels, either as impurities or deliberate additions. Small
amounts of the other elements such as chromium and nickel are also found in modern carbon steels as a
result of contaminated scrap.
➢ Carbon is the principle hardening element in all steel. Tensile strength increases as carbon
increases, although ductility, toughness and weldability decrease.
➢ Manganese is perhaps the most important alloying element in steel after carbon. It increases
hardenability and the strength and toughness of the steel. It is a ferrite strengthener and an austenite
stabilizer and lowers the A3 temperature. It combines with the sulphur in steel to form soft,
manganese sulphide inclusions preventing iron sulphide forming at the grain boundaries which
would cause brittleness. It also provides some deoxidation.
➢ Silicon is usually the principal deoxidizer used in steel-making, and the amount usually indicates
the degree of deoxidation. Fully killed steels usually contain from 0.1 to 0.35 per cent but
sometimes more, semi-killed usually less than 0.1 per cent and rimmed steel grades usually less
than 0.05 per cent. Silicon improves hardenability in heat treated steels. Silicon also increases the
hardness by strengthening the ferrite and some spring steels contain about 2 per cent silicon.
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➢ Phosphorus is an impurity and not deliberately added. It increases the hardness but has a
deleterious effect on the toughness so is usually restricted to a maximum limiting percentage.
➢ Sulphur is usually an undesirable element in steel because of its embrittling effect and a maximum
sulphur content is specified for most steels. However, sulphur is added to certain grades of steel,
the free-machining steels, for the sole purpose of improving machinability.

The following elements are added to so-called “Low alloy steels” to improve properties such as strength,
toughness or heat treatment properties.
➢ Aluminum is used as a deoxidizer, normally in conjunction with silicon, and as a grain refining
element. Also, it is added in amounts of about 1 per cent to produce steels suitable for surface
hardening by nitriding.
➢ Nickel is added primarily to increase toughness and impact resistance, particularly at low
temperatures. When used in conjunction with other elements, it is an austenite stabilizer so it
widens the temperature range for successful heat treatment.
➢ Chromium improves hardenability and forms chromium carbides with carbon to impart increased
strength, hardness and wear resistance. It is a ferrite stabilizer, causing the A 3 temperature to be
raised. Amounts more than approximately 12 per cent improve corrosion resistance.
➢ Molybdenum improves hardenability and increases strength and hardness. It eliminates the
problem of brittleness that follows quenching and tempering (temper embrittlement), particularly
in nickel-chromium steels. It also improves creep properties, retaining mechanical properties at
elevated temperatures.
➢ Vanadium is another alloying element that forms strong carbides that persist at high temperatures.
This means a finer austenite grain size resulting in an increase in strength without unduly reducing
the ductility, and improving the impact strength. It is often used in low alloy, high strength steels
in amounts up to 0.25 per cent.
➢ Niobium (known as Columbium in the USA) has a very strong affinity for carbon and nitrogen,
forming exceptionally stable carbo-nitrides. This results in fine-grained steels with increased
strength and improved low temperature impact properties.
➢ Titanium is used in carbon steels principally as a grain refining element by forming stable carbo
nitrides. It also can act as a deoxidizing agent.
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➢ Copper is added in amounts of 0.25 to 0.40 per cent to carbon steels to improve resistance to
atmospheric corrosion. In these amounts, it has little effect on arc welding and has no significant
effect on mechanical properties.
➢ Boron added to carbon and alloy steels in very small percentages, is a very powerful hardenability
agent. Its effect diminishes as carbon content increases. Boron has no significant effect on the
mechanical properties of carbon steel in the as-rolled condition.
➢ Tungsten is a primary alloying element in tool steels as it allows steel to retain its hardness at high
temperatures.
➢ Lead is virtually insoluble in steel and small amounts impart machinability.

1.6 ALLOY STEELS

As mentioned above, an alloy steel is one which contain deliberate additions of elements other than
carbon, manganese and deoxidation elements. In this section, we will look at the composition, properties
and uses of some of the common alloy steels, sometimes called engineering steels. These are inevitably
used in the quenched and tempered state.

