Metallurgy Ductile Iron V13-20171214 PDF

DUCTILE
IRON
METALLURGY
Ir G HENDERIECKX
GIETECH BV
DUCTILE IRON: METALLURGY Version 13
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METALLURGY
OF
DUCTILE IRON
GIETECH BV
Ir G D HENDERIECKX
No data from this book can be used without verification; the author cannot and
will not accept any responsibility for possible consequences due to data used
from this book.
Nothing from this book may be copied without written approval of the author.
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Ir G Henderieckx GIETECH BV December 2017
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CONTENT
1. INTRODUCTION
2. METALLOGRAPHY
3. GRAPHITE APPEARANCE
2.1 FREE GRAPHITE
2.1.1SHAPE
2.1.2 NODULARITY
2.1.3 SIZE
2.1.4 NODULE COUNT
2.1.5 EFFECT ON MECHANICAL PROPERTIES
2.2 CARBIDES
4. STRUCTURE
3.1 COMMON STRUCTURES
3.2 SPECIAL STRUCTURE: AUSTENITE
3.3 PERCENTAGE
3.4 EFFECT ON MECHANICAL PROPERTIES
5. INFLUENCE OF CHEMICAL COMPOSITION

5.1 COMMONLY USED ELEMENTS
5.2 SPHEROIDIZING ELEMENTS
5.3 ALLOYING ELEMENTS
5.4 SUBVERSIVE ELEMENTS
5.5 GASEOUS ELEMENTS
5.6 OVERVIEW
5.7 TOLERANCES ON TEST RESULTS
6. INFLUENCE OF METALLURGICAL TREATMENTS

6.1 PRETREATMENT IN FURNACE
6.2 DESULFURISING
6.3 NODULISING
6.4 INOCULATION
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7. NON-CONFORM METALLURGY
7.1 GRAPHITE MORPHOLOGY
7.2 AMOUNT & TYPE OF GRAPHITE IN CASTING
7.3 STRUCTURE
7.4 INCLUSIONS
8. CONCLUSION
ATTACHMENT: EFFECT OF MELTING ON THE CHEMISTRY
ATTACHMENT: EFFECT OF THE METALLURGICAL TREATMENTS

ON THE NUCLEI
ATTACHMENT: MELTING IN NEUTRAL & BASIC LINED FURNACES
No data from this book can be used without verification; the

author cannot and will not accept any responsibility for possible
consequences.
Nothing from this book may be copied without specific approval of

the author.
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1. INTRODUCTION
The text will first describe the metallography, which is the tool for studying the
metallurgy of the metal.
Then the graphite appearance is described. The free graphite is important

concerning shape, number and amount as well as the location.
The bounded graphite, not the one that stays dissolved in the matrix, but the
carbides, is mostly to avoid due to its negative influence on the properties.
The metal structure is important for the strength and ductility. The special structure,
special because it normally does not appear at room temperature, is austenite and is
present in the nickel alloyed irons, mostly known as “niresists” (high nickel irons).
The non-conformities as well in graphite appearance as in structure will be described

and discussed, trying to indicate the reasons of its appearance.
The influence of the chemical composition is discussed separately. The range of

elements, commonly used, is described. Per element the influences are given.
At latest, the influence of the metallurgical treatments, which are desulfurising,

nodulising and inoculation are explained.
Two other comments should be made to understand the next text:
1. Ductile irons do not solidify in the same way as grey cast iron as there is no
eutectic cell structure in which the graphite can form. The graphite grows as
individual spheroids and unlike grey irons where the properties are principally
dictated by the graphite, in ductile irons the properties are principally dictated
by the matrix.
2. A distinction should be made between subversive and tramp elements:
* Tramp elements influence the matrix structure and hence the

properties of ductile iron but do not affect the graphite structure.
* Subversive elements impact graphite structure and hence the

properties of ductile iron. They may also affect the matrix constituents.
Pay attention to the fact that the material is (very) prone on the section
thickness (especially the pearlitic structure), unless the chemical composition
is adapted to it.
Ductile iron should be delivered in the “as cast” condition, accept the special
alloyed ADI ductile iron, which falls out of the scope of this text.
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Ductile iron is concerning the materials as described in the latest version of the
below mentioned standards:
EN 1563 Founding – Spheroidal graphite cast irons
ISO 1083 Spheroidal graphite cast irons - Classification
ASTM A536 Standard Specification for Ductile Iron Castings

ASTM A395 Standard Specification for Ferritic Ductile Iron Pressure-Retaining
Castings for Use at Elevated Temperatures
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2. METALLOGRAPHY
2.1 GENERAL NOTION
2.2 LIGHT MICROSCOPES
2.3 SEM
2.4 TEM
2.5 DIFFRACTION
2.1 GENERAL NOTION

Metallography is one of the most valuable tools available to the metallurgist. As
each other metal, the metallography will be deciding for the properties of the material,
mechanical as well as physical properties, and their behaviour during solidification.
Metallography is the science dealing with the constitution and structure of metals and
alloys as revealed to the unaided eye or by using tools such as low-power
magnification, optical microscopy, electron microscopy and diffraction or X-Ray
techniques.
By the late 19th century, optical examination of metals, in particular iron and steel,
had become the foundation upon which all our present understanding of the
relationship between microstructure and mechanical properties is based.
Despite significant advances in electron microscopy, the use of the optical

microscope and / or unaided visual examination should remain the first stage of any
metallurgical investigation and may suggest the course of subsequent steps using
more sophisticated techniques and equipment.
Photomicroscopy and modern video techniques are important metallographic tools as

they can accurately reproduce the features for others to view.
For meaningful results, it is essential that the samples chosen are representative of
the material (refer comments on section sensitivity) and that they are flawlessly
prepared for examination.
Metallography is both an art and a science. The artistry lies in the techniques used to
prepare a section and the science lies in the interpretation of the structures.
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2.2 LIGHT MICROSCOPES
The light microscopes are well known since centuries and used in all industries.
The well-known type, used in education, is shown in figure 1.
Later the stereo microscope entered the market (figure 2) and the last decade the
microscope relates to computers to analyze and evaluate the picture (figure 3) with
the use of software.
Figure 1 Light microscope Figure 2 stereo microscope
Fig
ur
e3
a/
b
Mi
cr
os
co
pe
co
nnected with computer
2.3 SEM
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SEM stands for scanning electron microscope.
The SEM is a microscope that uses electrons instead of light to form an image.
Since their development in the early 1950's, scanning electron microscopes have
developed new areas of study in the medical and physical science communities. The
SEM has allowed researchers to examine a much bigger variety of specimens.
The scanning electron microscope has many advantages over traditional

microscopes. The SEM has a large depth of field, which allows more of a specimen
to be in focus at one time. The SEM also has much higher resolution, so closely
spaced specimens can be magnified at much higher levels. Because the SEM uses
electromagnets rather than lenses, the researcher has much more control in the
degree of magnification. These advantages, as well as the actual strikingly clear
images, make the scanning electron microscope one of the most useful instruments
in research today.
Figure 4 Beam scheme
Figure 5 Schematic view microscopes
The SEM is an instrument that produces a largely magnified image by using

electrons instead of light to form an image. See figure 4 and 5.
A beam of electrons is produced at the top of the microscope by an electron gun.

The electron beam follows a vertical path through the microscope, which is held
within a vacuum. The beam travels through electromagnetic fields and lenses, which
focus the beam down toward the sample. Once the beam hits the sample, electrons
and X-rays are ejected from the sample.
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Detectors collect these X-rays, backscattered electrons, and secondary electrons and
convert them into a signal that is sent to a screen like a television screen. This
produces the final image.
2.4 TEM
TEM stands for Transmission Electron Microscope (Figure 6).
TEM is analogous to the optical microscope. It provides very high resolution which
can reach approximately 0,1 nm in the case of lattice images.
Consequently, very high magnification (Close to 1 million times) can be obtained.
TEM is used to examine very thin sections (<60 nm in thickness) through the cells
and tissues or through materials as well as replicas of the surfaces of the samples.
Figure 6
Transmission Electron
microscope
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2.5 DIFFRACTION
An X-ray microscope (see figure 7) uses electromagnetic radiation in the soft X-ray
band to produce images of very small objects.
Unlike visible light, X-rays do not reflect or refract easily, and they are invisible to the
human eye. Therefore the basic process of an X-ray microscope is to expose film or
use a charge-coupled device (CCD) detector to detect X-rays that pass through the
specimen. It is a contrast imaging technology using the difference in absorption of
soft x-ray in the water window region (wavelength region: 2,3 – 4,4 nm, photon
energy region: 0,28 – 0,53 keV) by the carbon atom (main element composing the
living cell) and the oxygen atom (main element for water).
The resolution of X-ray microscopy lies between that of the optical microscope and
the electron microscope. It has an advantage over conventional electron microscopy
in that it can view biological samples in their natural state.
Electron microscopy is widely used to obtain images with nanometer level resolution,
but the relatively thick living cell cannot be observed as the sample has to be
chemically fixed, dehydrated, embedded in resin, and then sliced ultra thin.
Additionally, X-rays cause fluorescence in most materials, and these emissions can
be analyzed to determine the chemical elements of an imaged object. Another use is
to generate diffraction patterns, a process used in X-ray crystallography. By
analyzing the internal reflections of a diffraction pattern (usually with a computer
program), the three-dimensional structure of a crystal can be determined down to the
placement of individual atoms within its molecules. X-ray microscopes are sometimes
used for these analyses because the samples are too small to be analyzed in any
other way.
Figure 7
X-ray microscope
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3. GRAPHITE APPEARANCE
3.1 FREE GRAPHITE

3.1.1 SHAPE
3.1.2 NODULARITY
3.1.3 SIZE
3.1.4 NODULE COUNT
3.2 CARBIDES
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3.1 FREE GRAPHITE
3.1.1 SHAPE
The standards that deal with the identification of the free graphite are:
1. German VDG-Merkblatt P441 (august 1962)

Richtreihen zur Kennzeichnung der Graphitausbildung
2. European standard (DIN) EN ISO 945-1994

Designation of Microstructure of Graphite
3. American ASTM-standard A 247-67 (Reapproved 1998).

