Introduction

CAST IRON, like the term steel, identifies a large family of ferrous alloys.
Cast irons primarily are iron alloys that contain more than 2% carbon and
from 1 to 3% silicon. Wide variations in properties can be achieved by
varying the balance between carbon and silicon, by alloying with various
metallic elements, and by varying melting, casting, and heat treating
practices.
The five types of commercial cast iron are gray, ductile, malleable,
compacted graphite, and white iron. With the exception of a white cast iron,
all cast irons have in common a microstructure that consists of graphite
phase in a matrix that may be ferritic, pearlitic, bainitic, tempered
martensitic, or combinations thereof. The four types of graphitic cast irons
are roughly classified according to the morphology of the graphite phase.
Gray iron has flake-shaped graphite, ductile iron has nodular or spherically
shaped graphite, compacted graphite iron (also called vermicular graphite
iron) is intermediate between these two, and malleable iron has irregularly
shaped globular or "popcorn-shaped" graphite that is formed during
tempering of white cast iron. Table 1 shows the correspondence between
commercial and microstructural classification, as well as final processing
stage in obtaining common cast irons.
Table 1 Classification of cast irons by commercial designation, microstructure,
and fracture

Commercial
designation

Carbon-rich
phase

Matrix(a) Fracture
P

Gray iron

Lamellar graphite

Ductile iron

Spheroidal graphite F, P, A

Silver- Solidification or heat

gray
treatment

Compacted
graphite iron

Compacted
(vermicular)
graphite

F, P

Gray

Solidification

White iron

Fe3C

P, M

White

Solidification and
heat treatment(b)

Mottled iron

Lamellar Gr + Fe3C

Malleable iron

Temper graphite

Austempered
ductile iron

Spheroidal graphite

Gray

Final structure
after
Solidification

Mottled Solidification

F, P

Silver- Heat treatment

gray

At

Silver- Heat treatment

gray

(a) F, ferrite; P, pearlite; A, austenite; M, martensite; At, austempered (bainite).

(b) White irons are not usually heat treated, except for stress relief and to
continue austenite transformation.
White cast irons, so named because of the characteristically white fracture
surfaces, do not have any graphite in the microstructures. Instead the
carbon is present in the form of carbides, chiefly of the types Fe 3C and Cr7C3.
Often, complex carbides are also present, such as (Fe,Cr) 3C from additions of
3 to 5% Ni and 1.5 to 2.5% Cr, (Cr,Fe) 7C3 from additions of 11 to 35% Cr, or
those containing other carbide-forming elements.

Cast irons may also be classified as either unalloyed cast irons or alloy cast
irons. Unalloyed cast irons are essentially iron-carbon-silicon alloys
containing small amounts of manganese, phosphorus, and sulfur. The range
of composition for typical unalloyed cast irons is given in Table 2. Figure 1
shows the range of carbon and silicon for common cast irons as compared
with steel.
Table 2 Range of compositions for typical unalloyed common cast irons

Composition, %
Type of iron
Gray

Si

Mn

2.5-4.0 1.0-3.0 0.2-1.0 0.002-1.0 0.02-0.25

Compacted graphite 2.5-4.0 1.0-3.0 0.2-1.0 0.01-0.1 0.01-0.03

Ductile

3.0-4.0 1.8-2.8 0.1-1.0 0.01-0.1 0.01-0.03

White

1.8-3.6 0.5-1.9 0.25-0.8 0.06-0.2

0.06-0.2

Malleable

2.2-2.9 0.9-1.9 0.15-1.2 0.02-0.2

0.02-0.2

Fig. 1 Approximate ranges of carbon and silicon for steel and various cast irons

The Iron-Iron Carbide-Silicon System

A section through the ternary Fe-Fe 3C-Si diagram at 2% Si (which
approximates the silicon contents of many cast irons) provides a convenient
reference for discussing the metallurgy of cast iron. The diagram in Fig. 2
resembles the binary Fe-Fe3C diagram but exhibits important differences
characteristic of ternary systems. Eutectic and eutectoid temperatures
change from single values in the Fe-Fe 3C system to temperature ranges in
the Fe-Fe3C-Si system; the eutectic and eutectoid points shift to lower
carbon contents.