1.6.1 HIGH STRENGTH LOW ALLOY STEELS

The early development of structural steels for bridges, ships, etc., was based on the use of low carbon
steel (up to 0.25 per cent carbon). The structures were assembled with rivets and bolts. However, with
time, welding became more widely used as a means of assembly and problems involving lack of toughness
and weldability were encountered. Furthermore, there has been increased demand for lighter, more elegant
structures requiring higher strength steels, as well as resistance to brittle fracture at very low temperatures.
Reduction in the carbon content was necessary, along with the development of new strengthening
mechanisms, to meet these demands. The key to the development of improved strength, toughness and
ductility at low carbon contents lies mainly in the refinement of the ferrite grain size.
Grain refinement of the austenite, and therefore the ferrite, can be achieved by additions of small amounts
(usually 0.05 to 0.10%) of niobium, vanadium or titanium either singly or in combination. They also
provide precipitation hardening by carbo-nitrides. However, hardening by precipitation causes an increase
in the impact transition temperature, so development of stronger steels has concentrated on grain
refinement using controlled rolling or other thermo-mechanical treatments to low finishing temperatures.
A further development to improve impact properties and ductility, and to reduce lamellar tearing in welds,
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Ferrous Alloys Engineering Materials 4th. Year / 1st. Semester

is the reduction of sulphur content and the development of inclusion shape control in which the plasticity
of the inclusions is altered.
There is a large number of high strengths, low alloy (sometimes called micro-alloyed steels) on the
market today with a wide range of end uses. Universal columns and beams and other sections are now
available with guaranteed low-temperature toughness properties. These include vanadium and vanadium-
niobium steels with minimum yield strengths in the range 300-450 MPa. High strength cold pressing
steels, particularly for use in the automobile industry, require inclusion modification to ensure that
sulphide stringers are not present to cause splitting or cracking when deformed. Such steels tend to be
supplied to mechanical specifications, leaving the chemical composition to the steelmaker. Pipelines are
also major application for modern HSLA steels.
The factors which contribute to the strength of HSLA steels can be looked at from a fundamental
point-of-view. The measured yield strength of a metal is a result of the combination of all the strengthening
factors described earlier which block dislocation movement. This can be expressed as:

1.6.2 WEATHERING STEELS

Weathering steels are higher strength steels (normally approximately 350 MPa yield strength) that
have superior atmospheric corrosion resistance compared to plain carbon steels due to the presence of
small amounts of copper, phosphorus, chromium and nickel. These elements cause the rust that forms on
the surface to be dense and adherent, restricting further significant corrosion. These steels, commonly
referred to as Corten steels, can be used in the unpainted condition but are not suitable in an aggressive
environment or one which is continually damp. Staining on adjacent materials which may be aesthetically
unacceptable can be caused by rainwater draining from weathering steel. Furthermore, weld areas may
discolor and corrode at a different rate from the rest of the steel. In the USA, weathering steel is usually
specified to ASTM A242 (Corten A) or ASTM A588 (Corten B).For piling in marine environments,
ASTM A690 steel, commonly known as Mariner grade, has similar composition but used for marine
piling. It is claimed to reduce the corrosion rate in the splash zone by two to three times as long as the
steel is exposed to the washing action of rain and the drying effect of sun and wind.
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1.6.3 STEELS FOR LOW TEMPERATURE APPLICATIONS

Alloys for low temperature applications can be divided into two main groups. The first group are for those
intended for use in cold climates, such as Alaska and Siberia, where the temperature may go down to
about – 60°C. Carbon steels and HSLA steels can be used for such applications if the correct steps are
taken to meet impact properties. The second group are used in machines and equipment for manufacture,
transport and storage of liquefied gases. These are known as cryogenic alloys and operate at temperatures
below -150°C; such as -161°C for methane (LNG), -183°C for oxygen, -196°C for nitrogen and -253°C
for hydrogen. As well as operating satisfactorily at such temperatures, cryogenic metals also need to
operate at room temperature.
Strength generally increases with decreasing temperature, although ductility and toughness decrease.
Therefore, a low temperature material should have guaranteed strength at room temperature (since its
strength at lower temperatures will be higher) and guaranteed values of ductility and toughness at the
lowest temperature of operation. The strength, ductility and toughness of face-centered cubic metals all
improve as the temperature falls and such metals are ideal for use at low temperatures. Copper, nickel and
aluminum alloys are widely used for equipment operating below -100°C. Hexagonal close packed titanium
and its alloys with their high strength/weight ratio are used for low temperature aerospace applications.
However, extra low interstitial grades with very low levels of oxygen, carbon, nitrogen and iron must be
used for critical applications and oxygen must be kept away from titanium alloys as it causes severe
embrittlement. Austenitic stainless steels, again with an FCC structure with no ductile-brittle transition,
are perhaps the most important materials for cryogenic applications down to -270°C, ranging from use in
small research equipment to large storage tanks. However, their cost and low strength may limit
applications. Strength can be increased by cold working or cold rolling.
Generally, the most stable are those highest in nickel, such as Type 310 (25%Cr, 20%Ni). Most
other 300 series stainless steels can form small amounts of martensite at low temperatures during cold
working or thermal cycling, effecting dimensions and magnetic properties. Nitrogen-containing austenitic
steels appear more resistant to this problem and, with their higher strength, are especially desirable for
such applications.
Body centered cubic metals such as ferritic steels undergo a ductile-brittle transition at some
temperature below room temperature so selection has to be undertaken with care. The basic requirement
for their successful selection and use is that they have adequate toughness at their minimum operating
temperature so that they can not only withstand their design stresses but also any accidental impact or
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Ferrous Alloys Engineering Materials 4th. Year / 1st. Semester

