85

BASIC DUCTILE IRON ALLOYING

by
James D. Mullins, Sorelmetal Technical Services

One of the characteristics of alloying is that it affects

the diffusion rate of the carbon, which is the ability of
the carbon to move within the matrix. Upon cooling
and depending upon the rate of cooling, after
solidification, but before we reach the point where
transformation stops, we find that the carbon is able to
move/diffuse. The amount of this movement will vary
and as a result if it is not fast enough (limited by
alloys) to clear all of the matrix structure before the
end of transformation; this is one of the major reasons
why we get various mixtures of matrix microstructures
in Ductile Irons.
Ductile Irons form ferrite much more easily than gray
irons even with the same alloy content. Graphite
morphology is the reason for this. Graphite nodules
are encased within an austenite shell.
The
composition of the austenite affects the microstructure
and subsequent iron properties, again because if
affects the ease of carbon to move away from pearlite
leaving ferrite, as mentioned earlier. Ferrite contains
practically zero carbon. The average thickness of the
ferrite shell around a nodule of graphite does not
change whether the structure is from an as-cast or
heat treated sample. The other reason is that when
the nodule count is increased the amount of ferrite is
also increased, since the shell thickness remains
essentially the same but the number of places where
the carbon can diffuse to is increased. And so by
increasing the nodule count we see changes in the
structure and properties.
Another factor that we must consider is that during
solidification some elements are pushed into or
segregate to the last areas to freeze. These areas are
located between the graphite nodules and are called
the intercellular regions. Elements that have high
tendencies to segregate are P, Mn, Cr, V, Ti and Mo
in increasing order of tendency to segregate. (For
further information about this see Chapter 4, The
Sorelmetal Book of Ductile Iron). See Figure 1. Even
when the concentration of an element appears to be
low or in a normal range we find that they can
concentrate up to extremely high levels in those
intercellular areas. And when they do, they influence
what happens there. So we must be careful which

elements that we use for alloying to avoid forming

carbides in these intercellular regions. They increase
the hardenability in those areas, and the structures
change becoming harder, less ductile and more brittle.
Increasing the nodule count will reduce this effect and
then it may not make as much difference or it will
make less difference.
SEGREGATION OF VARIOUS ELEMENTS

Element
Mo
Ti
V
Cr
Mn
P
Si
Co
Ni
Cu

Segregation Factor
25.3
25.0
13.2
11.6
1.7 3.5
2.0
0.7
0.4
0.3
0.1

Figure 1.

There are some alloying elements, specifically

antimony, copper and tin, which surround the graphite
spheroids and act as barriers to the diffusion of
carbon. The use of these elements gives us the ability
to form nearly 100% pearlite in the matrix, stabilizing it
to keep it from transforming further.
Most of the time when we are talking about
hardenability we are talking about the ability to form
martensite. The term hardenability by itself means the
response to heat treating. But in cast irons we are
primarily interested in pearlitic hardenability. The
ability to form pearlite is the function of those items
previously mentioned. Matrix structures are functions
of cooling rate, nodule count and alloy content.
Looking at what some of the individual elements do.
Silicon has an effect on carbon equivalent. Its a solid
solution strengthening agent, so increasing silicon
greatly effects the embrittlement of Ductile Iron,
particularly at lower temperatures. For these reasons
the overall amount must be controlled. However,
silicon reduces chill and undercooling and promotes
graphite. It segregates negatively, which means that
the highest concentration is near the graphite nodule.

Nickel is also a graphitizing element and acts similarly

to silicon except that it does not embrittle, but rather
increases the toughness of the matrix. It contributes
to the carbon equivalent in the same way that silicon
does but not as effectively. It promotes pearlite but it
does not stabilize pearlite. With nickel you get more
pearlite but the pearlite breaks down more easily
during heat treatment. It increases hardenability and
through hardenability, it promotes the formation of
austenite and it also makes it easier to heat treat to
form martensite or ADI structures. It segregates
negatively in the same way that silicon does. It
doesnt cause problems.

All the allowing/trace elements that have been

mentioned above are recovered upon remelting, so
when calculating subsequent additions, the addition
must be reduced by the amounts recovered from the
return scrap.

Copper is similar to nickel in many ways, except that

is a much stronger pearlite promoter. At a 1% level,
usually a 100% pearlitic matrix can be obtained. It is
the most widely used alloy for pearlitic Ductile Iron
production, because of its effectiveness and cost. It
only gives a modest increase in hardenability (See
Figure 2).
Manganese is generally a pearlite former/stabilizer,
and forms carbides. It segregates strongly to grain
boundaries and increases hardenability.
Chromium is not a strong pearlite former, but is a
carbide stabilizer and can cause many problems with
respect to segregation as mentioned earlier.
Molybdenum is a pearlite stabilizer and promotes
hardenability. It is most often used in combination
with copper or nickel, but at a much lower addition
rate, because of its serious segregation tendency.
Looking at some of the other elements that we might
use. Antimony is a fantastic pearlite former, but is
used only in heavy sections with balanced cerium
additions, otherwise it can certainly change the nodule
structure/shape towards flake. Arsenic is another very
potent pearlite stabilizer, but for some reason or
another people are not enthusiastic about having
arsenic around in the foundry, but it is very good. It is
another one like antimony in that with a combination
with rare earth, it increases the nodule count and
produces better nodule shape.
The last major alloying element is tin. It is used in
small amounts because it is a strong pearlite former
and stabilizer. It can form flake graphite if the
additions are too large. Tin also strongly segregates if
you have excess tin. If there is not enough room for
the tin atoms to line up around the graphite spheroids,
the excess tin segregates into the last areas to freeze
and it greatly deteriorates the toughness of the
material.
See Figure 3 for the relative pearlite promoting
strength of some elements.

Figure 2. Comparison between the pearlite promoting effects of Mn and Cu

(TC: 3.85%, Si: 2.00%. Unalloyed Mn: 0.25%).

Cerium and magnesium are not used specifically as

alloying elements in Ductile Iron, but they can act to
change the structure and promote carbides. It is best
to add only the necessary amounts. Excessive cerium
causes graphite shape problems especially when you
have high purity charge materials. You must always
balance these things out.
If you want to change the mechanical properties you
must change the microstructure. With no other
process changes this can be done easily with alloys.
The alloying elements can affect both the solidification
process and the cooling from red heat to black heat
where changes to the structure occurs.
Relative
Element
Pearlite Promoting Effectiveness
39.00
Sn
7.90
Mo
5.60
P
4.90
Cu
4.40
Ti
0.44
Mn
0.37
Ni or Cr
Figure 3.

Rev March 2006