Standard Test Method for Evaluating the Microstructure of Graphite in
Iron Castings
The graphite shape is set during the solidification process and cannot be modified
afterwards, whatever the treatment performed. The exception is malleable iron, in
which, after an extended heat treatment, the graphite is changed or removed partly.
There are six classes for the graphite shape (according to EN-ISO 945), named
class I to VI (see figure 8).
Shape I is the “flake (lamellar) shape”,

with a ratio length / width > 50.
Shape II is a “special shape”, seldom

appearing shape, (Quasi lamellae).
Shape III is the “vermicular or worm

shape” and has a ratio length /
width between 2 and 10.
Shape IV is the “shape of aggregates”

of malleable cast iron.
Shapes V and VI are the “nodular or

spheroidal shapes” with a ratio
length / width that equals 1.
Figure 8 Graphite shape acc EN
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Shape VI is the preferred shape for ductile iron; but also shapes V is frequently
present.
The above-mentioned classification is the appearing in the European EN ISO 945

standard. The classification is different from the ASTM A247 standard, in which
there are 7 classes. Class I and II are those, which are preferred for the ductile irons.
See figure 9.
Figure 9 Graphite shape acc to ASTM
A comparison between the standards EN ISO 945 and ASTM A247 is as follows:
EN ISO 945 kind of graphite ASTM A 247 Kind of graphite
I flake graphite, lamellar VII flakes, lamellar

II crab-form graphite VI irregular or open nodules (exploded)
III vermicular shape, quasi-flakes, compacted V, IV irregular graphite
IV graphite aggregates, temper carbon III graphite aggregates (malleable iron)
V less perfect nodules I, II nodules
VI nodules
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In the next figure 10, some of the possibilities concerning the appearing shapes of
free graphite in ductile iron, target one as well as the non-accepted ones, are shown.
They are made with a magnification of 100 x.
Magnification: 100 x
Figure 10 Irregular graphite shapes
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3.1.2 NODULARITY
European standard
The “nodularity” is the ratio of the number of nodules with shape VI (European
standard) compared to the total number of nodules. See figure 11.
Mostly, it is agreed between purchaser and supplier (in the specification of the metal)
that is the ratio of the number of nodules with shape (V + VI), compared to the total
number of nodules.
Magnification: 100 x
Figure 11 Example of nodularity
The most common requirement is a minimum nodularity of 85 %. For special

applications (high stressed), a higher nodularity is preferred.
Anyhow, the lower the nodularity, the lower the ductility expressed in elongation of
tensile test or shock resistance in Charpy V test.
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American standard
For the ASTM standard, the nodularity is the amount of class (I + II), compared to the
total amount of free graphite.
But this is not correct, is mixing 2 systems, because this standard, as well as most
Anglo-Saxon literature, has another evaluation, another factor.
The ASTM standard deals with a graphite shape number, which is deducted from the
area of the graphite compared to the area of the smallest circle drawn around the
graphite segregation. See figure 12.
Figure 12 Graphite shape factor
Note:
The Anglo-Saxon literature indicates that, for ASTM A247 shape I and II, a graphite
shape factor. This is the ratio between the graphite and the smallest circle, drawn
around the graphite (see previous chapter).
If the factor is > 0, 75 and there is no chunky, flake or exploded graphite, there will be
any influence on the mechanical properties.
Pay attention when using the graphite shape evaluation software. It should
clearly mention according to which international standard it is working.
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3.1.3 SIZE
The size of the free graphite has been divided into 8 classes, named 1 to 8. The
lowest numbers indicate the largest sizes.
They are valid for all shapes of graphite and the spheroid (nodular) shape is used as
example. The higher the class number, the smaller the dimensions of the graphite.
The figures for the different standards are shown in the table hereafter:
Table Review of Graphite size
DIN and ISO 945-1994 ASTM A 247

Number Size in microscope Real size Maximum size Real
Magnification x100 range Magnification x100 maximum
In mm in mm in mm size in mm
1 > 100 >1 128 1,28
2 50 – 100 0,5 – 1,0 64 0,64
3 25 – 50 0,25 – 0,5 32 0,32
4 12 – 25 0,12 – 0,25 16 0,16
5 6 – 12 0,06 – 0,12 8 0,08
6 3–6 0,03 – 0,06 4 0,04
7 1,5 – 3 0,015 – 0,03 2 0,02
8 < 1,5 < 0,015 1 0,01
A cast iron with small sized free graphite will have, in case of the same structure, a
higher strength compared to another with bigger sized graphite. Bigger free graphite
mostly gives, with an equal structure, better slide wear resisting capacities.
In the figure 13, the classes are given for nodules class V and VI, according to the
European standard.
For the graphite shapes class 1 and 2, only the flake shape exists. Therefore, it is not
shown for the spherical (nodular) shape.
Magnification 100 x
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Figure 13 Graphite size
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3.1.4 NODULE COUNT
Another key factor for ductile iron is the number of nodules per mm2. Nodule Count,
expressed as the number of graphite nodules/mm2, also influences the mechanical
properties of Ductile Iron, although not as strongly and directly as graphite shape
(nodularity). Especially the fatigue strength is increasing with an increasing nodule
count. Also, the tendency to form porosity and grain boundary segregations is
decreasing with an increasing number of nodules.
Generally, high nodule count indicates good metallurgical quality, but there is
an optimum range of nodule count for each section size of casting, and nodule
counts more than this range may result in a degradation of properties.
Nodule count as such does not strongly affect tensile properties, but it influences
microstructure, which significantly influence the mechanical properties:
• Nodule count influences the pearlite content of as-cast Ductile Iron. Increasing
the nodule count decreases the pearlite content and consequently, decreasing
strength (tensile and yield) and increasing elongation.
• Nodule count affects carbide content. Increasing the nodule count improves
tensile strength, ductility and machinability by reducing the volume fractions of
chill carbides, segregation carbides and carbides associated with "inverse
chill". The impact test results are decreasing quickly with carbides, even with
small intercellular carbides (MoC…). Carbides also increase the tendency to
micro-porosity.
• Matrix homogeneity is influenced by nodule count. Increasing the nodule count

produces a finer and more homogeneous microstructure. This refinement of
the matrix structure reduces the segregation of harmful elements which might
produce intercellular carbides, pearlite or degenerate graphite.
• Nodule count affects graphite size and shape. Increasing nodule count results
in a decrease in nodule size (total amount of free graphite is depending on the
chemical composition), which improves tensile and fatigue strength as well as
the fracture properties. Inoculation practices used to improve nodule count
often make the nodules smaller and more spherical. Thus, high nodule count
is generally associated with improved nodularity. The growth of nodules is not
spheroidal due to different influences (section size, heat flow, location in the
mould, segregation…).
The factor “nodule count” is not yet present in the standards. Most customers request
that the ductile iron should have a minimum nodule count of 50 nodules / mm2,
whatever the section size of the material is. The smaller the section, the higher the
nodule count should be.
A first series of pictures (figure 14) does give this for a value from 25 nodules per
mm2 up to 300 nodules per mm2. The second series (figure 15) gives several
pictures, combining the size of the free graphite with the number of nodules per mm2.
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Figure 14 Series 1: Nodule count
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Pay attention when using the nodule count evaluation software. It should
clearly mention according to which international standard it is working and
what is the minimum size of indication it will count as a nodule.
The indication must have a diameter > 5 µm or an area > 20 µm2.
Series 2: combination of diameter of nodules and nodule count
Figure 15 Nodule count and size
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The nodule count is depending on the wall thickness.
The next pictures give the nodule count for the same casting, ferritic ductile iron,
depending on different sections. See figure 16 to 18.
Figure 16 a and b Nodule count and size Wall thickness 10 mm
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3.1.5.1 Type of free graphite
3.1.5.2 Nodularity & size
3.1.5.3 Degenerated graphite
3.1.5.4 Influence elements
3.1.5.1 Type of free graphite

It is clear that the graphite morphology has a very important influence on the
mechanical properties of each type of iron.
The shape must be class V and VI for the European standard EN ISO 945 (class I
and II for the ASTM A247) to achieve the best properties.
No other shape has an equal ductility (elongation, notched shock test) as the nodular
shape. The lamellar (flake) shape has no elongation (< 1 %) and the wormlike,
vermicular (compacted) graphite has an elongation of about 2 to 3 %.
Both, lamellar and compacted graphite, have a notched shock value in the order of
the measurement tolerances, which means not measurable correctly.
But an amount of flake or intercellular flake graphite > 5 % is not accepted,

although the nodularity or shape factor is conforming to the requirements.
3.1.5.2 Nodularity & size

To quantify the nodular graphite shape, the European literature does use the factor
“nodularity” and the Anglo-Saxon literature has established the “shape factor” (see
previous chapter, see figure 12 page 16).
For the nodularity, it is accepted to have a level > 85 % and it is preferred a level > 95
%.
If the shape factor (American system, ASTM A247) is between 0,75 and 1,00 % and
there is no chunky, flake or exploded graphite, the mechanical properties (tensile
strength, yield strength and ductility, even the fatigue strength) are very few (nearly
not) affected. With lower nodularity levels the properties will decrease very quickly.
If the graphite shape of the material is near to the preferred shape (V and VI for the
European standards and I and II for the American standard), the properties
(mechanical and physical) still can be not perfect, not good.
The effect on the dynamic elastic modulus (Young’s modulus) is important as can be
seen in figure 19. This modulus is used by the designers to calculate a component
strength and geometry.
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Figure 19 Young’s modulus
Figure 20 Influence nodularity on

fatigue strength
Figure 20 shows the influence of nodularity on the notched and unnotched fatigue
limits of pearlitic ductile Iron. The notched fatigue limit varies very little over a wide
range of nodularity, while the unnotched fatigue limit increases rapidly with nodularity,
especially at very high nodularity.
These results indicate that non-spherical graphite initiates fatigue failure in

unnotched Ductile Iron, while in v-notched specimens, the crack initiates prematurely
in the notch, over-riding any effect of nodularity.
The net result of the different effects of nodularity of pearlitic ductile iron on notched
and unnotched specimens is the variation of fatigue strength reduction factor (notch
sensitivity ratio) with nodularity shown in figure 21, in which notch sensitivity
increases with increasing nodularity.
Figure 21
Fatigue strength factor according
nodularity
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The size of the graphite shall not be too large because it can act as a real section
decrease. On the other hand, in applications with a sliding wear (two metal surfaces
moving along each other) and or with vibrations, a larger size can be better.
A high nodule count (mostly smaller graphite size) will especially increase the fatigue
strength of the iron and reduce the solidification shrinkage tendency. See figure 22.
Figure 22
Fatigue strength according
nodule size
3.1.5.3 Degenerated graphite

Chunky graphite will also decrease the mechanical properties very quickly and the
preferred amount is zero, anyhow the maximum is 5 %.
Locally there can be more, but the area must be restricted, especially in heavy
stressed sections.
The presence of carbides, which are not free graphite but combinations of graphite
with iron or another element like chromium (Fe3C or Cr6C); will decrease the
toughness very rapidly. If these carbides form a network at the grain boundaries, a
crack will growth very quickly.
For this reason, the carbides are mostly restricted to 5 %, sometimes they are even
not allowed (in case of shock resistance testing). See chapter 3.2 CARBIDES.
3.1.5.4 Influence of elements
The tensile and yield strength of pearlitic ductile irons are decreasing according to the
figure above. The nodularity difference is initiated by a variance of Mg and by Pb
(appearance of spiky graphite). Figure 23 and 24.
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Influence Mg content
Tensile Yield
500
450
Strength in MPa
400
350
300
250
Influence Pb content 200

Tensile Yield 20 30 40 50 60 70 80 90
500
Strength in MPa
Nodularity
450
400 Figure 23 Influence Mg

350
300
250
200
50 60 70 80 90
Figure 24 Influence Pb
Nodularity
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3.2 CARBIDES
The graphite, present in the molten iron, will finally be in:
1. Matrix (like steel), it is invisible

2. Free graphite
3. Carbides.
The graphite in the matrix will influence the structure (see next chapter).
The free graphite is discussed in previous chapter.
The graphite that forms carbides is the least wanted one. It mostly decreases the
ductility (elongation as concerned the tensile test, and shock resistance) very
extensively and decrease the machinability.
The first form is the Fe3C or iron carbides. They also are present in the pearlite and
are not that dangerous unless large concentrations are large sizes are present.
The carbides that are formed with elements as are Cr, Mo, Ti, V… are very harmful to
machinability, ductility and shock resistance and should be avoided to the maximum.
The carbides with Mg are also to avoid because they take Mg away from the reaction
to decrease the oxygen and sulfur content. So, the consequence is that more
FeSiMg is required and that the ductility of the ductile iron will decrease very much.
The effect on the yield strength and tensile strength for pearlitic iron is shown in next
figures. The presence of carbides in ferritic iron is not common because carbide
promoting elements are avoided to the maximum extend.
The tensile strength of pearlitic

ductile iron does decrease
substantially for high nodularity
irons. See figure 25.
It is less for low nodularity iron.
Figure 25
Tensile strength acc nodularity
and carbides
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Contrary to the tensile strength, the yield strength of pearlitic ductile iron increase
with increasing amount of carbides.
The increase is few for high nodularity iron but large for low nodularity iron.
See figure 26.
Figure 26 Yield strength according to nodularity and carbides
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4. STRUCTURE
4.3 PERCENTAGE

