Engineering Materials

Ferrous Alloys

1- Introduction

Metallic materials are normally combinations of metallic elements. Metals are

extremely good conductors of electricity and heat and are not transparent to visible
light; a polished metal surface has a lustrous appearance. Furthermore, metals are
quite strong, yet deformable, which accounts for their extensive use in structural
applications.

Engineering metals are generally alloys, alloys being metallic materials formed by
mixing two or more elements. For example, mild steel is an alloy of iron and
carbon, stainless steel an alloy of iron, chromium, carbon, manganese, and other
elements. The reason for adding elements to the iron is to improve the properties
since pure metals are weak materials. The carbon improves the strength of the iron,
and the chromium in stainless steel improves the corrosion resistance.

2- Ferrous alloys

Ferrous alloys those in which iron is the prime constituent are produced in larger
quantities than any other metal type. They are especially important as engineering
construction materials. Their widespread use is accounted for by three factors: (1)
iron-containing compounds exist in abundant quantities within the earth’s crust; (2)
metallic iron and steel alloys may be produced using relatively economical
extraction, refining, alloying, and fabrication techniques; and (3) ferrous alloys are
extremely versatile, in that they may be tailored to have a wide range of
mechanical and physical properties. The principal disadvantage of many ferrous
alloys is their susceptibility to corrosion. This section discusses compositions,

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microstructures, and properties of a number of different classes of steels and cast
irons.

2.1 Steels

Steels are iron–carbon alloys that may contain appreciable concentrations of other
alloying elements; there are thousands of alloys that have different compositions
and/or heat treatments. The dividing point between “steels” and “cast irons” is
about 2.1% C, where the eutectic reaction becomes possible. For steels, we
concentrate on the eutectoid portion of the diagram (Figure 1) in which the
solubility lines and the eutectoid isotherm are specially identified. The A3 shows
the temperature at which ferrite starts to form on cooling; the Acm shows the
temperature at which cementite starts to form; and the A1 is the eutectoid
temperature.

Almost all of the heat treatments of steel are directed toward producing the mixture
of ferrite and cementite that gives the proper combination of properties. Pearlite is
a microconstituent consisting of a lamellar mixture of ferrite and cementite. The
mechanical properties are sensitive to the content of carbon.

2.1.1 Carbon Steels:

Carbon steels contain trace amounts of alloying elements and account for 90% of
total steel production. Carbon steels can be further categorized into three groups
depending on their carbon content:

 Low Carbon Steels/Mild Steels contain up to 0.25% carbon.

 Medium Carbon Steels contain 0.3% to 0.6% carbon.

 High Carbon Steels contain between 0.60 and about 1.4 wt. % C carbon.

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  Ultra-high carbon steel contain between 1.4% up to 2.1% carbon.

Subclasses also exist within each group according to the concentration of other
alloying elements. Plain carbon steels contain only residual concentrations of
impurities other than carbon and a little manganese. For alloy steels, more alloying
elements are intentionally added in specific concentrations.

Figure (1) Fe-C Diagram

Low-Carbon Steels: Of the different steels, those produced in the greatest

quantities fall within the low-carbon classification. These generally contain less
than about 0.25 wt. % C and are unresponsive to heat treatments intended to form
martensite; strengthening is accomplished by cold work. Microstructures consist of
ferrite and pearlite constituents. As a consequence, these alloys are relatively soft
and weak but have outstanding ductility and toughness; in addition, they are

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machinable, weldable, and, of all steels, are the least expensive to produce. Typical
applications include automobile body components, structural shapes (I-beams,
channel and angle iron), and sheets that are used in pipelines, buildings, bridges,
and tin plated cans. They typically have yield strength of 275 MPa, tensile
strengths between 415 and 550 MPa, and a ductility of 25%EL.

Medium-Carbon Steels: The medium-carbon steels have carbon concentrations

between about 0.25 and 0.60 wt. % C. These alloys may be heat-treated by
austenitizing, quenching, and then tempering to improve their mechanical
properties. They are most often utilized in the tempered condition, having
microstructures of tempered martensite. The plain medium-carbon steels have low
hardenability and can be successfully heat-treated only in very thin sections and
with very rapid quenching rates. Additions of chromium, nickel, and molybdenum
improve the capacity of these alloys to be heat-treated, giving rise to a variety of
strength–ductility combinations. These heat-treated alloys are stronger than the low
carbon steels, but at a sacrifice of ductility and toughness. Applications include
railway wheels and tracks, gears, crankshafts, and other machine parts and high-
strength structural components calling for a combination of high strength, wear
resistance, and toughness.

