Engineering Materials Ferrous Alloys

CHAPTER ONE
FERROUS ALLOYS
The ferrous alloys are based on iron, one of the oldest metals known to humans. The properties and
other data relating to iron are listed in Table 1(a).
TABLE 1 Basic data on the metallic elements: (a) Iron.
Symbol: Fe Principal ore: Hematite (Fe2O3)
Atomic number: 26 Alloying elements: Carbon; also chromium, manganese,
Specific gravity: 7.87 nickel, molybdenum, vanadium, and
Crystal structure: BCC silicon
Melting temperature: 1539○C Typical applications: Construction, machinery,
Elastic modulus: 209,000 MPa automotive, railway tracks and
equipment

Ferrous alloys 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. These
alloys divide into two major groups: steel and cast iron. A taxonomic classification scheme for the
various ferrous alloys is presented in Figure 1.

Figure 1 Classification scheme for the various ferrous alloys.

 THE IRON–CARBON PHASE DIAGRAM

The iron–carbon phase diagram is shown in Figure 2. Pure iron melts at 1538℃. During the rise in
temperature from ambient, it undergoes several solid phase transformations, as indicated in the
diagram. Starting at room temperature the phase is alpha (α), also called ferrite. At 912℃, ferrite
transforms to gamma (γ), called austenite. This, in turn, transforms at 1394 ℃ to delta (δ), which

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remains until melting occurs. The three phases are distinct; alpha and delta have body-centered cubic
(BCC) lattice structures, and between them, gamma is face-centered cubic (FCC).

Figure 2 The iron–iron carbide phase diagram.

Solubility limits of carbon in iron are low in the ferrite phase—only about 0.022% at 727 ℃. Austenite
can dissolve up to about 2.14% carbon at a temperature of 1147 ℃. This difference in solubility
between alpha and gamma leads to opportunities for strengthening by heat treatment. Even without
heat treatment, the strength of iron increases dramatically as carbon content increases, and the metal is
called steel. More precisely, steel is defined as an iron–carbon alloy containing from 0.02% to 2.14%
carbon. A eutectic composition at 4.3% carbon can be seen in the diagram. There is a similar feature in
the solid region of the diagram at 0.76% carbon and 727℃. This is called the eutectoid composition.
Steels below this carbon level are known as hypoeutectoid steels, and above this carbon level, from
0.76% to 2.14%, they are called hypereutectoid steels. In addition to the phases mentioned, one other
phase is prominent in the iron–carbon alloy system. This is Fe3C, also known as cementite, an
intermediate phase. It is a metallic compound of iron and carbon that is hard and brittle. Cast irons are
classified as ferrous alloys that contain between 2.14 and 6.70 wt% C. However, commercial cast irons
normally contain less than 4.5 wt% C.

 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. Some of the more
common steels are classified according to carbon concentration into low-, medium-, and high-carbon
types. 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.
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

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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 machinable, weldable, and, of all steels, are the least
expensive to produce. Typical applications include automobile body components, structural shapes,
and sheets that are used in pipelines, buildings, bridges, and tin cans.
Medium-carbon steels
The medium-carbon steels have carbon concentrations between about 0.25 and 0.60 wt%. They are
specified for applications requiring higher strength than the low-C steels. Applications include
machinery components and engine parts such as crankshafts and connecting rods.
High-carbon steels
The high-carbon steels have carbon contents between 0.60 and 1.4 wt%. They are specified for still
higher strength applications and where stiffness and hardness are needed. Springs and cutting tools,
and wear-resistant parts are examples. Increasing carbon content strengthens and hardens the steel, but
its ductility is reduced. Also, high carbon steels can be heat treated to form martensite, making the steel
very hard and strong.