There are 4 main structures, which are frequently met in ductile iron: ferrite, pearlite,
bainite and martensite.
The ferritic structure is a “single” structure, composed of one type of crystal: α-crystal.
The other structures are a mixture of ferrite and cementite, which is an iron-carbide.
In a first series of pictures (figure 27), the structure is shown as located around a
nodule. In the second series (figure 28) a larger area is shown.
First series
Figure 27 Structure
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Second series
Figure 28 Ferrite, pearlite and mixture
When there is little ferrite structure present in a pearlite matrix, the ferrite surrounds
mostly the graphite. This typical phenomenon is called “bulls eye” (Figure 29 and 30).
Figure 29
Pearlite – ferrite mixture, type bulls eye
Figure 30
Pearlite – ferrite mixture, type bulls eye
The pearlite structure is a mixture of ferrite and cementite (Fe3C), of which the growth
mechanism is shown in figure 31.
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Figure 31
Pearlite growth mechanism
The last structures are bainite (figure 32) and martensite (figure 33), which normally
require a quenching heat treatment.
Figure 32 a and b
Bainite or ADI
structure
Figure 33 a and b
Martensite
structure
All series of pictures give the structure as it reveals after an etching with 1 %
alcoholic nitric acid and a magnification of 100 x.
The structure is depending on:
1. Chemical composition
2. Cooling rate (which is depending on the wall thickness and mould
material).
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If the cooling rate is very high, the solidification is white and most (if not all) graphite
forms carbides. See figure 34 a and b.
Figure 34 a and b
High cooling rate
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If the cooling rate is very low, the structure will be without carbides unless at the end
some carbides can be formed. See figure 35 a and b.
Figure 35 a and b
Low cooling rate
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With intermediate cooling rates, a mix-solidification appears. See figure 36 a and b.
Figure 36 a and b
Intermediate cooling
rate
It is mostly the case, especially for grey iron, that very thin sections and corners are
solidified white.
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The amount of graphite, present as “free graphite”, is depending on the temperature
and structure. In eutectic iron, this is:
Time Mass % Volume %
Just solidified 2,35 % 9,11 %
Eutectic temperature 3,53 % 11,31 %
Pearlite, room temperature 3,53 % 11,31 %

Ferrite, room temperature 4,28 % 13,51 %
This indicates that it will be easier to pour ferritic iron without shrinkage in comparison
with pearlitic iron.
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High alloyed (nickel and nickel – copper) ductile irons can have an austenitic
structure and are known as “niresists”. The austenitic structure will mostly contain
carbides between 5 and 15 %.
It is possible to cast the metal without carbides, but a more frequent technique is to
remove the carbides by a heat treatment.
In a first series of pictures (figure 37), the structure is shown with carbides. In the
second series (figure 38), the structure without carbides is shown.
The first series of pictures give the structure as it reveals after an etching with 5 %
alcoholic nitric acid, the second after an etching with V2A Mordant etch and both with
a magnification of 100 x.
Figure 37 Austenitic structure with carbides
Figure 38 Austenitic structure “as cast” and “heat treated”
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4.3 PERCENTAGE OF FERRITE & PEARLITE
In the following series of pictures (figure 39), a ferritic / pearlitic material is classified
according to the amount of ferrite and pearlite.
This is important because of the distinctive characteristics of these structures:

strength, ductility, hardness, heat conductibility…
Figure 39
Ferritic – pearlitic
structure
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4.4.1 INFLUENCE
4.4.2 SEGREGATION EFFECT
4.4.3 WALL THICKNESS
4.4.4 REMARK
4.4.1 INFLUENCE
The tensile strength, yield strength and hardness will increase with an increasing
amount of pearlite. The elongation will decrease.
The hardness is mostly influenced by the presence of carbides.
Mostly accepted data:

Ferrite ferrite-pearlite Pearlite
Tensile strength MPa 350 – 425 475 – 600 > 650

Yield strength MPa 220 – 275 320 – 380 > 440
Elongation % 15 – 22 5 – 12 >2
Hardness HB 120 – 180 160 – 250 > 220
High strength, low hardness and high elongation are not possible!
It is very important to investigate the confidence level of results, which means that, if
the foundry uses the same chemical composition and treatments, the result should
be similar within a small range. It must be that a foundry practice will lead to nearly
identical results. This is the case of the alloying and cooling is within narrow limits.
Several formulas are given in the literature, but no one can be used without any
adaption to the foundry applied. It must be clear that the use of formula requires a
production that is regulated by strict rules, which are followed consequently (process
control). An example is given below:
Tensile strength T = 0,69 + 2,48 MMH

Yield strength E0,2 = 82,70 + 1,24 MMH
Elongation % L = 37,85 – 0,093 MMH
MMH is micro hardness in HV: MMH = {HVF * (% ferrite) + HVP * (% pearlite)} / 100
HVF = 64 + 44 (% Si) + 9 (% Mn) + 114 (% P) + 10 (% Cu) + 7 (% Ni)

+ 22 (% Mo) + 7 (% Cr)
HVP = 249 + 26 (% Si) + 12 (% Mn) + 234 (% P) + 16 (% Cu) + 17,5 (% Ni)

+ 26 (% Mo) + 16 (% Cr)
Especially the castings that should be delivered as cast will require a very good
controlled production, especially shake out time.
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4.4.2 SEGREGATION EFFECT
But, because of the segregation tendency of several alloying elements, this

confidence level will decrease very much for real, (especially difference in wall
thickness, temperature, pouring time…) situations.
The higher the segregation factor, the lower the confidence level will be. Figure 40
gives an example for manganese.
Figure 40
Segregation effect of Mn
The segregation tendency is ranked as follows (segregation factor), stating that a

figure < 1,00 indicates an element that stays maximum in the “first freezing” liquid
and a figure > 1,00 indicates an element that segregates to the “last freezing” liquid.
Element Mo Ti V Cr Mn P
Factor 25,3 25,0 13,2 11,6 1,7 – 3,5 2,0
Element Si Co Ni Cu
Factor 0,7 0,4 0,3 0,1
The higher the segregation factor, the more important the cooling time will be. A slow
cooling (up to solidification), will increase the segregation.
Manganese, as molybdenum, titanium and phosphorus, segregates to the last to

freeze areas during solidification of Ductile Iron, while graphitizing elements (Si, Cu,
and Ni) behave in the opposite way. This is also indicated in figure 41.
The segregation of manganese and especially molybdenum are clearly shown.
Tin segregates severely if its content is larger than 0,15 %.
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Figure 41
Segregation effects
As cited in “The Sorel metal Book of Ductile Iron”, a casting with a global
manganese content of 0,35 % may exhibit manganese levels more than 2,5 % (if
segregation occurs) at the grain boundaries. Too high manganese content (not able
to match with sulfur because of the Mg treatment) will lead to carbides at the grain
boundaries in ductile iron.
For this reason, the recommended maximum manganese level in heavy section
Ductile Iron (sections with a modulus > 25 mm or 2,5 cm) is 0,30 %. In fact, Sorel /
Rio Tinto has consistently promoted a maximum of 0,35 % manganese regardless of
section modulus.
The reverse behaviour is valid for Si, Cu and Ni. They will concentrate more in the
first solidifying metal.
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4.4.3 WALL THICKNESS

The influence of the wall thickness is different according to the structure.
1. In ferritic irons, the tensile strength is little affected by an increase in section

size whereas there is a significant reduction in ductility.
2. In pearlitic irons, the tensile strength is reduced by an increase in section size,

but the already low ductility is little affected.
3. In all irons an increase in section size has insignificant effect on proof strength
which is normally the property on which the design is based.
Example:
Section Pearlitic iron Ferritic iron
Size Tensile Yield Elongation Tensile Yield Elongation

mm MPa MPa % MPa MPa %
30 700 420 4 425 290 25

45 650 385 4 425 288 23
150 570 360 3 425 285 18
300 495 340 2,5 385 283 7
4.4.4 REMARK
The lower properties found in heavy sections result from deterioration in nodule
number, shape and size, together with a segregation of carbide promoting elements
resulting from the slower speed of solidification.
The properties of ductile iron in heavy sections can be improved using good
inoculation practice particularly late inoculation techniques, the selection of charges
containing low levels of carbide forming elements and by additions of elements which
improve nodule shape and nodule count in slow cooling sections.
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5. INFLUENCE OF CHEMICAL
COMPOSITION
5.2 SPHEROIDIZING ELEMENTS
5.6 OVERVIEW
Element Carbon C
Extreme range limits % 2,50 to 4,00
Preferred range limits % 3,40 to 3,60
Be aware that the C-testing by spectrometer does never give the correct result.
The higher the C-content, the less accurate the test result. It is preferred to use
a combustion method.
The solubility limits are depending on CE (C + Si/3 + P/3) and the temperature. The
high Si-irons (> 3 %) have a lower C-content due to the high Si-content. The more
detailed formula for the CE is:
CE = %C + 0,31 (%Si) + 0,33 (%P) + 0,047 (%Ni) + 0,40 (%S) – 0,015 (%Mo)
– 0,063 (%Cr) – 0,135 (%V) – 0,027 (%Mn) + 0,074 (%Cu) + 0,25 (%Al)
The maximum soluble carbon, Cmax, is:
Cmax = 1,30 % + 0,00257 * T (°C) – 0,31*(% Si) – 0,33*(% P)

– 0,4*(% S) + 0,027*(% Mn)
The carbon is partly dissolved in the metal matrix (± 2,1 %), the other part appears as
free graphite with nodule shape and / or as carbides. The correct amount of dissolved
carbon (in austenite) can be calculated with following formula:
% Caust = 2,11 – 0,023 x (%Si) + 0,006 x (%Mn) – 0,35 x (%P) – 0,08 x (%S)
This allows us to calculate the free carbon :
% Cfree = % Ctotal - % Caust

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Effects:
1. too high carbon content (as well as CE) will promote graphite flotation
(depending on wall thickness). See description later.
2. Too high C-content also increase the mould expansion due to thigh
pressure when the graphite segregates. This can lead to porosity
formation, especially in case of green sand moulds and thick wall
castings.
3. too low carbon level (as well as CE level) will promote porosity during
solidification
4. has a very low influence on metal structure, slightly increase ferrite

structure
5. the influence on the mechanical properties are: 0,1 % extra carbon will
• decrease yield strength by 3 MPa

• decrease the tensile strength by 3 MPa
• decrease the elongation by 0,3 %
• decrease the hardness by 0,7 HB
• decrease the Charpy V value by 1 to 2 J
• does not influence the transformation temperature for the Charpy
V value (ductile to brittle fracture temperature).
6. too extended stay in the melting or holding furnace at temperatures

above Tc (Si-C equilibrium temperature in acid lined melting furnace),
will decrease the carbon content
7. the spheroidizing treatment will decrease the carbon content (0,05 –