High-Carbon Steels: The high-carbon steels, normally having carbon contents

between 0.60 and about 1.4 wt. % C, are the hardest, strongest, and yet least ductile
of the carbon steels. They are almost always used in a hardened and tempered
condition and, as such, are especially wear resistant and capable of holding a sharp
cutting edge. The tool and die steels are high carbon alloys, usually containing
chromium, vanadium, tungsten, and molybdenum. These alloying elements
combine with carbon to form very hard and wear-resistant carbide compounds
(e.g., Cr23C6, V4C3, and WC). These steels are used as cutting tools and dies for

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forming and shaping materials, as well as in knives, razors, hacksaw blades,
springs, and high-strength wire.

Ultra high-carbon steel: Composition up to 2.1% carbon is known as very-high

carbon steel. Its ultra-high carbon content makes it an extremely strong material,
but because of this high content of carbon it has high hardenability, so, event at
slow cooling, austenite will transform to very brittle phase called “martensite” (M)
when crossing (A1) temperature line. Due to its brittleness, this grade has limited
applications.

Phases in Steel: (slow cooling)

Ferrite (α)

 solid solution of carbon in iron

 BCC structure
 carbon only slightly soluble in the matrix
 maximum solubility of 0.02%C at 723°C to about 0.008%C at room
temperature.
 soft, ductile and relatively low strength phase.

Austenite (γ)

 solid solution of carbon in iron

 FCC structure: can accommodate more carbon than ferrite
 maximum of 2.08%C at 1148°C, decreases to 0.8%C at 723°C

Difference in Carbon solid solubility between γ and α is the basis for hardening of
most steels.

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Delta (δ) iron

 solid solution of carbon in δ−iron

 BCC crystal structure
 maximum solubility of ferrite being 0.09%C at 1495°C

Cementite (Fe3C)

 metastable intermetallic (Fe-C) compound

 Fe3C : (6.67%C and 93.3%Fe by weight).
 orthorhombic crystal structure
 strong, hard, and brittle

Pearlite (P)

 A fine mixture of ferrite and cementite arranged in lamellar form. It is stable

at all temperatures below 723o C.
 strong, tough, and relatively ductile

Eutectoid steel has a eutectoid composition (about 0.76% carbon), the austenite
transform totally to pearlite (when cooled slowly below A1). Steel with
composition less than 0.76% C is called hypoeutectoid, and the austenite changes
to (austenite + ferrite) when cooled below A3, and changes to (pearlite + ferrite)
below A1. Steel with composition more than 0.76% C called hypereutectoid and
the austenite changes to (austenite + ferrite) when cooled below Acm, and changes
to (pearlite + cementite) below A1. As illustrated in figure (2).

Martensitic transformation: (rapid cooling)

Sufficiently rapid cooling of austenite containing carbon will prevent the formation
of ferrite + cementite which would happen with adequately slow cooling, i.e. if the

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diffusion of carbon atoms is allowed. The carbon atoms soluted in austenite remain
trapped, causing the tetragonal distortion of the bcc lattice and the formation of a
very hard metastable phase: martensite, BCT (body centered tetragonal).

Figure (2). A. Eutectoid transformation. B. Hypoeutectoid

transformation. C. Hypereutectoid transformation.

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2.1.2 Alloy Steels:

Alloy steels contain alloying elements (e.g. manganese, silicon, nickel, titanium,
copper, chromium and aluminum) in varying proportions in order to manipulate
the steel's properties, such as its hardenability, corrosion resistance, strength,
formability, weldability or ductility. Applications for alloys steel include pipelines,
auto parts, transformers, power generators, electric motors …etc.

2.1.2.1 Stainless Steels:

Stainless steels generally contain between 10-20% chromium as the main alloying
element and are valued for high corrosion resistance. With over 11% chromium,
steel is about 200 times more resistant to corrosion than mild steel. These steels
can be divided into three groups based on their crystalline structure:

Austenitic: Austenitic steels are non-magnetic and non heat-treatable, and

generally contain 18% chromium, 8% nickel and less than 0.8% carbon. Austenitic
steels form the largest portion of the global stainless steel market and are often
used in food processing equipment, kitchen utensils and piping.

Ferritic: Ferritic steels contain trace amounts of nickel, 12-17% chromium, less
than 0.1% carbon, along with other alloying elements, such as molybdenum,
aluminum or titanium. These magnetic steels cannot be hardened with heat
treatment, but can be strengthened by cold working.