other overload without failing in a catastrophic brittle manner. Grain refinement is the key to low
temperature impact properties of ferritic steels and micro-alloying, a high level of deoxidation (fully
killed), a high manganese-carbon ratio and controlled rolling are all desirable. A wide range of low carbon
and low alloy high strength steels can be used for low climatic temperature applications, such as bridges,
pipelines, storage tanks and offshore oil rigs. Carbon steels have better fabrication properties and
weldability than alloys steels and, with grain refinement, can be made to meet low temperature impact
requirements. However, their low strength limits applications, and high strength, low alloy steels are
usually specified for low temperature applications. Their low-cost per unit strength and good strength-
toughness relationship makes then popular. To meet toughness requirements down to -60°C or so will
require low sulphur content along with the grain refinement procedures mentioned earlier. Nickel-alloy
steels are most widely used at and below temperatures of around -60°C. Nickel will lower the ductile to
brittle transformation temperature and low carbon iron-nickel alloys are used for cryogenic applications
down to about -160°C. Figure 1-4 shows the beneficial effect of nickel on notch toughness of a series of
Charpy keyhole curves for a range of nickel steels.

Figure 1- 4 Effect of nickel content on the impact properties of several nickel steels.
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Table 2
Summary of characteristics and intended uses of HSLA steels described in ASTM specifications

ASTM Alloying
Title Available mill forms Special characteristics Applications
specification elements(a)

A 242 High-strength low- Cr, Cu, N, Ni, Plate, bar, and shapes Atmospheric-corrosion Structural members in
alloy structural steel Si, Ti, V, Zr ≤100 mm (4 in.) in resistance four times that of welded, bolted, or riveted
thickness carbon steel construction

A 588 High-strength low- Nb, V, Cr, Ni, Plate, bar, and shapes Atmospheric-corrosion Welded, bolted, or riveted
alloy structural steel Mo, Cu, Si, Ti, ≤200 mm (8 in.) in resistance four times that of structures, but primarily
with 345 MPa (50 ksi) Zr thickness carbon steel; nine grades of welded bridges and
minimum yield point similar strength buildings in which weight
≤100 mm (4 in.) in savings or added durability
thickness is important
A 633 Normalized high- Nb, V, Cr, Ni, Plate, bar, and shapes Enhanced notch toughness; Welded, bolted, or riveted
strength low-alloy Mo,,Si ≤150 mm (6 in.) in yield strengths of 290 to 415 structures for service at
structural steel thickness MPa (42 to 60 ksi) in five temperatures at or above
grades −45 °C (−50 °F)
A 690 High-strength low- Ni, Cu, Si Structural-quality H- Corrosion resistance two to Dock walls, sea walls,
alloy steel H-piles and piles and sheet piling three times greater than that of bulkheads, excavations,
sheet piling carbon steel in the splash zone and similar structures
of marine structures exposed to seawater
A 656 High-strength, low- V, Al, N, Ti, Si Plate, normally ≤16 Yield strength of 552 MPa (80 Truck frames, brackets,
alloy, hot-rolled mm (5/8 in.) in ksi) crane booms, rail cars, and
structural vanadium- thickness other application for which
aluminum- nitrogen weight savings is important
and titanium-
aluminum steels
A 714 High-strength low- V, Ni, Cr, Mo, Pipe with nominal Minimum yield strengths ≤345 Piping
alloy welded and Cu, Nb pipe size diameters of MPa (50 ksi) and corrosion
seamless steel pipe 13 to 660 mm (1/2 to resistance two to four times that
26 in.) of carbon steel
A 808 High-strength low- V , Nb Hot-rolled steel plate Charpy V-notch impact Railway tank cars
alloy steel with ≤65 mm (21/2 in.) in energies of 40–60 J (30–45 ft.-
improved notch thickness Ibl) at −45 °C (−50 °F)
toughness
A 841 Plate produced by V, Nb, Cr, Mo, Plates ≤100 mm (4 in.) Yield strengths of 310–345 Welded pressure vessels
thermomechanical Ni in thickness MPa (45–50 ksi)
controlled processes