0,20 %) due to:
1. adding 1,0 – 1,5 % nodulizing material does decrease the carbon by

this percentage of its original value
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2. stirring during the treatment (graphite enters the slag or escapes as
CO).
8. Fluidity increase with increasing C-content, with maximum at the

eutectic point.
Carbon content:
GJL 3,2 %
SiMo 3,0 %
Nir 2,7 %
Length of filled spiral part:
L (cm) = 37,85 * CEL + 0,23 * T (°C) - 392
CEL = % C + % Si / 4 + % P / 2
9. The higher the C-content the lower the viscosity. See figure.
10. Estimation of the density at 20 °C is:
8,105 – 0,223 x (%C) – 0,091 x (%Si)
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Viscosity depending on C-content and temperature
VISCOSITY IN IRON & STEEL

0,0085
0,0075
Viscosity kg/m.s
1600 °C
1550 °C
1500 °C
0,0065
1450 °C
1400 °C
1350 °C
0,0055
0,0045
0,0 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5
Carbon in %
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Element Silicon Si
Extreme range limits % 1,80 – 3,00
Preferred range limits % 2,30 to 2,70
1,70 to 2,20 for low temperature applications
Special material % 2,75 to 4,5 % solution strengthened ferrite
Easy to test with spectrometer.
Effects:
1. Si < 2,75 % to obtain pearlite, bainite or martensite and to avoid the formation
of silicates that increase the brittleness (old guideline!)
2. Si > 2,75 % will lead to a solution strengthened matrix of ferrite. Anyhow the
CE must be such that porosity and graphite flotation are controlled.
3. increasing silicon will increase the amount of ferrite
4. increasing silicon will increase the strength and hardness of the ferrite
structure present
5. an important influence on the free graphite morphology if added as inoculant:

increases the nodule count and decrease carbide formation tendency.
6. a high Ni + Si content (niresist irons) will increase the presence / promote

chunky graphite in sections > 50 mm
7. increases the transition temperature in shock resistance test (cold brittleness)
8. increases the Ac1- and Ac3-temperature (formation of austenite).
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Element Manganese Mn
Extended range limits % 0,00 – 0,80

Preferred range limits % 0,30 to 0,40 for pearlitic (<25 mm)
0,50 to 0,60 for pearlitic (>25 mm)
0,15 to 0,25 for ferritic
Easy to test with spectrometer.
It does decrease the carbon equivalent a little:
CE = % C + 0,31 (%Si) + 0,33 (%P) + 0,41 (%S) – 0,027 (%Mn) or
CE = %C + 0,31 (%Si) + 0,33 (%P) + 0,047 (%Ni) + 0,40 (%S) – 0,015 (%Mo)
– 0,063 (%Cr) – 0,135 (%V) – 0,027 (%Mn) + 0,074 (%Cu) + 0,25 (%Al)
Manganese has a considerable influence on the structure. To obtain a complete

ferritic structure in as cast condition, the percentage of manganese must be lower
than 0,20% for a wall thickness over 60 mm, independent of the amount of silicon.
The preferred contents are:
* Mn < 0,25 %: preferred for ferrite ductile iron

* Mn < 0,60 %: preferred for pearlitic ductile iron.
Figure 42
Preferred maximum Mn-
content
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Microstructure influence (ferrite – pearlite) of Mn-addition
Effects:
1. has a high segregation effect, so it will be difficult for thick section castings to
have ferritic structure in the center, increase porosity tendency in the center
and increase the presence of center and grain boundary located carbides. Mn
< 0,60 %
2. pearlite promoter / stabilizer and forms carbides. If Mn > 0,70 %, intercellular

manganese carbides will be present. If Mn > 0,75 %, even a heat treatment
cannot remove the pearlite anymore.
3. does increase of the tensile strength and yield strength slightly
4. decrease the ductility (elongation) and confidence level under dynamic loads
5. decrease the Charpy V result and shift transition temperature slightly to higher
temperatures
6. decrease the machinability (phosphide eutectic) and hardness
7. increase hardenability
8. increase the tendency to hydrogen pickup (danger for pinholes)
9. lowers both eutectic and eutectoid temperatures
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Element Phosphorus P
Extreme limit range % 0,02 to 0,05 with a maximum 0,08 %

Preferred limit range % 0,02 to 0,04
Easy to measure with spectrometer if proper calibration samples are used.
For ferrite P < 0,035 %, especially if cold temperatures are involved. Preferred:
P + Si < 2,53 % for P < 0,03 % (Charpy V at -40 °C) See figure.
For pearlite P < 0,050 %.
Absolute maximum is 0,08 %!
IMPACT TRANSITION TEMPERATURE
% Si
Transition temperature 2,9
visible with Charpy V test 2,7
2,5
With 0,08 %P and 2,7 % Si, 2,3

the transition temperature will
-10°C
be around room temperature 2,1
(depending on the other 1,9 -20°C

-60°C -40°C
elements present).
1,7 -30°C
-50°C
1,5
0,01 0,03 0,05 0,07 0,09
0,02 0,04 0,06 0,08 %P
Effects:
1. Promotes pearlite
2. It has a high segregation effect (see chapter 4.4.2), which indicates problems
for thick wall castings. There will be phosphide eutectic, steadite, which have a
negative influence on elevated temperature (low melting point). It will also
increase the porosity tendency in the center.
0,01 % P forms about 0,064 % of Fe3P
Because other elements as Ti and Cr, but especially Mo, also segregate to the
center, causing more complex and more brittle eutectic / constituents!
P-eutectics cannot be removed by heat treatment!
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The P-eutectic is difficult to identify at 100 x magnification. It is clearly visible at

500 x
3. Phosphorus also forms, together with magnesium, some very hard and brittle
magnesium-phosphide! Too high phosphorous (> 0,040 %) and magnesium (>
0,045 %) will result in a Charpy V non-complying metal at minus temperatures.
4. Forms intercellular carbide network (in combination with Mn, Cr...)
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5. Increase the tensile slightly (in as cast condition, with maximum at about 0,10
to 0,12 % P), yield strength is increased more, but the ductility (elongation and
Charpy V) will decrease much. This happens as well in as-cast as heat treated
condition. It will also increase the transition temperature, visible with the
Charpy V test result (see figure before).
Tensile test at
20 °C
Test at 20 °C
6. Decrease the dynamic strength / fatigue strength
7. Decrease the weldability (which is anyhow already low for ductile iron).
Remark:
No other element can compensate the negative influence of P!
The brittleness (tensile elongation, Charpy V) due to P-eutectic cannot be

removed by heat treatment!
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Element Sulfur S
Extreme limit range % 0,004 to 0,015

Preferred limit range % 0,008 to 0,012
Easy to detect with spectrometer if it is properly calibrated for this element.

Pay attention because the indicated S-content is not the free S-content! It is:
Sspectrometer = Sfree + SMgS

It is preferred to have an initial (before nodulizing) S-content of < 0,025 % to avoid a
too high required Mg-addition and the formation of an excess amount of slag.
Effects:
1. reacts with Mg and RE (rare earths, especially Ce) present in the nodulizers as
well as Ca and Ba (present in some inoculants)
2. will not react with manganese (too high free energy required)
3. increasing S-content will increase the effect of subversive elements
4. the small sulphides (MgS, CeS, CaS, BaS) are important for the inoculation
efficiency: increasing sulfur content increases the inoculation efficiency
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5. preferred minimum content is 0,008 %, to prevent carbides (manganese and
magnesium carbides). If the level is S = 0,004 % and the Mg level is > 0,04 %,
there will be carbides.
% S (spectrometer)
after nodulising
0,016
0,014
Low nodularity
target range
0,010
Carbides, low nodule count,

0,006 shrinkage
0,002
0,02 0,03 0,04 0,05 0,06
% Mg (spectrometer)
Typical degenerated
graphite due to too low
sulfur (red arrow)
Also, carbides can be present

(yellow arrow)
Structure with too low S-content
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5.2 SPHEROIDISING ELEMENTS
These are the elements that tend to form free spheroidal graphite with a higher
nodularity.
Element Magnesium Mg
Extreme limit range % 0,02 – 0,06

Preferred limit range % 0,028 – 0,040 for thin sections
% 0,040 – 0,045 for high wall thickness
It is easy to measure with spectrometer on the condition that it is properly calibrated.
The measured Mg-content is not only the free Mg, but:
Mgspectrometer = Mgfree + MgMgS + Mgdross + Mgother components

For this reason, the sample should be free of slag and other inclusions.
Pay attention, the mentioned contents are tested in the casting or pouring box.
The fading (Mg-content decrease), depending on the transport time, type of
ladle and type of pouring will be minimum 0,001 % / minute!
Effects:
1. decreases amount of S and O in the metal to increase the nodularity and act
as potential binder for oxygen during transport and pouring
2. increases the nodularity up to about 0,06 %; if more, it will form exploded

graphite, especially if the iron has a high CE
3. forms intergranular carbides if Mg > 0,07 % (see figure) and consequently an

increasing shrinkage leading to an increasing porosity tendency
4. forms exploded graphite, tend to form crab graphite and flake graphite clusters
on cell boundaries if Mg > 0,06 %
5. forms “dross” if the silicon and or sulfur content are high and the pouring is
done turbulent. The potential dross is a combination of MgS, MgSiO3,
Mg2SiO4…
6. the Mg-content of returns is removed by re-melting
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% S (spectrometer)
after nodulising
0,016
0,014
Low nodularity
target range
0,010

0,006 shrinkage
0,002
0,02 0,03 0,04 0,05 0,06
% Mg (spectrometer)
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Element RE (Rare Earths containing cerium, lithium…. Ce, Li…

Preferred limit range % 0,00 – 0,020; depending on wall thickness and
the presence of subversive elements
It is easy to measure with spectrometer on the condition that it is properly calibrated.
The Ce-content measured is not the free Ce, but contains also the CeS and the
reaction with the degenerating elements as are Ti, Te, As, Pb, Sb, Bi
Especially the element Ce is very active and the activity of it is known. Latest types
contain the element Yt, of which very few is known.
RE (Ce) are, compared to Mg, less fading in practice: factor 0,0008 / minute
compared to up to 0,0022 / minute for Mg.
Effects:
1. The Ce content (Ce is about 50 % of the RE-material) must be matched with

the Mg-content. If not, incorrect shaped graphite can appear as is Exploded
graphite (Mg + RE) and Chunky graphite (Ce-content).
Practically maximum as RE: < 0,035 %, preferred 0,020 %
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2. Ce is added to compensate the subversive elements: neutralises the effect of
Ti, Te, As, Pb, Sb, Bi
Ceactive = Cespectro - (Ti/5) - (Sb/0,5) - (Pb/0,5) - (Bi/2) - (Te/0,5)
If too much, chunky graphite will appear. Si and Ni will increase this tendency.
Chunky graphite
Minimum additions:
% Ce > (%Ti/5) + (%Sb/0,5) + (%Pb/0,5) + (%Bi/2) + (%Te/0,5)

to avoid degenerated graphite
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%Ce < 0,02013 – 0,000249 * W + 0,000001 * W 2 – 0,00000001 * W3
to avoid chunky graphite
W is all thickness in mm
If too few (compared to the graphite degenerated elements), intercellular flake

graphite will appear.
3. Ce will increase the number of nodules per mm2 by formation of CeS (nuclei)
4. an excess promotes carbides in thick sections, especially if Mg-content and

CE is high
5. the RE in the returns (Ce-content) is removed by re-melting
Remark
Nearly all FeSiMg-alloys contain RE! It is not always indicated and should be
specified at the purchasing order.
FeSiMg without RE is more expansive than with RE.
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Element Calcium Ca
Preferred limit range % 0,00 – 0,005
It can be measured by spectrometer, if properly calibrated, which is not easy. It is

non-soluble in iron. The Ca-content measured, is always the Ca from components.
This element is mostly added by the inoculant.