Fig. 2 Section through the Fe-Fe3C-Si ternary equilibrium diagram at 2% Si

Figure 2 represents the metastable equilibrium between iron and iron

carbide (cementite), a metastable system. The silicon that is present
remains in solid solution in the iron, in both ferrite and austenite, and so
does not affect the composition of the carbide phase but only the conditions
and the kinetics of the carbide formation on cooling. The designations , ,
and Fe3C, therefore, are used in the ternary system to identify the same
phases that occur in the Fe-Fe 3C binary system. Some of the silicon may
precipitate along with the carbide, but it cannot be distinguished as a
different phase. The solidification of certain compositions does not occur in
the metastable system, but rather in the stable system, where the products

are iron and graphite rather than iron and carbide. These compositions
encompass the gray, ductile, and compacted graphite cast irons.
If the section through the ternary diagram at 2% Si is to be used in tracing
the phase changes that occur, its use can be justified only on the
assumption that silicon concentration remains at 2% in all parts of the alloy
under all conditions. This obviously is not strictly true, but there is little
evidence that silicon segregates to any marked degree in cast iron.
Carbon Equivalence
Both carbon and silicon influence the nature of iron castings, so it is
necessary to develop an approximation of their impact on solidification. This
has been accomplished through development of the concept of carbon
equivalence, CE. Using this approach, carbon equivalence is calculated as:
or more precisely, taking phosphorus into consideration:

Comparison of CE with the eutectic composition in the Fe-C system (4.3% C)

will indicate whether a cast iron will behave as a hypoeutectic or
hypereutectic alloy during solidification. When CE is near the eutectic value,
the liquid state persists to a relatively low temperature and solidification
takes place over a small temperature range. The latter characteristic can be
important in promoting uniformity of properties within a given casting.
In hypereutectic irons (CE greater than about 4.3%), there is a tendency for
kish graphite--proeutectic graphite that forms and floats free in the molten
iron--to precipitate on solidification under normal cooling conditions. In
hypoeutectic irons, the lower the CE, the greater the tendency for white or
mottled iron to form on solidification.
Characteristics of Cast Irons
White Cast Iron. White iron is formed when the carbon in solution in the

molten iron does not form graphite on solidification but remains combined
with the iron, often in the form of massive carbides. White irons are hard
and brittle and produce white, crystalline fracture surfaces.
White cast irons have high compressive strength and good retention of
strength and hardness at elevated temperature, but they are most often
used for their excellent resistance to wear and abrasion. The massive
carbides in the microstructure are chiefly responsible for these properties.
Gray Cast Iron. When the composition of the iron and the cooling rate at
solidification are suitable, a substantial portion of the carbon content
separates out of the liquid to form flakes of graphite. When a piece of the
solidified alloy is broken, the fracture path follows the graphite flakes, and
the fracture surfaces appear gray because of the predominance of exposed
graphite.
Gray cast iron has several unique properties that are derived from the
existence of flake graphite in the microstructure. Gray iron can be machined
easily at hardnesses conducive to good wear resistance. It resists galling
under boundary-lubrication conditions (conditions wherein the flow of
lubricant is insufficient to maintain a full fluid film). It has outstanding
properties for applications involving vibrational damping or moderate
thermal shock.

Ductile Cast Iron. Ductile iron, which is also known as nodular iron or

spheroidal graphite cast iron, is very similar to gray iron in composition, but
during casting of ductile iron the graphite is caused to nucleate as spherical
particles, or spherulites, rather than as flakes. This is accomplished through
the addition of a very small but definite amount of magnesium and/or
cerium to the molten iron in a process step called nodulizing.
Ductile iron is produced from the same types of raw material as gray iron,
but usually requires slightly higher purity, especially in regard to sulfur.
Casting properties of ductile iron, such as fluidity, are comparable to those
of gray iron.
The chief advantage of ductile iron over gray iron is its combination of high
strength and ductility--up to 18% minimum elongation for ferritic ductile iron
with a tensile strength of 415 MPa (60 ksi) as opposed to only about 0.6%
elongation for a gray iron of comparable strength. Martensitic ductile irons
with tensile strengths of about 830 MPa (120 ksi) exhibit at least 2%
elongation, and the newer austempered ductile irons exhibit in excess of 5%
elongation at even higher tensile strengths (1000 MPa, or 145 ksi).
For most applications, some deviation from true spherical shape can be
tolerated without unacceptable loss of properties. However, the quasi-flake
and crab form (see Table 3) are unacceptable for most applications.
Table 3 Summary and description of ASTM and equivalent ISO classification of
graphite shapes in cast iron