A 860 High-strength butt- Cu, Cr, Ni, Mo, Normalized or Minimum yield strengths ≤485 High-pressure gas and oil
welding fittings of V, Nb, Ti quenched-and- MPa (70 ksi) transmission lines
wrought high-strength tempered wrought
low-alloy steel fittings
A 871 High-strength low- V, Nb, Ti, Cu, As-rolled plate ≤35 Atmospheric-corrosion Tubular structures and
alloy steel with Mo, Cr mm (13/8 in.) in resistance four times that of poles
atmospheric corrosion thickness carbon structural steel
resistance
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1.6.4 STAINLESS STEELS

Stainless steels are iron alloys which depend on a very thin, transparent, passive surface film of chromium
oxide to provide resistance to corrosion. This film will form, stay intact and repair in air and many
solutions at room temperature as long as two conditions are met:
1- The matrix material must have at least 11 per cent chromium dissolved in it.
2- There must be a ready supply of oxygen.
Stainless steels will exhibit excellent resistance to many corrosive environments. However, pitting
corrosion can arise due to localized loss of the passive film in the presence of chlorides and crevice
corrosion occurs in narrow fissures where access to oxygen is poor. Resistance to pitting corrosion
increases with increasing chromium, molybdenum and nitrogen content. Stress corrosion cracking arises
in austenitic stainless steels due to the combined influence of a chloride-containing environment, a tensile
stress and temperatures above about 60°C. Intergranular corrosion occurs when the grain boundaries
become depleted in chromium due to the formation of chromium carbides at temperatures between 550°C
and 850°C, a process known as sensitization. The most likely occurrence is due to welding where the
problem is known as weld decay and discussed with welding. In addition, high strength stainless steels
can suffer hydrogen embrittlement.
Dealing with these potential problems, along with the need to provide stainless steels with a range of
mechanical properties that can be fabricated by all types of manufacturing methods, has led to
development of numerous grades of stainless steels. Stainless steels are generally divided according to
their metallurgical structure.
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(a) (b)
Figure 1-5: (a) Iron-Chromium and (b) Iron-nickel phase diagrams.

1) Ferritic Stainless Steels

Typically contain 11 to 20 per cent chromium therefore consist of the ferrite (α) phase, with no phase
changes during heating and cooling. Figure 1-6 (a) shows a typical microstructure. They are magnetic,
cannot be hardened by heat treatment, and are hardened principally by cold working. They are mainly used
as sheet or coil in sizes up to 1.6 millimeters and rarely used for structural applications. The gamma loop
can be made smaller by addition of other ferrite formers, such as molybdenum and niobium. Also seen on
the phase diagram is the presence of sigma (σ) phase at about 50 per cent chromium. This is a brittle,
intermetallic compound and can cause problems in some alloys at high temperatures, discussed later.
Type 430 is the best-known ferritic stainless steel, contains about 16 per cent chromium and is used
for mildly corrosive conditions such as interior decoration, appliance trim and some moderate temperature
heat-resistant applications. Type 409 and 3CR12 or 5CR12 (trade names), with 11.5 per cent chromium are
sometimes referred to as ‘utility’ stainless steels and provide a lower cost material for use in less corrosive
conditions. These grades will usually contain titanium stabilizers to prevent sensitization during welding.

2) Martensitic Stainless Steels

A chromium stainless steel with a high carbon content can form austenite when heated to a sufficiently
high temperature. Quenching such an alloy result in the formation of martensite, in exactly the same manner
as carbon steels. So stainless steels with chromium and higher carbon contents can be transformed to
martensite. Figure 1-6 (b) shows a typical microstructure. With intermediate amounts of carbon, the amount
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of hardening is less since the transformation to austenite is incomplete, and the martensite contains less
carbon. Martensitic stainless steels have around 12 to 18 per cent chromium with little or no other alloy
elements and are magnetic. They have high mechanical strength and hardness, but limited corrosion
resistance and are difficult to weld.
The most common grade is Type 410 with 12.5 per cent chromium, and there is a free machining
version 410S (also known as 416) containing sulphur with lower corrosion resistance. Type 420 has a
similar chromium content but a higher carbon content so can achieve greater hardness and is used for
cutlery, surgical instruments and general engineering applications.