It reacts as well with S as with O2. It forms very liquid slag, which is very difficult to
remove. For this reason, it is mostly combined with Ba, which is same type of
element as Ca, see Table of Mendeljev).
Effects:
1. unsolvable in iron, so it forms very liquid slag, difficult to remove
2. increases the efficiency of the inoculation and the number of nodules per mm2
(CaS act as nuclei)
3. increases nodularity (react with sulfur and oxygen)
4. if in excess: it can promote carbides, but seldom
5. the Ca in the returns is removed by remelting.
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Element Barium Ba

This element is mostly added by the inoculant. It is many times used

to be combined with Ca because it produces a dry and crumbly
slag, which can, even if mixed with the liquid slag of Ca, easily be
removed.
Same type of element (see table of Mendeljev): alkaline earth

metals.
Effects:
1. is not solvable in iron, so it forms dry and crumbly slag
2. increases the number of nodules per mm2 (extra nuclei BaO / BaS)
3. increases the efficiency of inoculation treatment.by reducing the fading
Component Density 20°C

kg/dm3
Knowing that the density of liquid
SiO2 2,29
ductile iron will be around 6,6
AlN 3,26
kg/dm3, the BaO inclusion (with a
CaO 3,32
density of 5,72 kg/dm3) will float
the slowest and be longer active MgO 3,58
as nuclei (decrease the fading) Al2O3 3,7
Ti5O5 4,6
BaS density 4,25 kg/dm3 TiN 5,22
CaS 2,18 MnO 5,44
MgS 2,85 ZrO 5,6
CeS 5,90 BaO 5,72
ZrN 7,09
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If these elements are not intentionally added and their percentage is low, they
are called “tramp or residual elements”.
The most common elements are described.
Element Nickel Ni
Extended limit range % 0,00 – 2,00, exceptionally to 4 %

The measuring by spectrometer is easy if the calibration is done properly.
The solubility is very high, and the C-solubility decrease by 0,05 % if 1 % of Ni is

added.
There are ductile iron types with much higher content of Ni, the Niresists (15 to 35 %
Ni). These types are not considered / discussed here.
There are 2 major applications where Ni is intentionally added:
1. to get a 100 % pearlitic structure (percentage depends on the wall

thickness) and
2. if the ductile iron is used for low temperature applications (need to get an
additional ferritising heat treatment).
Ni can be added partly by using Nickel-Magnesium as nodulizers (a little less

accurate because the additional Ni – from the NiMg – is calculated and a sample
after nodulizing does not allow anymore to correct the chemistry (lack of time due to
Mg-fading).
Effects:
1. promotes fine-grained pearlite but does not stabilize it. The effect is increasing
quickly if Ni > 0,75 %. The effect is anyhow lower than Cu and Mn and surely
much lower than Sn for equal additions. The by Ni formed pearlite is easy to
transform by a heat treatment
Reduce eutectoid temperature (austenite to ferrite) by about 22 °C

Reduce the distance between stable and metastable eutectic temperatures
Will avoid ferrite in the “as cast” condition
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2. increase the hardenability (also for surface hardening), but less than Cu and
Mo for equal additions. Martensite only forms if Ni > 5 %. If it is used in
combination with Cu and or Mo, a bainite matrix can be achieved
(austempered ductile iron).
3. Ni is a negative segregating element (Ni-content at the surface is higher

compared to the center. Due to its graphitising effect, the chill tendency will
decrease. The graphitising factor is:
GF = (%C) x [(%Si) – 0,2 x{(%Mn) – 1,7 x (%S) – 0,3} – 1,2 x (% Cr)

– 0,4 x (%Mo) – 2 x (%V) – 8 x (%Mg) + 0,1 x (%P) + 0,4 x (%Ni)
+ 0,5 x (%Al) +0,4 x (%Ti) + 0,2 x (%Cu)]
4. Promotes chunky graphite in presence of Ce (especially if also high Si-content

is present), especially in thick wall castings
5. Does not increase the porosity tendency.
6. Mechanical properties:
* increase the strength of ferrite

* increase the tensile strength and yield strength (yield strength more
than the tensile strength), especially for ferritic iron
Tensile strength = 286 + 85,6 * (% Ni) + 84,6 * (% Si)

Yield 0,2 strength = 135 + 118 * (% Ni) + 105 * (% Si)
* increase the hardness

* reduce the elongation
* the transition temperature (Charpy V test) is raised about 10 °C per 1
% of Ni. This is less compared to Cu and Mo.
The change of mechanical properties, especially the elongation, is less

after heat treatment.
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Element Molybdenum Mo
Extended limit range % 0,10 – 0,75, exceptionally up to 1,5 %

It is a very expensive (and large price fluctuating) element. Therefore, it is mostly

used for austempered (bainitic) ductile iron and hardened ductile iron.
CCT-diagram depending on
Mo-content
Fairhurst & Rohrig
Effects:
1. It has no influence on nodularity or nodule count
2. segregates very much, so that It will form a network of small carbides

(especially in the center of thick wall castings). This effect will be increased in
the presence of Cr and V. The P-content must be ≤ 0,02 % to avoid brittle and
low-melting point MoP-constituents.
This segregation will increase, to a large extend, the porosity tendency in the
center and hot spots of thick wall castings.
This segregation (and consequently carbide formation) will decrease the

Charpy V -value and fatigue strength.
3. promotes pearlite but less than Cu and Sn. It is mostly added together with
one of them (Cu or Sn).
4. Increase the hardenability very much, especially if the Mo > 0,5 %. It will be
easy to form bainite and or martensite.
5. increase the Ac3-temperature
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6. is mainly used for higher temperature applications (> 450 °C) due to its
resistance to decompose the pearlite and the higher resistance to creep.
7. The tensile and yield strength are increasing, as well as the hardness. The
elongation is decreasing. The Charpy V-value is decreasing and the transition
temperature increasing.
Remark:
Ductile iron, alloyed with Mo, is mostly heat treated.
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Element Copper Cu
Extended limit range % 0,00 – 1,90

Copper is soluble up to 3,5 % in iron; the solubility decreases in ductile iron due to
the Mg: 0,08 % Mg reduce the solubility to 1,5 % Cu. If more copper is added, free
Cu-particles will show up.
An addition of about 0,75 % Cu can be used if a 100 % pearlitic structure as-cast is

required (percentage depends on the wall thickness). It has a similar effect as Nickel.
If added < 0,30 %, nearly no effect.
In case of fully ferritic structure as-cast: Cu < 0,05 %.
Effects:
1. promotes strongly fine-grained pearlite, decreases ferrite formation as-cast

condition. The increase in pearlite is the most for Cu ranging from 0,2 % till 0,6
% (depending on wall thickness). If Cu > 0,75 %, even an ferritising heat
treatment will not be able to obtain a fully ferritic matrix.
2. reduce eutectoid temperature and the temperature difference between stable

and metastable eutectic temperatures
3. it has no influence on machinability
4. increase hardenability in combination with Mo (less than Mo if used single)

and Ni. Bainitic and martensitic matrix are obtainable by quenching.
5. does not increase the shrinkage tendency and is a negative segregating

element (content at the surface is higher than in center of the section).
6. promotes flake graphite in combination with Ti or and Pb. The effect on the
tensile strength for 1 % of Cu (and Ti not compensated by Ce), can be:
750 MPa for 0 % Ti; 650 MPa for 0,05 % Ti; 350 MPa for 0,12 % Ti
• Increase the tensile strength (about 70 MPa for 1 % of Cu). In normalised

condition, the tensile as-cast will decrease if Cu > 1,2 % and not increase
anymore by normalising if Cu > 0,8 %.
• Yield strength will increase in as-cast as normalized condition.
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• Hardness increase in as-cast as well as normalized condition (25 HB in case
of 1 % Cu).
• Elongation is decreasing in as-cast as well as normalised condition (6 % in

case of 1 % Cu)
• Charpy V-test: for 1 % Cu, the value decrease by 15 % (example from 16 to

13,5 J) and the transition temperature increase by 45 °C.
Remark:
When a pearlitic ductile iron with Cu > 0,75 % is annealed, the nodules will
have several small extensions of secondary graphite. See picture.
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Element Chromium Cr

Is seldom used as alloying element in ductile iron.
Effects:
1. < 0,04 % for ferritic type (carbide formation)
2. < 0,15 % for pearlitic type if not used as alloying element
3. not a strong pearlite promoter but a very powerful carbide former,

especially in center of section and this effect is increased with the
combination of Mn and Cr
4. chromium-carbides are very resistant to annealing (heat treatment)
5. small influence on promotion of pearlite
6. increase shrinkage tendency
7. decrease the machinability
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Element Tin Sn

Ferritic type: < 0,01 % (strong pearlite former)

Pearlitic type: < 0,15 % for pearlitic type
Pay attention for the purity of the added tin. Alloys contain many times Pb and As,
which influence the graphite shape (degeneration).
Effects:
1. is a very strong pearlite promoter and stabilizer. Pearlite is nearly

(commercially) impossible to transform to ferrite if Sn > 0,03 %.
2. Formation (restricted amount) of intercellular structure with flake graphite (if Sn

> 0,15 %)
3. No increase in shrinkage tendency
• Tensile is increasing till 0,15 % in as-cast condition and till 0,10 % in heat
treated condition. Above 0,15 %, it is decreasing quickly.
• Yield strength shows a small increasing (more in heat treated material than in
as-cast material)
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• The hardness in as-cast material is rapidly increasing. In heat treated

conditions, the hardness is higher, but the increasing is smaller.
• The elongation is sharply decreasing up to 0,08 %; with higher contents, the

decrease is smaller.
• The Charpy V value is decreasing due to the presence of pearlite (not

particularly due to Sn). Also, the transition temperature is increasing quickly.
See figure.
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Element Vanadium V

Nearly never used in ductile iron! If present, it will be a residual element from the
charged material.
Effects:
1. very powerful carbide former if % V > 0,03 %
2. light promotion of pearlite
3. increase the creep resistance (formation of carbides)
4. vanadium-carbides are resistant to annealing (heat treatment)
5. strong decrease of machinability
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These elements are normally not intentionally added to the metal due to their effect
on the graphite shape and appearance. For this reason, only a preferred range will
be indicated.
Sometimes a combination is used to avoid a negative effect of the single elements.
Element Boron B
Mostly not intentionally added.