 HEAT TREATMENT
Heat treatment involves various heating and cooling procedures performed to effect microstructural
changes in a material, which in turn affect its mechanical properties. Heat treatment operations can be
performed on a metallic workpart at various times during its manufacturing sequence. In some cases,
the treatment is applied before shaping (e.g., to soften the metal so that it can be more easily formed
while hot). In other cases, heat treatment is used to relieve the effects of strain hardening that occur
during forming, so that the material can be subjected to further deformation. Heat treatment can also
be accomplished at or near the end of the sequence to achieve the final strength and hardness required
in the finished product. The principal heat treatments are annealing, martensite formation in steel,
precipitation hardening, and surface hardening.
Annealing consists of heating the metal to a suitable temperature, holding at that temperature for a
certain time (called soaking), and slowly cooling. Different terms are used in annealing, depending on
the details of the process and the temperature used relative to the recrystallization temperature of the
metal being treated. Figure 3 shows the portion of the iron–iron carbide phase diagram in the vicinity
of the eutectoid. The horizontal line at the eutectoid temperature, conventionally labeled A1, is termed
the lower critical temperature, below which, under equilibrium conditions, all austenite has
transformed into ferrite and cementite phases. The phase boundaries denoted as A3 and Acm represent
the upper critical temperature lines for hypoeutectoid and hypereutectoid steels, respectively. For
temperatures and compositions above these boundaries, only the austenite phase prevails.
Steels that have been plastically deformed by, for example, a rolling operation, consist of grains of
pearlite, which are irregularly shaped and relatively large and vary substantially in size. An annealing
heat treatment called normalizing is used to refine the grains (i.e., to decrease the average grain size)
and produce a more uniform and desirable size distribution. Normalizing is accomplished by heating
at least 55℃ above the upper critical temperature—that is, above A3 for compositions less than the
eutectoid (0.76 wt% C), and above Acm for compositions greater than the eutectoid. After sufficient
time has been allowed for the alloy to completely transform to austenite, the treatment is terminated by
cooling in air.

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A heat treatment known as full annealing is often used in low- and medium-carbon steels that will be
machined or will experience extensive plastic deformation during a forming operation. In general, the
alloy is treated by heating to a temperature of about 50℃ above the A3 line (to form austenite) for
compositions less than the eutectoid, or, for compositions in excess of the eutectoid, 50℃ above the A1
line (to form austenite and Fe3C phases). The alloy is then furnace cooled—that is, 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 full-anneal cooling procedure is time consuming; however, a microstructure having
small grains and a uniform grain structure results.

Figure 3 The iron–iron carbide phase diagram in the vicinity of the eutectoid, indicating heat-treating
temperature ranges for plain carbon steels.

Martensite Formation in Steel

The iron–carbon phase diagram in Figure 2 indicates the phases of iron and iron carbide (cementite)
present under equilibrium conditions. It assumes that cooling from high temperature is slow enough to
permit austenite to decompose into a mixture of ferrite and cementite (Fe3C) at room temperature. This
decomposition reaction requires diffusion and other processes that depend on time and temperature to
transform the metal into its preferred final form. However, under conditions of rapid cooling, so that
the equilibrium reaction is inhibited, austenite transforms into a nonequilibrium phase called
martensite. Martensite is a hard, brittle phase that gives steel its unique ability to be strengthened to
very high levels.
The successful heat treating of steels to produce a predominantly martensitic microstructure throughout
the cross section depends mainly on three factors: (1) the composition of the alloy, (2) the type and
character of the quenching medium, and (3) the size and shape of the specimen.
Severity of quench is a term often used to indicate the rate of cooling; the more rapid the quench, the
more severe is the quench. Of the three most common quenching media—water, oil, and air—water
produces the most severe quench, followed by oil, which is more effective than air. As far as specimen
shape is concerned, because the heat energy is dissipated to the quenching medium at the specimen
surface, the rate of cooling for a particular quenching treatment depends on the ratio of surface area to
the mass of the specimen. The larger this ratio, the more rapid is the cooling rate and, consequently, the
deeper is the hardening effect. Irregular shapes with edges and corners have larger surface-to-mass
ratios than regular and rounded shapes (e.g., spheres and cylinders) and are thus more amenable to
hardening by quenching.

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 LOW ALLOY STEELS

Low alloy steels are iron–carbon alloys that contain additional alloying elements in amounts totaling
less than about 5% by weight. Owing to these additions, low alloy steels have mechanical properties
that are superior to those of the plain carbon steels for given applications. Superior properties usually
mean higher strength, hardness, wear resistance, toughness, and more desirable combinations of these
properties. Heat treatment is often required to achieve these improved properties. Common alloying
elements added to steel are chromium, manganese, molybdenum, nickel, and vanadium, sometimes
individually but usually in combinations.