Martensitic: Martensitic steels contain 11-17% chromium, less than 0.4% nickel
and up to 1.2% carbon. These magnetic and heat-treatable steels are used in knives,
cutting tools, as well as dental and surgical equipment.

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2.1.2.2 Maraging Steels

Maraging steels are iron-nickel alloys (about 18% Ni) and with additions of
cobalt, molybdenum, titanium and aluminium. The term maraging is derived from
the strengthening mechanism, which is transforming the alloy to martensite with
subsequent age hardening ("martensitic" and "aging").

With yield strength between 1400 and 2400 MPa maraging steels belong to the
category of ultra-high-strength materials. The high strength is combined with
substantially greater resistance to oxidation in air at high temperatures. Maraging
steels are known for possessing superior strength and toughness without losing
malleability, and excellent toughness properties and weldability.

2.1.2.3 Dual Phase Steels

Dual-phase steel (DPS) is an ultra-high-strength steel that has a ferrite and

martensitic microstructure. DPS starts as a low or medium carbon steel and is
quenched from a temperature above A1 but below A3 on a continuous cooling
transformation diagram. This results in a microstructure consisting of a soft ferrite
matrix containing islands of martensite as the secondary phase (martensite
increases the tensile strength). For achieving these microstructures, DPS typically
contain 0.06–0.15 wt.% C and 1.5-3% Mn, Cr , Mo, V and Nb. DPS have high
ultimate tensile strength with high ductility. These features render DPS ideal
materials for automotive-related sheet forming operations.

2.1.2.4 Interstitial-Free Steels

Alloy steel containing very low content of carbon. The Added alloying elements
(Ti/Nb) will react with residual carbon and sulfur to form carbides and sulfides,

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and leave the ferrite virtually free from carbon. The ductility of steel will increase
substantially and it is has best applications in automobiles industries.

2.2 Cast Irons

Generically, cast irons are a class of ferrous alloys with carbon contents above 2.14
wt.%; in practice, however, most cast irons contain between 3.0 and 4.5 wt% C
and, in addition, other alloying elements. A reexamination of the iron–iron carbide
phase diagram Figure (1) reveals that alloys within this composition range become
completely liquid at temperatures between approximately 1150 ºC and 1300 ºC,
which is considerably lower than for steels. Thus, they are easily melted and
amenable to casting. Furthermore, some cast irons are very brittle, and casting is
the most convenient fabrication technique.

Cementite (Fe3C) is a metastable compound, and under some circumstances it can

be made to dissociate or decompose to form α-ferrite and graphite, according to the
reaction (1)

Fe3C → 3Fe (α) + C (graphite) ….. (1)

This tendency to form graphite is regulated by the composition and rate of cooling.
Graphite formation is promoted by the presence of silicon in concentrations greater
than about 1 wt% Si. Also, slower cooling rates during solidification favor
graphitization (the formation of graphite). For most cast irons, the carbon exists as
graphite, and both microstructure and mechanical behavior depend on composition
and heat treatment. The most common cast iron types are gray, nodular, white,
malleable, and compacted graphite.

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Silicon also reduces the amount of carbon contained in the eutectic. We can take
this effect into account by defining the carbon equivalent (CE):

CE = C % + 1/3 Si % ………..… (2)

The eutectic composition is always near 4.3% CE. A high carbon equivalent
encourages the growth of the graphite eutectic. Also, slower cooling rates during
solidification favor graphitization (the formation of graphite).

Example: you would like to produce a gray iron casting with carbon equivalent of
4.3. If the carbon content in the iron is 3.5%, what percentage of silicon must you
add?

Answer: CE = C % + 1/3 Si % . . . . (Complete it).

For most cast irons, the carbon exists as graphite, and both microstructure and
mechanical behavior depend on composition and heat treatment. The most
common cast iron types are gray, nodular, white, and malleable.

2.2.1 Gray Iron

The carbon and silicon contents of gray cast irons vary between 2.5 and 4.0 wt% C
and 1.0 and 3.0 wt% Si, respectively. For most of these cast irons, the graphite
exists in the form of flakes (similar to corn flakes), which are normally surrounded
by an α-ferrite or pearlite matrix; the microstructure of a typical gray iron is shown
in Figure (3). Because of these graphite flakes, a fractured surface takes on a gray
appearance hence its name.

Mechanically, gray iron is comparatively weak and brittle in tension as a

consequence of its microstructure; the tips of the graphite flakes are sharp and

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pointed and may serve as points of stress concentration when an external tensile
stress is applied. Strength and ductility are much higher under compressive loads.