B is not soluble in austenite structure.
The presence of B is due to the use of “hardened steel scrap” or malleable iron
scrap. When acid lined melting furnaces are used (and especially when boron-acid is
the sinter agent), the sintering and first melts can introduce B into the metal.
Effects:
1. B decrease the hardenability; it promotes the ferrite content and an addition of

6 to 14 ppm will decrease the hardness by about 25 HB.
2. B forms carbides, mostly as an intercellular carbide network, which decrease

the ductility (especially the shock resistance)
3. boron-carbides are resistant (difficult to remove) to annealing (heat treatment).
Element Arsenic As
Is not intentionally added. Can be introduced by certain steel returns.
Effects:
1. As > 0,02 % will definitely give problems for graphite morphology (favours
flake graphite)
2. Is sometimes used to balance too high Ce content (but it is preferred to use Sb

for this reason)
3. Very strong pearlite promoter and stabilizer, effective from 0,008 %.
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Element Tellurium Te
Safe range % < 0,002
Is mostly not intentionally introduced and can be present due to steel charge.
Effects:
1. Decrease decreases the nodularity in the absence of rare earths (should be

compensated by Ce)
2. Increase the tendency to carbide formation
3. Decrease the formation of pinholes.
Element Lead Pb
Is never intentionally added. Mostly introduced by painted (anti-corrosion) steel scrap

or returns or addition of tin alloys.
Effects:
1. promotes flake and spiky graphite and must be compensated by Ce
2. will give serious problems if % Pb > 0 ,003 %.
Element Titanium Ti
Safe range % < 0,05
Is never intentionally added. Mostly introduced by (especially painted) steel scrap or

returns (de-oxidation of steel) or pig iron.
Effects:
1. promotes worm-like (vermicular, compacted) and flake graphite and must be

compensated by Ce
2. forms intergranular carbides if % Ti > 0,03 %
3. decrease the ductility, especially the shock resistance
Is very dangerous for thick wall castings due to the high segregation tendency!
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Element Aluminium Al
Safe range % < 0,03 %
Is never intentionally added. Mostly introduced by steel scrap or returns (de-oxidation

of steel) or pig iron and especially by FeSi-alloys and inoculants.
Effects:
1. promotes pin holing, especially in the presence of Ti
2. decreases carbides in thin sections, corners…
3. increases the resistance to oxidation
4. promotes the worm-like (vermicular, compacted) and flake graphite, which

should be compensated by the addition of Ce.
Element Antimony Sb

Safe range % < 0,003 %
It is many times intentionally added to compensate too much Ce (if the addition of RE
is not under control or in case of thick section castings).
It is not removed by re-melting and can build-up to too high contents.
Effects:
1. it is the strongest pearlite promoter
2. can avoid the formation of chunky-graphite in thick sections (due to too high
Ce-content)
3. decreases nodularity (by the formation of flake graphite) in the absence of rare
earths (especially Ce)
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Element Bismuth Bi
Safe range % < 0,002
Is mostly added by the inoculant for increasing the nodule count.

It is not removed by re-melting and can build-up to a high content.
Effects:
1. promotes the worm-like (vermicular, compacted), flake and chunky graphite in

the absence (or too low content) of rare earths
2. increases number of nodules, especially in the presence of rare earths (Ce)
3. pearlite promoter
Element Zirconium Zr
Safe range % < 0,01
Is added by inoculants.
Effects:
1. promotes worm-like (vermicular, compacted) and flake graphite
2. promotes intercellular flake graphite
Element Zink Zn
Safe range % < 0,01
Introduced by galvanised and or painted charge material.
Effects:
1. promotes worm-like (vermicular, compacted) and flake graphite
2. promotes intercellular flake graphite
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Element Oxygen O
Effects:
1. forms gas bubbles in thick sections
2. deteriorate graphite shape if too low nodularity level
Is nearly never a problem for ductile iron due to the nodulising (Mg + O  MgO).
The content can increase during uncovered transport to the mould and too turbulent
filling of the mould. Oxygen will increase the dross formation.
Element Hydrogen H
Effects:
1. promotes pin holing
2. promotes worm-like gas paths (especially in combination with N)
3. promotes carbide formation, especially “inverse chilling” in the center of the

section
Element Nitrogen N
Presence (in ductile iron):
* electrical furnace, low and high frequency: 0,0050 %

* cupola 0,0090 %
* cupola iron desulfurized 0,0070 %
Effects:
1. promotes flake graphite

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2. promotes pearlite
3. it is a catalyst for pinholing
4. tendency to form porosity and gas bubbles (0,0035 % soluble in iron if no Ti or

V is present)
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5.6 OVERVIEW
5.6.1 EFFECTS
5.6.2 EFFECT QUANTIFYING
5.6.3 PREFERRED LIMITS
5.6.4 EXTRA RULES
5.6.1 EFFECTS
5.1.1 Segregation behaviour
5.1.2 Influence on graphite shape
5.1.3 Tendency to promote pearlite
5.1.4 Tendency to promote ferrite
5.1.5 Tendency to promote carbides
5.1.1 SEGREGATION BEHAVIOUR
The tendency to segregate is indicated in a relative ranking:
Element Mo Ti V Cr Mn P Si Co Ni Cu
Factor 25,3 25,0 13,2 11,6 1,7-3,5 2,0 0,7 0,4 0,3 0,1
If the factor is < 1,0: segregates in first freezing metal

> 1,0: segregates in last freezing metal.
5.1.2 INFLUENCE ON GRAPHITE SHAPE
Promoting chunky graphite in decreasing order:
Ce, Ca, Si, Ni
Promoting intercellular flake graphite and decreasing chunky graphite in case of too
high Ce-content, in decreasing order:
Bi, Pb, Sb, As, Cd, Al, Sn, Cu, S
Promoting intercellular flake graphite in decreasing order:
Zr, Zn, Se
Promoting flake graphite
Ti, N (if both present, there is no tendency to form flake graphite)

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5.1.3 TENDENCY TO PROMOTE PEARLITE
The pearlite promoting effect is as follows:
Element Sn Mo P Cu Ti Mn Ni Cr
Effectiveness 39,0 7,9 5,6 4,9 4,4 0,44 0,37 0,37
Complete list: As, Cr, Cu, Mn, Mo, N, Ni, P, Sb, Sn, Ti, V
Pearlite factor Pprl:
Pprl = 3,0 x (%Mn) – 2,65 x (%Si – 2,0) + 7,75 x (%Cu) + 90 x (%Sn) + 357 x (%Pb)
+ 333 x (%Bi) + 20,1 x (%As) + 9,6 x (%Cr) + 71,7 x (%Sb)
5.1.4 TENDENCY TO PROMOTE FERRITE.
The elements Si and C are ferrite promoters. This tendency can be calculated with
the formula for the graphitising factor K:
K = %C * {%Si – 0,2 *(%Mn – 1,7 * %S – 0,3) – 1,2 * %Cr – 0,4 * %Mo – 2 * %V

– 8 * %Mg + 0,1 * %P + 0,4 * %Ni + 0,5 * %Al + 0,4 * %Ti + 0,2 * %Cu}
5.1.5 TENDENCY TO PROMOTE CARBIDES
The following elements, in alphabetic order, do promote carbides:
B, Ca, Cr, H, Mg, Mn, Mo, Se, Te, Ti, V
The combination of Mg and S is also important, because high Mg-content compared

to low S-content (less nuclei and mostly lower nodule count) leads to carbide
formation.
Metal with Mg ≥ 0,04 % and S ≤ 0,004 % will have carbides!
The K-factor in chapter 5.1.4 is the reverse from the carbide formation tendency.
Note
Pay attention for the elements that are recovered upon remelting!
1. Mg and RE are not recovered

2. Si, Mn, Cr are recovered depending on the furnace lining and melting method
3. Ni, Cu, Mo, Sb, As. Sn are nearly completely recovered
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5.6.2 EFFECT QUANTIFYING
SUMMARY OF INFLUENCES OF ELEMENTS
Element Segregation Pearlite Anti- Promotion Promotion Promotion

factor Promotion nodulising Intercellular Chunky Carbides
Effectiveness factor graphite Graphite
C
Si 0,7 X
Mn 1,7 – 3,5 0,44 X
P 2,0 5,60
S X
Ni 0,3 0,37 X
Cu 0,1 4,90 X
Ti 25,0 4,40 4,4 X X
V 13,2 X X
Cr 11,6 0,37 X
Co 0,4
Sn 39,0 2,3 X
Mo 25,3 7,90 X
Bi X 370 X
Pb 290 X
Sb X 5,0 X
As X 2,0 X
Cd X
Al 1,6 X
Mg X
Ce X X
Ca X
Zn X
Zr X
N X
B X
H X
Se X
Te X
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5.6.3 PREFERRED LIMITS
Preferred
Element Remarks
limits
Few requirements, try to get CE on 4,33 – 4,37

C without risk for graphite flotation (wall thickness,
pouring temperature)
Si < 2,75 Thick wall castings
Si < 2,1 Low temperature applications
Look at the consequences on CE and tensile
Si
strength in case of ferritic structure DI
Mn < 0,60 Due to the segregation effect
Mn < 0,25 Charpy V testing
Mn < 0,15 Low temperature Charpy V testing
P 0,05 All non-pressurised applications
P 0,035 Preferred
P 0,030 Applications at low temperature
S 0,008 – 0,012 Best range
Tested in pouring box; depending on RE content

Mg 0,03 – 0,04
and wall thickness
Depending on Ce-content and wall thickness to
RE < 0,05
prevent chunky graphite
Even in the thinnest walls.
Ce < 0,02 Compensates the graphite degenerating effect of
Ti, Al, Sb, Pb, Bi
Ce 0,00 In section > 200 mm
Pay attention for fluid slag, which effect can be
Ca 0,00 – 0,005
decreased in combination with Ba.
Ba 0,00 – 0,005 Used in inoculant for furnace metal pre-treatment
Depending on wall thickness.

Used for low temperature ferritic iron to increase
Ni 0,20 – 0,80
the tensile strength; heat treatment required for
ferritising the structure.
Used in ADI ductile iron, mostly in combination with
Ni
Mo for thicker sections
Depending on wall thickness. Pay attention for the
Mo 0,25 – 0,50 tendency to increase porosity in centre of the
section.
Cu 0,25 – 1,75 Pearlite promoter; depending on section thickness
Cr Pearlite and carbide promoter
Pearlite promoter; limited by graphite degenerating
Sn 0,05 – 0,15
effect is > 0,15 % - decrease of tensile strength
Strong carbide former. Machinability decrease
V 0,00 – 0,03
strongly.
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Preferred
Element Remarks
limits
B 0,002 Forms intergranular carbides.