Figure 1-6 Microstructure of (a) ferritic stainless steels, (b) martensitic stainless steels

3) Austenitic Stainless Steels

The most common type of stainless steel. They typically have 17 to 20 per cent chromium and 8 to 22 per
cent nickel. Figure 1-7(a) shows a typical microstructure. Like ferritic alloys, these alloys will not undergo
phase changes on heating and cooling, and can only be hardened by cold working. Austenitic grades are
characterized by good ductility, reasonable strength, ease of formability, good weldability and good
corrosion resistance.
The 18/8 group, such as 301, 302 and 304 with approximately 18 per cent chromium and 8 per cent
nickel are the ‘basic’ type. They are used for a wide variety of applications such as kitchen sinks, tubs,
piping, vessels for food and chemical processing and indoor and outdoor architectural work. Carbide
precipitation which can result in intergranular corrosion is prevented in austenitic stainless steels by either
lowering the carbon content below 0.03 per cent (the "L" grades) or by adding carbide-forming elements
such as niobium (Type 347) or titanium (Type 321). Type 316 contains 2 to 3 per cent molybdenum and is
used in more severely corrosive conditions such marine atmospheres and food and chemical processing
applications. Higher alloyed austenitics (super austenitics) contain higher percentages of alloying elements
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and have better resistance to general, pitting and crevice corrosion as well as stress corrosion cracking
resistance.

Figure 1-7 Microstructure of (a) Austenitic stainless steels, (b) Duplex stainless steels

4) Duplex Stainless Steels

These grades have a chromium content from 18 to 28 per cent chromium and 4 to 8 per cent nickel.
This results in a structure that contains approximately equal amounts of austenite and ferrite as observed in
Figure 1-7(b). This gives them higher strength and better corrosion performance, especially resistance to
stress corrosion cracking, compared to the austenitic grades.
Alloy 2304 is a lower alloy duplex, with performance similar to 316, but resistance to stress corrosion
cracking. Alloy 2205 with 22 per cent chromium, 5.5 per cent nickel, 3 per cent molybdenum and a small
amount of nitrogen is the most widely used duplex alloy. ‘Super duplex’ grades such as 2507 contain high
amounts of chromium, molybdenum and nitrogen and have excellent pitting and crevice corrosion
resistance and used in severe marine applications.

5) Precipitation (or Age) Hardening (PH) Stainless Steels

These steels have elements such as copper or aluminum which form strengthening precipitates when
the material is heated to moderately elevated temperatures (ageing). They tend to be used for specialized
applications where the combination of high strength and reasonable corrosion resistance (about that of 304)
is required.
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Selection of the correct type of stainless steel to be used for a particular application requires knowledge of
the service conditions to which the steel will be subjected. Corrosion resistance is normally the most
important selection factor and generally the higher the alloy content, the better the corrosion resistance.
However, this also means a greater cost and more difficult fabrication, especially welding. It is important
therefore to select the optimum grade

Figure 1-8 Composition and property linkages in the stainless-steel family of alloy
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Table 3: Typical Applications for Austenitic, Ferritic, Martensitic, and precipitation hardenable Stainless
Steels
Type AISI APPLICATIONS
Number

304 Architecture [exterior & interior]; food processing; handling and serving
equipment; saucepans; hospital equipment; rainwater goods; household
appliances; domestic sinks and laundry troughs, general deep drawing
Austenitic applications; brewing and dairy equipment; evaporators; drums; barrels; heat
exchangers and refrigerator parts.

304 L Chemical plant; food processing equipment; and for use in coal and petroleum
industry.
310 Furnace parts and equipment, baffles; heat treatment; boxes; retorts; furnace
linings; heat exchangers.
316 Exterior applications subject to severe industrial or marine atmospheres;
chemical; textile; photographic and paper making equipment; wine vats.
316 L Chemical plant and food processing equipment.
409 Automotive exhaust components.
Ferritic
430 Interior architecture and automotive trim; domestic appliances; restaurant
equipment; stove and heater components.
410 Rifle barrels; cutlery and jet engine parts
Martensitic
440 A Cutlery; bearings and surgical tools

Precipitation 17-7PH Springs; knives and pressure vessels

Hardenable

1.7 CAST IRONS

Alloys of iron that have more than about 2 per cent of carbon are called cast irons. They are
relatively inexpensive and can be cast into intricate shapes because of their good fluidity and low melting
points. As with carbon steels, they can have a matrix of ferrite, pearlite, martensite or other steel phase
depending on composition but, apart from the white irons, most carbon is in the form of graphite. They
can be alloyed for improvement of corrosion resistance and strength.
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1.7.1 Grey cast irons

Grey cast irons contain from 2 to 4 per cent carbon and 1 to 3 per cent silicon and are the least
expensive of the engineering metals. The carbon is in the form of graphite flakes and, when fractured, the
exposed surface has a grey appearance. They possess excellent compressive strength and machinability,
good wear resistance and vibration dampening characteristics. Their main disadvantage is their brittleness.
Grey iron most applications are listed in table 4

1.7.2 White cast irons

White cast irons have a lower silicon content (usually less than 1 per cent) which results in
practically all their carbon in the form of iron carbide (Fe3C) rather than graphite in a pearlite matrix and,
as a result, give a white fracture appearance. These alloys are extremely hard, brittle and difficult to
machine and rarely used for engineering purposes. They are used for rolls, grinding equipment and other
purposes requiring abrasion resistance.