Gray irons have some desirable characteristics and are used extensively. They are
very effective in damping vibrational energy. Base structures for machines and
heavy equipment that are exposed to vibrations are frequently constructed of this
material. In addition, gray irons exhibit a high resistance to wear. Furthermore, in
the molten state they have a high fluidity at casting temperature, which permits
casting pieces that have intricate shapes; also, casting shrinkage is low. Finally,
and perhaps most important, gray cast irons are among the least expensive of all
metallic materials.

2.2.2 Ductile (or Nodular) Iron

Adding a small amount of magnesium (Mg) and/or cerium (Ce) to the gray iron
before casting produces a distinctly different microstructure and set of mechanical
properties. Graphite still forms, but as nodules or sphere like particles instead of
flakes. The resulting alloy is called nodular or ductile iron, and a typical
microstructure is shown in Figure (3). The matrix phase surrounding these particles
is either pearlite or ferrite, depending on heat treatment Figure (3); it is normally
pearlite for an as-cast piece. However, a heat treatment for several hours at about
700 ºC will yield a ferrite matrix. In fact, ductile iron has mechanical characteristics
approaching those of steel. For example, ferritic ductile irons have tensile strengths
between 380 and 480 MPa and ductilities (as percent elongation) from 10% to
20%. Typical applications for this material include valves, pump bodies,
crankshafts, gears, and other automotive and machine components.

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2.2.3 White Iron

For low-silicon cast irons (containing less than 1.0 wt% Si) and rapid cooling rates,
most of the carbon exists as cementite instead of graphite, as indicated in Figure
(3). A fracture surface of this alloy has a white appearance, and thus it is termed
white cast iron. Thick sections may have only a surface layer of white iron that was
“chilled” during the casting process; gray iron forms at interior regions, which cool
more slowly. As a consequence of large amounts of the cementite phase, white iron
is extremely hard but also very brittle, to the point of being virtually unmachinable.
Its use is limited to applications that necessitate a very hard and wear-resistant
surface, without a high degree of ductility for example, as rollers in rolling mills.
Generally, white iron is used as an intermediary in the production of yet another
cast iron, malleable iron.

2.2.4 Malleable Iron

Heating white iron at temperatures between 800 ºC and 900 ºC for a prolonged time
period and in a neutral atmosphere (to prevent oxidation) causes a decomposition
of the cementite, forming graphite, which exists in the form of clusters or rosettes
surrounded by a ferrite or pearlite matrix, depending on cooling rate, as indicated
in Figure (3). Ferritic malleable irons have relatively high strength and appreciable
ductility or malleability. Representative applications include connecting rods,
transmission gears, and differential cases for the automotive industry, and also
flanges, pipe fittings, and valve parts for railroad, marine, and other heavy-duty
services.

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2.2.5 Compacted Graphite Iron

A relatively recent addition to the family of cast irons is compacted graphite iron
(abbreviated CGI). As with gray, ductile, and malleable irons, carbon exists as
graphite, whose formation is promoted by the presence of silicon. Silicon content
ranges between 1.7 and 3.0 wt%, whereas carbon concentration is normally
between 3.1 and 4.0 wt%.

Microstructurally, the graphite in CGI alloys has a wormlike (or vermicular) shape.
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. Compositions of magnesium,
cerium, and other additives must be controlled so as to produce a microstructure
that consists of the wormlike 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.

As with the other types of cast irons, the mechanical properties of CGIs are related
to microstructure: graphite particle shape, as well as the matrix
phase/microconstituent. An increase in degree of nodularity of the graphite
particles leads to enhancements of both strength and ductility. Furthermore, CGIs
with ferritic matrices have lower strengths and higher ductilities than those with
pearlitic matrices. Tensile and yield strengths for compacted graphite irons are
comparable to values for ductile and malleable irons yet are greater than those

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observed for the higher-strength gray irons. In addition, ductilities for CGIs are
intermediate between values for gray and ductile irons. Compared to the other cast
iron types, desirable characteristics of CGIs include the following:

• Higher thermal conductivity

• Better resistance to thermal shock (i.e., fracture resulting from rapid temperature
changes)

• Lower oxidation at elevated temperatures

Compacted graphite irons are now being used in a number of important

applications, including diesel engine blocks, exhaust manifolds, gearbox housings,
brake discs for high-speed trains, and flywheels.

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Figure (3). From the iron–carbon phase diagram, composition ranges for commercial cast
irons. Also shown are schematic microstructures that result from a variety of heat
treatments. Gf, flake graphite; Gr, graphite rosettes; Gn, graphite nodules; P, pearlite; α,
ferrite.

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