Tends to form flake graphite (can be compensated
As 0,02
by Ce)
Forms carbides and promotes flake graphite (can
Te 0,02
be compensated by Ce)
Forms spiky graphite (can be compensated by Ce)
Pb 0,002
and flake graphite
Forms intergranular, very embrittling carbides (can
Ti 0,03
be compensated by Ce)
Promotes pin holing and flake graphite (can be
Al 0,05
compensated by Ce). Can also be present in dross.
Very strong pearlite former.
Sb 0,001 Promotes flake graphite.
Can be used to compensate to high Ce-contents.
Increase the tendency for chunky graphite in the
absence of Ce.
Bi 0,002
Increase the nodule count.
Increase the pearlite tendency.
Zr 0,010 Increase tendency for flake graphite formation
Zn 0,01 Increase the tendency for flake and spiky graphite
Increase the tendency for intercellular flake
Se 0,03
graphite
Cd 0,005
(8 to 50 ppm)
O 0,0008 – 0,005
Oxygen is required for nuclei formation.
High tendency for pinhole formation.
H 0,000 – 0,0015
Tendency to promote inverse chilling.
High tendency for pinhole formation.
N 0,000 – 0,009
Tendency to form flake graphite
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5.6.4 EXTRA RULES
% S (spectrometer)
after nodulising
0,016
0,014
Low nodularity
target range
0,010

0,006 shrinkage
0,002
0,02 0,03 0,04 0,05 0,06
% Mg (spectrometer)
PREFERRED CHEMISTRY DUCTILE IRON

% Si
3,5
Graphite
flotation
3,0 Impact
low
2,5
Preferred
Excessive range
shrinkage
2,0
Tendency to form white iron
1,5
3,4 3,5 3,6 3,7 3,8 3,9 %C
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The chemistry is mostly measured by the spectrometer (quick result). But be aware
that the spectrometer needs a proper usage and the samples must be in the best
condition.
The most common accuracy of spectrometers is the following:
%C 0,03 % % Mg 0,0015 % %P 0,002 %

% Si 0,015 % % Ce 0,002 % %S 0,0015 %
% Mn 0,006 % % La 0,0003 % % Al 0,002 %
% Ti 0,001 %
% Cr low 0,005 % % Ni low 0,005 % % Sn 0,0015 %
% Cr high 0,05 % % Ni high 0,05 % % Bi 0,002 %
% Mo 0,005 % % Cu 0,005 % % Te 0,0005 %
% Pb 0,002 % % Sb 0,002 % % Zn 0,002 %
The tolerances on the chemical analysis, done on poured test blocs and or castings
(for steel and applicable for iron) by spectrometer, are:
ELEMENT STANDARD VALUE TOLERANCE ON

LIMITS IN % LIMITS IN %
C < 0,03 + 0,005

0,03 < < 0,08 +/- 0,01
0,08 < < 0,30 +/- 0,02
0,30 < < 0,60 +/- 0,03
0,60 < < 1,20 +/- 0,05
1,20 < < 2,00 +/- 0,06
2,00 < +/- 0,08
Si < 2,00 +/- 0,10
2,00 < +/- 0,20
Mn < 0,70 +/- 0,06
0,70 < < 2,00 +/- 0,10
2,00 < < 10,00 +/- 0,25
10,00 < +/- 0,40
S, P < 0,040 +/- 0,005
Cr < 2,00 +/- 0,10
2,00 < < 10,00 +/- 0,20
10,00 < < 15,00 +/- 0,30
15,00 < < 20,00 +/- 0,40
20,00 < +/- 0,50
Mo < 1,00 +/- 0,07
1,00 < < 2,00 +/- 0,10
2,00 < < 5,00 +/- 0,15
5,00 < < 30,00 +/- 0,20
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ELEMENT STANDARD VALUE TOLERANCE ON
LIMITS IN % LIMITS IN %
Ni < 1,00 +/- 0,07

1,00 < < 2,00 +/- 0,10
2,00 < < 5,00 +/- 0,15
5,00 < < 10,00 +/- 0,20
10,060 < < 20,00 +/- 0,25
20,00 < < 30,00 +/- 0,30
30,00 < +/- 0,50
Nb < 1,00 +/- 0,05
1,00 < +/- 0,10
V < 0,30 +/- 0,03
0,30 < < 1,00 +/- 0,07
N < 0,30 +/- 0,02
Cu < 2,00 +/- 0,12

2,00 < < 5,00 +/- 0,25
W < 1,00 +/- 0,05
1,00 < < 3,00 +/- 0,10
3,00 < < 6,00 +/- 0,15
Co < 25,00 +/- 0,40
25,00 < +/- 0,70
It is important to realize that this method (light spectrometer) is a “comparative”

method, meaning that the test result is compared with the result of certified samples.
If the equipment is not properly calibrated and standardized, the result will be
incorrect. See figure.
Figure
Standardizing samples with
certificate
If the samples are not matching the liquid metal (especially concerning
inclusions, as can be slag…), the result will be incorrect. See next figure.
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Figure
Sample with slag
If the testing is done incorrectly (spark above previous spark or overlapping

sparks or incorrect location on sample), the result will not be correct. See next
figures.
Figure
Incorrect sparked sample
Figure
Correct location of spark
The optical spectrometer is not usable for iron if the sample is not white
solidified due to the influence of the free graphite.
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6. INFLUENCE OF
METALLURGICAL TREATMENTS
6.1 INTRODUCTION
6.2 FURNACE PRETREATMENT
6.3 DESULFURIZING
6.4 SPHEROIDIZING
6.5 INOCULATION
6.6 FADING EFFECT
6.7 INTERESTING GUIDELINES
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6.1 INTRODUCTION
“Metallurgical” treatments are the treatments, of any kind what so ever, those are
done to:
1. To convert the base iron into ductile iron

2. Increase and or stabilize the quality of the material.
The quality of the metal concerns the strength (microstructure), ductility (nodularity,
carbides and microstructure) and section and surface quality (nodule count, porosity,
inclusions). The result of ductile iron conversion is measured or evaluated by the
following factors:
1. Nodularity - maximized
2. Nodule count – maximized but limited by the section of the casting
3. Chill carbides - minimized
4. Inverse chill - minimized
5. Shrinkage porosity - minimized
6. Inclusions metallurgical – minimized.
The metallurgical treatments will mainly influence the nodularity (desulfurising,

nodulising), nodule count (pre-treatment in furnace, inoculation) and carbide (pre-
treatment in furnace, inoculation) and inclusion presence (nodulising, desulfurising).
These treatments are the furnace pre-treatment, desulfurising (if required),

spheroidizing and inoculation for the irons.
Sometimes it is necessary to desulfurise the metal. This is mostly done during

melting (by adding chalk). This chalk adding must be done before the other
treatment.
The metallurgical treatments are done in furnace, during or after tapping the metal
from the furnace. Furnace pre-treatment is done in furnace, desulfurising can be
done in the furnace or a special ladle, nodulising is done in the ladle and inoculation
can be done in the ladle and or pouring box.
For series-casting mould spheroidizing as well as can be used. In this case it is

preferred to use filters to avoid reaction products (MgS) entering the casting.
This text will describe the procedure and effect of the treatment on the metallurgical
quality of the metal.
In the attachments, the effect of melting on the chemistry and the effect of the melting
and metallurgical treatments on the nuclei will be described.
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6.2 FURNACE PRETREATMENT
6.2.1 TARGET
6.2.2 TYPES
6.2.3 PROCEDURE
6.2.1 TARGET
The target of the furnace pre-treatment is: “To get a controlled condition for the liquid
metal, which requires a constant amount of nodulisers and inoculant and leads to a
constant and predictable metal strength and casting quality”.
To achieve this, the iron must be “pre-conditioned”. This means that it is treated in a
way that a nearly constant amount of oxygen and nuclei are present.
An efficient preconditioning can increase the number of nodules by 20 to 25 %.
Anyhow it is very important to keep the melting temperature low and constant
according to the melting instruction. This avoids a lot of variation in the liquid metal
quality (presence of oxygen and nuclei).
In principle the preconditioning should be done after the desulfurization, if this is

required. But some of the preconditioning activities are done during melting, so the
preconditioning will require another procedure in case of desulfurization.
6.2.2 TYPES
Knowing that the preconditioning is performed in the melting furnace with the target
to increase the number of nuclei in the liquid metal, it must be performed according to
the result of a test.
This test will mostly be a wedge test (see figure xx on next page) or the cooling curve
shown by the CE-meter (undercooking or ΔT).
When the melting charge consists of a high amount of steel, it is necessary to count
on the preconditioning from the start (steel does not contribute to the nuclei).
The preconditioning is mostly done by:
• Adding a significant percentage of the pig iron at the end

• Adding SiC (amount of +/- 0,4 %), especially when steel is involved
• Adding FeSiBa in furnace before tapping
• Adding extra inoculants during the first inoculation.
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One of the best pre-conditioners, if the oxygen content is normally high, is silicon-
carbide (SiC), added in the furnace before tapping. This is acting as follows:
1. carbon is reacting with oxygen and disappears as CO

2. silicon is entering the metal, increasing the silicon content.
A pre-conditioned iron will have a more effective inoculation (lower fading effect), see
figure 44, showing the white solidification in a wedge test.
The inoculation is done with FeSi.
Figure 44 Metal quality test by wedge
These very simple solutions are known by every foundry, but only the third one, extra
inoculation, which is not a real preconditioning because it is done after the tapping, is
mostly used and even without a high consistency concerning the amount.
The added amount varies, depending on the foundry, from 0,1 to 0,4 % SiC.
Some of the literature also mention that the preconditioning with SiC with decrease
the fading of the later inoculation effect.
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6.2.3 PROCEDURE
6.2.3.1 No desulfurization
The necessary procedure does include the way of charging and melting and can be
the following:
1. First charge, which has a high loading density, consisting of a mixture of steel
and returns
2. Than charging a mixture of returns and pig iron
3. Latest charge is pig iron and the preconditioning SiC
4. Melting up to 1400 – 1450 °C, depending on the chemical composition of the

liquid metal (see table with Tg and Tc temperatures for any material). The
temperature should stay below Tc till the chemical analysis is checked and
found correct.
Tg is the temperature below which Si + O2  SiO2 and Tc is the temperature
above which SiO2  Si + O2 and C + O  CO.
5. Taking test samples for the chemical analysis and the cooling curve / CE
6. Depending on the result, modifying the composition and/or adding the extra
preconditioning product, which can be:
• No extra addition in the furnace but 0,1 % extra inoculants if the

undercooling is 3 – 5 °C
• Extra pig iron in the furnace if the undercooling is 5 – 7 °C
• Extra SiC and pig iron if the undercooling is > 8 °C
• If the undercooling is near to 10 °C, it will be impossible to restore the
metallurgical quality level to an acceptable level.
Adding FeSiBa can be beneficial because it will bring the oxygen content to
a low (more or less constant for that melting procedure) level so that the
amount of added Mg can be minimized and optimized.
7. Heating to the tapping temperature, remove slag and tap.
As it should be in every procedure or instruction, the action must be related to test

results and the amount of action should also be prescribed. Only in this way,
subjective reactions of the operator can be avoided.
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6.2.3.2 With desulfurization
The necessary procedure does include the way of charging and melting and can be
the following:
1. First charge, which has a high loading density, consisting of a mixture of steel
and returns
3. Latest charge is pig iron
4. Melting up to 1400 – 1450 °C, depending on the chemical composition of the

liquid metal (see table with Tg and Tc temperatures for any material). The
temperature should stay below Tc.
5. Desulfurization
7. Depending on the result, modifying the composition and/or adding the extra
preconditioning product, which can be:
• No extra addition in the furnace but 0,1 % extra inoculants if the

undercooling is 3 – 5 °C
• Extra pig iron in the furnace if the undercooling is 5 – 7 °C
• Extra SiC and pig iron if the undercooling is > 8 °C
• If the undercooling is near to 10 °C, it will be impossible to restore the
metallurgical quality level to an acceptable level.
Adding FeSiBa can be beneficial because it will bring the oxygen content to
a low (more or less constant for that melting procedure) level so that the
amount of added Mg can be minimized and optimized.