1.7.3 Malleable irons

Malleable irons are produced by heat treatment of white irons which results in cementite
decomposing into graphite in the form of clusters or rosettes, instead of flakes. This results in a material
with similar properties to grey irons but much improved ductility. The matrix can be ferritic or pearlitic.
Because of the additional processing, they are more expensive and largely replaced by ductile irons.

1.7.4 Ductile iron

Ductile iron (also known as spheroidal graphite (SG) or nodular iron) contains graphite present as
spheroids or nodules as a result of special treatment of the molten metal with cerium or magnesium. This
results in a stronger and more ductile material than grey iron. The mechanical properties can be altered by
heat treatment similar to ordinary steel. The combination of properties makes ductile iron a rather desirable
engineering material and it has replaced grey and malleable cast iron and steel castings in numerous
applications such as water pipes and automobile crankshafts.
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1.7.5 Compacted Graphite Iron

With silicon content ranges between 1.7 and 3.0 wt.%, and carbon concentration is normally
between 3.1 and 4.0 wt.%. Microstructurally, the graphite in CGI alloys has a worm-like (or vermicular)
shape; a typical CGI microstructure is shown in the optical micrograph of Figure 1-10.
In a sense, this microstructure is intermediate between that of gray iron and ductile (nodular) iron,
and, in fact, some of the graphite (less than 20%) may be as nodules. However, sharp edges (characteristic
of graphite flakes) should be avoided; the presence of this feature leads to a reduction in fracture and
fatigue resistance of the material. Magnesium and/or cerium is also added, but concentrations are lower
than for ductile iron. The chemistries of CGIs are more complex than for the other cast iron types;
compositions of magnesium, cerium, and other additives must be controlled so as to produce a
microstructure that consists of the worm-like graphite particles, while at the same time limiting the degree
of graphite nodularity, and preventing the formation of graphite flakes. Furthermore, depending on heat
treatment, the matrix phase will be pearlite and/or ferrite

Figure 1-9: Typical microstructures of cast irons: (a) ferritic grey, (b) white, (c) pearlitic malleable, (d) ferritic ductile
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Figure 1-10: Typical microstructures of compact graphite cast iron

1.8 ALLOY CAST IRON

Alloy cast irons are considered to be those casting alloys based on the iron-carbon-silicon system that
contain one or more alloying elements intentionally added to enhance one or more useful properties. Alloy
cast irons can be classified as white cast irons, corrosion-resistant cast irons, and heat-resistant cast irons.

1.8.1 Austenitic cast irons

Austenitic cast irons contain between 12 and 36 per cent nickel (with or without chromium and
copper) and have improved corrosion, abrasion and heat resistance and mechanical properties. They are
produced in flake and spheroidal graphite types. Austenitic irons (also known as the NiResist series) have
greatly increased corrosion resistance over the grey irons; for example, in flowing sea water the corrosion
resistance of a NiResist is ten times that of a grey or low alloy iron. Austenitic irons are used for valve
and pump bodies, and for condenser water boxes in refinery, marine and electricity generating systems.

1.8.2 High chromium irons

High chromium irons are basically white cast irons alloyed with 12 to 30 per cent chromium, where
the chromium confers greatly enhanced corrosion resistance. These grades are intended to provide
abrasion resistance under corrosive environments at high temperatures, and are used for impellers and
other moving parts of pumps handling corrosive and abrasive slurries.
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Table 4: Typical properties and uses of cast irons.

1.9 HEAT TREATMENTS

Most of the engineering properties of metals and alloys are related to their atomic structure, crystal
structure and microstructure. Mechanical properties are structure-sensitive in nature and their magnitude
depend largely on size, shape and distribution of various micro-constituents. Equilibrium microstructure
can be predicted for an alloy with the help of an equilibrium diagram. Mechanical properties can be
changed by varying the relative proportions of micro-constituents. In practice, change in mechanical
properties is achieved by a process known as heat treatment.Therefore, heat treatment may be defined as
heating and cooling operation(s) applied to metals and alloys in solid state so as to obtain the desired
properties.
Heat treatment of metals is an important operation in the final fabrication process of many
engineering components. The object of this process is to make the metal better suited, structurally and
physically, for some specific applications. Figure 11-1 shows the temperature range and heat treatment
processes.
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Figure 1-11 : Heat treatment range of carbon steel

HEAT TREATMENT PROCESSES

According to cooling rate we can distinguish three main heat treatment operations:
• Annealing – upon slow cooling rate (in a furnace)
• Normalizing – upon medium cooling (in air)
• Hardening – upon fast cooling (in oil or in water)
• Tempering