ASTM Equivalent
type(a) ISO form(b)

Description

VI

Nodular (spheroidal) graphite

II

VI

Nodular (spheroidal) graphite, imperfectly formed

III

IV

Aggregate, or temper carbon

IV

III

Quasi-flake graphite

II

Crab-form graphite

Irregular or "open" type nodules

Flake graphite

VI
(c)

VII

(a) As defined in ASTM A 247.

(b) As defined in ISO/R 945-1969 (E).
(c) Divided into five subtypes; uniform flakes; rosette grouping; superimposed
flake size; interdendritic, random orientation; and interdendritic, preferred
orientation
Compacted graphite (CG) cast iron, also known as vermicular graphite cast

iron, is characterized by graphite that is interconnected within eutectic cells

as is the flake graphite in gray iron. Compared with the graphite in gray iron,
however, the graphite in CG iron is coarser and more rounded, similar in
metallographic appearance to ASTM type IV, quasi-flake graphite (Table 3).
The structure can be considered intermediate between those of gray iron
and ductile iron. Individual properties can also be considered intermediate
between those of gray and ductile irons, but the unique combinations of
properties obtainable in CG irons make them superior to either gray or
ductile iron in applications such as disc-brake rotors and diesel-engine
heads.

Compacted graphite cast iron can be obtained by very carefully controlling

the amount of magnesium added as an inoculant in a process very similar to
the process used to make ductile iron. Unfortunately, either undertreatment,
resulting in a gray iron structure, or overtreatment, resulting in a ductile iron
structure, can occur if the ideal quantity of magnesium is missed by as little
as 50 ppm. Current commercial production of CG iron is accomplished by
inoculation with magnesium to give a residual content of 50 to 600 ppm in
the presence of 0.15 to 0.5% titanium and 10 to 150 ppm of rare earths,
such as cerium. In effect, the process is one in which the nodulizing reaction
due to the addition of magnesium is poisoned by the presence of a
controlled amount of titanium, and in which cerium is added to eliminate a
need to control sulfur at a low concentration.
Malleable cast iron encompasses yet another form of graphite called temper
carbon. This form of graphite is produced by the heat treatment of white
cast iron, which does not contain graphite, but does contain a high
percentage of cementite. When a white cast iron is heated for an extended
period of time (about 60 h) at a temperature of 960 C (1760 F), the
cementite decomposes into austenite and graphite. By slow cooling from
960 C (1760 F), the austenite transforms into ferrite or pearlite, depending
on the cooling rate and the diffusion rate of carbon. The ductility and
toughness of malleable iron falls between that of ductile cast iron and gray
cast iron. Because white iron can only be produced in cast sections up to
about 100 mm (4 in.) thick, malleable iron is limited in section size. In recent
years, malleable irons have been replaced by the more economically
processed ductile irons for many applications.
Selected References

Casting, Vol 15, ASM Handbook, ASM International, 1988

J.R. Davis, Ed., ASM Specialty Handbook: Cast Irons, ASM International, 1996
R. Elliot, Cast Iron Technology, Butterworths, 1988
H. Fredriksson and M Hillert, Ed., The Physical Metallurgy of Cast Iron, Proc.
Materials Research Society, North Holland, 1985
B. Lux et al., Ed., The Metallurgy of Cast Iron, Georgi Publishing, 1975
I. Minkoff, The Physical Metallurgy of Cast Iron, John Wiley & Sons, 1983
Properties and Selections: Irons, Steels, and High-Performance Alloys, Vol 1,
ASM Handbook, ASM International, 1990, p 3-104
C.F. Walton and T.J. Opar, Ed., Iron Castings Handbook, Iron Castings Society,
1981