 STAINLESS STEELS
Stainless steels are a group of highly alloyed steels designed to provide high corrosion resistance. The
principal alloying element in stainless steel is chromium, usually above 15%. The chromium in the
alloy forms a thin, impervious oxide film in an oxidizing atmosphere, which protects the surface from
corrosion. Nickel is another alloying ingredient used in certain stainless steels to increase corrosion
protection. Carbon is used to strengthen and harden the metal; however, increasing the carbon content
has the effect of reducing corrosion protection because chromium carbide forms to reduce the amount
of free Cr available in the alloy. In addition to corrosion resistance, stainless steels are noted for their
combination of strength and ductility. Although these properties are desirable in many applications,
they generally make these alloys difficult to work in manufacturing. Also, stainless steels are
significantly more expensive than plain C or low alloy steels. Stainless steels are traditionally divided
into three groups, named for the predominant phase present in the alloy at ambient temperature.
1. Austenitic stainless have a typical composition of around 18% Cr and 8%Ni and are the most
corrosion resistant of the three groups. Owing to this composition, they are sometimes identified as18-
8 stainless. They are nonmagnetic and very ductile; but they show significant work hardening. The
nickel has the effect of enlarging the austenite region in the iron–carbon phase diagram, making it stable
at room temperature. Austenitic stainless steels are used to fabricate chemical and food processing
equipment, as well as machinery parts requiring high corrosion resistance.
2. Ferritic stainless have around 15% to 20% chromium, low carbon, and no nickel. This provides a
ferrite phase at room temperature. Ferritic stainless steels are magnetic and are less ductile and
corrosion resistant than the austenitics. Parts made of ferritic stainless range from kitchen utensils to
jet engine components.
3. Martensitic stainless have a higher carbon content than ferritic stainlesses, thus permitting them to
be strengthened by heat treatment. They have as much as 18% Cr but no Ni. They are strong, hard, and
fatigue resistant, but not generally as corrosion resistant as the other two groups. Typical products
include cutlery and surgical instruments.

 CAST IRONS
Cast iron is an iron alloy containing from 2.1% to about 4% carbon and from 1% to 3% silicon. Its
composition makes it highly suitable as a casting metal. The overall tonnage of cast iron is second only
to steel among metals. There are several types of cast iron, the most important being gray cast iron.
Typical chemical compositions of gray and white cast irons are shown in Figure 4, indicating their
relationship with cast steel.

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Figure 4 Carbon and silicon compositions for cast irons, with comparison to steels (most steels have relatively
low silicon contents—cast steels have the higher Si content).

1. Gray Cast Iron

Gray cast iron accounts for the largest tonnage among the cast irons. It has a composition in the range
2.5% to 4% carbon and 1% to 3% silicon. This chemistry results in the formation of graphite (carbon)
flakes distributed throughout the cast product upon solidification. The structure causes the surface of
the metal to have a gray color when fractured; hence the name gray cast iron. The dispersion of graphite
flakes accounts for two attractive properties: (1) good vibration damping, which is desirable in engines
and other machinery; and (2) internal lubricating qualities, which makes the cast metal machinable.
The strength of gray cast iron spans a significant range. The compressive strength of gray cast iron is
significantly greater than its tensile strength. Properties of the casting can be controlled to some extent
by heat treatment. Ductility of gray cast iron is very low; it is a relatively brittle material. Products
made from gray cast iron include automotive engine blocks and heads, motor housings, and machine
tool bases.
2. Ductile Iron
This is an iron with the composition of gray iron in which the molten metal is chemically treated before
pouring to cause the formation of graphite spheroids rather than flakes. This results in a stronger and
more ductile iron, hence its name. Applications include machinery components requiring high strength
and good wear resistance.
3. White Cast Iron
This cast iron has less carbon and silicon than gray cast iron. It is formed by more rapid cooling of the
molten metal after pouring, thus causing the carbon to remain chemically combined with iron in the
form of cementite (Fe3C), rather than precipitating out of solution in the form of flakes. When fractured,
the surface has a white crystalline appearance that gives the iron its name. Owing to the cementite,
white cast iron is hard and brittle, its wear resistance is excellent, and strength is good. 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.
4. Malleable Iron
When castings of white cast iron are heat treated to separate the carbon out of solution and form graphite
aggregates, the resulting metal is called malleable iron. The new microstructure can possess substantial

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ductility—a significant difference from the metal out of which it was transformed. Typical products
made of malleable cast iron include pipe fittings and flanges, and railroad equipment parts.
5. Compacted Graphite Iron (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
shape (Figure 5e). 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.
Tensile and yield strengths for compacted graphite irons are comparable to values for ductile and
malleable irons, yet are greater than those 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, and brake discs for high-speed trains.

Figure 5 Optical photomicrographs of various cast irons. (a) Gray iron: the dark graphite flakes are embedded
in an α-ferrite matrix. (b) Nodular (ductile) iron: the dark graphite nodules are surrounded by an α-ferrite
matrix. (c) White iron: the light cementite regions are surrounded by pearlite, which has the ferrite–cementite
layered structure. (d) Malleable iron: dark graphite rosettes in an α-ferrite matrix. (e) Compacted graphite iron:
dark graphite wormlike particles are embedded within an α-ferrite matrix.