1.10 ANNEALING
Annealing, in general, involves heating to a predetermined temperature, holding at this temperature,
and finally cooling at a very slow rate. The temperature, to which steel is heated, and the holding time are
determined by various factors such as the chemical composition of steel, size and shape of steel component
and final properties desired. Depending on the specific purpose, annealing is classified into various types:
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A) Full Annealing : This operation remove all structural imperfections by complete recrystallization.
This operation is often utilized in low and medium carbon steel that will be machined or will
experience extensive plastic deformation during a forming operation. This operation consist of :
• Heating the hypoeutectoid steel to about 30-50 oC above the upper critical temperature and
by the same temperature above the lower critical temperature for hypereutectoid steels until
equilibrium is achieved. This ensure that the metal is heated thoroughly and phase
transformation has taken place throughout the whole volume.
• The alloy is then furnace cooled; i.e., the heat treating furnace is turned off and both furnace
and steel cool to room temperature at the same rate, which takes several hours. The
microstructure product of full anneal is coarse pearlite,(in addition to any or phase) that is
relatively soft and ductile.
B) Process Annealing (Recrystallization Annealing-Eliminating Cold Work): This is a heat
treatment that is used to negotiate the effects of cold work, i.e. to soften and increasing the ductility
of previously strain hardening metal. The process is as follows:
• The steel is heated to a temperature just below the lower critical temperature on iron-
carbon diagram for steel.
• Stresses throughout the metal are relived and recrystallization causes new grain to form
and grow. Heating period is followed by slow cooling .
C) Stress-Relief Annealing: Internal residual stresses may develop in metal pieces due to Plastic
deformation processes such as cold working processes, Non uniform cooling of piece that was
processes or fabricated at an elevated temperature, such as a weld or a casting; and a phase
transformation that is induced upon cooling where in parent and product phases have different
densities. They can be eliminated by this process in which, the piece is heated to the recommended
temperature , held there long enough to attain a uniform temperature, and finally cooled to room
temperature in air.
D) Spheroidizing: Tool steels for cutting tools, measuring instruments and cold forming dies have a
high concentration of carbon (0.7% of carbon and higher) which provides high hardness and makes
these steels poorly machinable. spheroidizing annealing of hypereutictoid steels prepares their
structure to hardening. This type of heat treatment produces carbide in the form of round or
globular(spheroids) instead of plate as in pearlit. This structure gives; good machinability, high
ductility and improvement in formability. The spheroidizing heat treatment consist of heating the
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alloy at a temperature just below the eutectoid phase diagram (line A1 or at about 700 oC) in the
(alpha+ Fe3C) region of the phase diagram. If the precursor microstructure contains pearlite,
spheroidizing times will ordinarily range between 15 and 25 hours.
1.11 NORMALIZING
This is used as a finishing treatment for carbon steel giving higher strength than annealing. There is
no serious los of ductility too. Heating and soaking in this process is same as in the full annealing but part
is allowed to cool in air so that cooling rate is faster. A normalizing treatment is used to refine the grains
(i.e., to decrease the average grain size) and produce a more uniform and desirable size distribution. Fine
grained pearlite steels are tougher than coarse-grained ones.
Normalizing is accomplished by heating at approximately to 30-50 oC above the upper critical temperature
in both hypo and hyper eutectoid steels.
Normalizing often applied to casting and forgings is stress relieving process. To same extent, it
increases strength of medium carbon steel. It improve machinability , when applied to low carbo steel.
Alloy steel in which the austenite a procedure termed austenizing is very stable can be normalized to
produce hard martensite structure.

Figure 1-12: Schematic summary of the simple heat treatments for (a) hypoeutectoid steels and (b) hypereutectoid steels
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Figure 1-13:The effect of carbon and heat treatment on the properties of plain carbon steels.

1.12 TRANSFORMATION OF AUSTENITE

Thus far the discussion has been confined to heating of the steel and the phases that result from various
combinations of temperature and carbon content. Now what happens when the alloy is cooled? Referring
to Figure (1-2) (iron-iron carbide phase diagram) , assume that a steel containing 0.50% C is heated to 815
o
C (1500 oF). All of the carbon will be dissolved (assuming, of course, that holding time is sufficient).
Under these conditions, all of the carbon atoms will dissolve in the interstices of the FCC crystal. If the
alloy is cooled slowly, transformation to the BCC or alpha phase begins when the temperature drops below
approximately 790 oC (1450 oF). As the temperature continues to decrease, the transformation is
essentially complete at 725 oC (1340 oF). During this transformation, the carbon atoms escape from the
lattice because they are essentially insoluble in the alpha crystal (bcc). Thus, in slow cooling, the alloy for
all practical purposes, returns to the same state (in terms of phase) that it was before heating to form
austenite. The same mechanism occurs with higher carbon steels, except that the austenite-to-ferrite
transformation does not go through a two-phase zone (Figure 1-2 ( Fe-Fe3C diagram)). A magnetic change
occurs at 770 oC.
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What happens when the alloy is cooled rapidly? When the alloy is cooled suddenly, the carbon
atoms cannot make an orderly escape from the iron lattice. This cause “atomic bedlam” and results in
distortion of the lattice, which manifests itself in the form of hardness and/or strength. If cooling is fast
enough, a new structure known as martensite is formed, although this new structure (an aggregate of iron
and cementite) is in the alpha phase.

Figure 1-14 Schematic representation of the formation of pearlite from austenite; direction of carbon diffusion indicated by
arrows

Figure 1-15 Effects of carbon content on the microstructures of plain-carbon steels. (a) Ferrite grains (white) and pearlite (gray streaks) in a
white matrix of a hypoeutectoid steel containing 0.4% C. 1000 X. (b) Microstructure (all pearlite grains) of a eutectoid steel containing
0.77% C. 2000X. (c) Microstructure of a eutectoid steel containing 0.77% C with all cementite in the spheroidal form. 1000X. (d)
Microstructure of a hypereutectoid steel containing ~1.0% C containing pearlite with excess cementite bounding the grains. 1000X.
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1.13 ISOTHERMAL TRANSFORMATION (TTT Digram) :

The foregoing discussion has been confined principally to phases that are formed by various
combinations of composition and temperature; little reference has been made to the effects of time. In
order to convey to the reader the effects of time on transformation, the simplest approach is by means of
a time-temperature-transformation (TTT) curve for some constant iron-carbon composition.
Such a curve is presented in Fig.16 for a 0.8% (eutectoid) carbon steel. TTT curves are also known as “S”
curves because the principal part of the curve is shaped like the letter “S.” In Figure 1-16, temperature is
plotted on the vertical axis, and time is plotted on a logarithmic scale along the horizontal axis. The reason
for plotting time on a logarithmic scale is merely to keep the width of the chart within a manageable
dimension.

Figure 1-16: Time-temperature-transformation (TTT) diagram for eutectoid(0.8%) carbon steel.

1.14 CONTINUOUS-COOLING TRANSFORMATION DIAGRAMS (CTT)

Most heat treatments for steels involve the continuous cooling of a specimen to room temperature.
An isothermal transformation diagram is valid only for conditions of constant temperature; this diagram
must be modified for transformations that occur as the temperature is constantly changing. For continuous
cooling, the time required for a reaction to begin and end is delayed. Thus the isothermal curves are shifted
to longer times and lower temperatures, as indicated in Figure 1-17 for an iron– carbon alloy of eutectoid
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composition. A plot containing such modified beginning and ending reaction curves is termed a
continuous-cooling transformation (CCT) diagram.

Figure 1-17 : Superimposition of isothermal and continuous-cooling transformation diagrams for a eutectoid iron–carbon
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Ferrous Alloys Engineering Materials 4th. Year / 1st. Semester

1.15 Hardening (Quenching) and Tempering :

Certain applications demand high tensile strength and hardness values so that the components may be
successfully used for heavy duty purposes. High tensile strength and hardness values can be obtained by
a process known as hardening. Hardening treatment consists of heating to a predetermined temperature,
usually known as hardening temperature (see Figure 1-11), holding at that temperature, followed by rapid
cooling such as quenching in water, oil or salt baths. The high hardness developed by this process is due
to the phase transformation accompanying rapid cooling. The term rapid cooling simply does not mean
that cooling rate is higher than that adopted in annealing and normalizing. What it really means is that
cooling rate is equal to or more than the upper critical cooling rate. Rapid cooling results in the
transformation of austenite at considerably low temperatures into non-equilibrium product. The product
of low temperature transformation of austenite is martensite which is a hard micro-constituent of steel.
The term hardening by quenching is used for this process in order to differentiate it from other hardening
processes.
Because of rapid cooling, high internal stresses are developed in the hardened steel. Therefore,
hardened parts are seldom used in as-hardened condition. Also, in hardened condition, steels are generally
brittle. Hardening, in general, is always followed by another treatment known as tempering which reduces
internal stresses and makes the hardened steel relatively stable. Hardening followed by tempering results
in improved wear resistance, optimum combination of strength and ductility and enhanced elastic
characteristics.

Figure 1-18: The effect of tempering temperature on the mechanical properties of a 1050 steel.