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6.3 DESULFURIZING
6.3.1 INTRODUCTION
6.3.2 TYPES
6.3.3 PROCEDURE
6.3.4 TOO LOW SULFUR
6.3.1 INTRODUCTION
Ductile iron should have a final S-content between 0,008 – 0,012 % to have the best
free graphite segregation.
Because of the presence of higher S-content in several raw materials, mostly also in
some of the pig irons, the metallurgical treatment can be done by Mg in the form of
FeSiMgRE or NiMg.
But this treatment leads to a lot of slag and the residual Mg content will keep reacting
until solidification of the metal. This can lead to “dross” (slag with mainly Mg-reaction
products) inclusions. Therefore, there is a limit on the initial S-content of the liquid
metal before the Mg-treatment; commonly set on 0,025 % (0,030 % definitely needs
desulfurising).
To decrease the sulfur content, a separate “desulfurization” treatment is done. This

treatment contains an introduction of calcium-carbide to the liquid metal and should
bring the sulfur content below 0,020 %, better to 0,015 %. The lower the sulfur
content, the less magnesium must be added during nodulising
6.3.2 TYPES
It is important to decide if this treatment will be used, which means the foundry must
decide about the maximum initial sulfur content in the liquid iron that can be used
without desulfurising.
Desulfurising is a costly and time-consuming treatment, which also does not improve
the metallurgical quality of the liquid metal concerning nuclei. It can be that some gas
stirring (nitrogen) is necessary to have a good and consistent result.
The treatment alloy is cheap, but it cost a lot of energy to treat the metal, as well as
an extra treatment ladle should be used.
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The time needed for this treatment is high and after the treatment, an extra chemical
analysis must be performed to be able to calculate the proper addition of the
magnesium.
The desulfurising products used for this treatment are:
1. Calcium carbide CaC2 most common

2. Caustic soda NaOH rarely used (physiological hazards)
3. Sodium carbonate Na2CO3
4. Lime CaCO
5. Limestone CaCO3 seldom used (needs to become lime)
6. Calcium Cyanamid CaCN2 never use, it produces N2, which will enter the metal
The treatment alloy must meet the following requirements:
1. achieve the largest contact surface possible between iron and desulfurization
agent
2. provide high reaction kinetics
3. ensure treatment economy, including an easy removing of the slag.
Calcium-carbide is the most effective desulfurising agent, especially for low S-content
iron. The bulk density of calcium-carbide is 1,1 – 1,3 ton / m³ and the grain size
depends on the type of addition:
0,1 – 1,0 mm for stirring treatment

0,01 – 0,06 mm for injection with N2 addition.
The chemical composition of calcium-carbide is mostly:
CaC2 68 – 75 %
CaO 10 – 16 %
CaC2/CaO 4–7
Cfree 3–6%
SiO2 + Al2O3 + Fe2O3 3–6%
It can also be done with “lime” (CaO), which needs more addition even if fluorspar
and salt is added.
The reactions involved are:
CaC2  Ca + 2 C
Ca + S  CaS
CaC2 + S  CaS + 2 C
CaO + S  CaS + O
Si + 2 O  SiO2
2 CaO + 2 S + Si  2 CaS + SiO2
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The addition is done in the following way:
1. Or injection with nitrogen from the bottom of the ladle or with lance
2. Or stirring (mechanically, electromagnetic...) and product addition on top of

the liquid metal.
If no stirring or nitrogen injection is used, the efficiency will be much lower.
Additions of 0,50 – 1,0 % of CaC2 are common (depending on the initial sulfur
content) and treatment efficiencies of > 50 % are normally achieved.
The temperature decrease of the metal during treatment will be between 30 – 55 °C.
The result is depending on:
1. Sinitial: a higher initial content will lead to more S-removal
2. time of treatment: an increasing treatment time leads to increasing removal

of S
3. CaC2 content of the desulfuriser: an increasing amount of this element will

increase the S-removal
4. intensity of the stirring is the most crucial factor
5. grain size: a decreasing grain size will slightly increase the S-removal due
to a higher contact surface.
The result is independent of the liquid metal temperature!
The time for the treatment is in the range of 5 to 10 minutes, knowing that the
desulfurising rate slows down as sulfur content decreases.
If the desulfurising treatment is done, the S-content should be brought to < 0,015 %
to benefit to the maximum from the possible lower Mg addition for the nodulising.
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6.3.3 PROCEDURE
The necessary procedure does take in account the preliminary sulfur content and can
be the following:
1. First charge, which has a high loading density, consisting of a mixture of

steel and returns
3. Latest charge is pig iron and the preconditioning SiC
4. Melting up to 1400 – 1450 °C, depending on the chemical composition of

the liquid metal (see table with Tg and Tc temperatures for any material).
The temperature should stay below Tc till the chemical analysis is checked
and found correct.
6. Depending on the result concerning the Spreliminary content, perform the

desulfurising, which is done as follows:
• Furnace temperature 1425 – 1450 °C (depending on Tc

temperature)
• Add 1 % CaC, size 0,5 – 1,5 mm
• Tap liquid metal in ladle and let react during about 5 – 10 minutes
7. Reload the metal back in the furnace, in which alloy modifications could be
added (FeSi, FeMn, C...).

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6.3.4 TOO LOW SULFUR
Sulfur plays a graphitizing role and is needed, even in ductile iron. The small MgS
particles act as nuclei.
With cupola melting, the sulfur content is always high and desulfurising is nearly
always necessary (S < 0,025 %, preferred S ≤ 0,020 %).
With electrical melting, especially when very clean pig iron and electrode carburizer is
used, it is possible that the sulfur content is too low. It should be, before the
magnesium treatment > 0,15 % (preferred 0,015 – 0,020 %).
If the sulfur is too low, the magnesium addition must be low to avoid that magnesium
is reacting too much with the oxygen (will split all silicon oxides and may be others),
which renders the metal less prone for the inoculation (which needs oxygen to form
SiO2).
It is also known that magnesium reacts with sulfur and forms MnS, which is, if the
size is ≤ 50 µm, acting as nuclei (and consequently increases the nodule count).
See figure 45.
Typical degenerated
graphite due to too low
sulfur (red arrow)
Also, carbides can be present

(yellow arrow)
Figure 45 Structure with too low S-content
The figure 46 on next page gives an idea what happens depending on the Mg- and
S-content.
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% S (spectrometer)
after nodulising
0,016
0,014
Low nodularity
target range
0,010

0,006 shrinkage
0,002
0,02 0,03 0,04 0,05 0,06
% Mg (spectrometer)
Figure 46 Effect of Mg and S
Example: Effect of low % Sulphur on ductile iron microstructure
Material: ferritic ductile iron.

Grade: 420 MPa minimum tensile strength, 12% minimum elongation.
Problem: low nodule count <100mm2 / 5% carbide / shrinkage porosity.
Cause: <0.005% S in metal treated with FeSiMg6RE1, 1,6% addition at 1500°C.

Inoculation: 0,5% addition FeSi75 in pouring ladle.
Remedy: increased % S to 0,010 – 0,015% after nodulising

Result: increased nodule count >100mm2, no carbide, no porosity.
So, foundries, and not only grey iron foundries, can need FeS (pyrite) to
correct the S level, especially for electrical melting and too high Mg-addition.
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6.4 SPHEROIDIZING (NODULISING)
6.4.1 PURPOSE
6.4.2 TYPE OF NODULISER
6.4.3 Mg-CONTENT REQUIRED
6.4.4 Mg-RE CONTENT REQUIRED
6.4.5 TREATMENT METHODS
6.4.6 PROBLEM
6.4.1 PURPOSE
Nodulising is done to degas the metal (mostly oxygen) and to decrease the sulfur
content to a set level (not below 0,006 %). This action creates an ideal environment
to make class VI nodules.
The nodulising reaction is a process, which means it take time to finish.
Due to the reaction with oxygen which happens in contact with the air during
transport, pouring and filling of the mould cavity, an excess of magnesium must be
added. This excess must be maintained after the metal treatment until the point of
solidification, because:
1. The metal will come in contact with oxygen during pouring and mould filling.
This contact will be very intensive if there is turbulence.
2. The metal can come in contact with sulfur, located in the slag or the mould
material (chemical bounded sand using a catalyst with sulfur).
6.4.2 TYPE OF NODULISERS

The nodulizers are on the base of FeSi and Mg-addition, combined with RE.
There are also Ni-Mg alloys used in case the nickel can be used as an alloying
element.
Magnesium is chosen for this nodulising because it has a low boiling point, high
reactivity with oxygen and low solubility in iron. These features make reliable
additions to iron difficult. To minimize Mg reactivity calcium is added to the master
alloy. Magnesium content of the alloy is also restricted to lower the reactivity. To
increase solubility silicon is raised near the alloy by using ferrosilicon as cover
material. To satisfy diverse needs many alloys were developed with combinations of
Mg and rare earths.
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6.4.3 Mg-CONTENT REQUIRED

By experience it is required to have 0,03 to 0,035 % residual magnesium (amount of
magnesium in the solidified material) if no RE (Rare Earths) are present. When the
real amount is less, vermicular (compacted) and lamellar graphite shapes will appear.
See figure 47.
Figure 47
Graphite shape in
relation to residual
magnesium (no RE)
But nowadays, it is found that the Mg-content can be lower due to the
combination of RE, which is given in figure 51 and 52, page 91.
The following reactions will be present:
Mg + O ---> MgO
Mg + S ---> MgS
Mg + S + O ----> MgO + S
2 Mg + SiO2 ----> Si + 2MgO
2 MgS + SiO2 ----> Si + 2MgO + S
The higher the sulfur level, the more manganese-sulphides are formed. In addition,
there are also magnesium-sulphides from the treatment. If these reaction-products
enter the casting, the section and surface quality of the casting will be negatively
influenced. The higher the original level of sulfur, the more problems with slag and
the costlier the required amount of nodulisers will be. Therefore, it is preferred to
keep the sulfur level before the treatment lower than 0,025 %, preferably 0,015 to
0,020 %.
How much magnesium must be added?
1. The added amount must be according to the following formula:
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% Mgt = (0,75 % Sin + % Mgr) / η
Mgt : added amount of magnesium
Sin : percentage sulfur before treatment
Sf : residual S-content after treatment
Mgr : percentage magnesium present in the metal after
solidification
η : efficiency of the magnesium-addition.
Amount of FeSiMg added (more complete formula):
WFeSiMg = Wladle x (% Mgr + 0,76 (% Sin - % Sf) + 10-3t) x {T (oC)}0,5

(% MgFeSiMg x ƞ) (1450 °C)0,5
WFeSiMg : weight of Mg alloy used for the treatment,

Wladle : weight of liquid iron to be treated,
MgFeSiMg : % Mg in the treatment alloy
t : time between treatment and pouring
T : temperature of metal during treatment.
2. The faster the cooling, the higher the efficiency of the treatment will be, and
the less magnesium will have to be added. The nodule count will be higher as
well as the nodularity in case of equal Mg-content.
3. A too elevated level of residual magnesium will promote carbides and increase
shrinkage.
4. The presence of RE will decrease the required amount of Mg.
5. If the unwanted elements aluminium, arsenic, antimony and others, are

present, some rare earths (RE) are added in the noduliser (for example
cerium, lanthanum...). The RE neutralise the negative effect of these
subversive elements.
6. The fast cooling metal (thin sections and or chilled sections) results in a better
nodularity for the equal Mg-content.
7. Large sections will require a higher Mg-content due to the fading effect (see in
detail in a later chapter).
It is preferred to do the magnesium treatment as close as possible (in time) to the

solidification of the metal. This will demand a minimum of treatment product.
The next figure 48 shows preferred ratio between the Mg- and S-content.
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Figure 48
Relation Mg-content to
S-content
But this figure is later replaced by figure 46, page 80 (also shown below).
% S (spectrometer)
after nodulising
0,016
0,014
Low nodularity
target range
0,010

0,006 shrinkage
0,002
0,02 0,03 0,04 0,05 0,06
% Mg (spectrometer)
Because the small sized MgS acts as nuclei, there is a need for a minimum of S-
content. In next figure, a content of less than 0,052 % will lead to MgS that are
completely solved in the metal.
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For this reason, it can be set that 0,06 % is the minimum S-content after nodulising.
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6.4.4 Mg-RE REQUIRED
Over the years it was noticed that some tramp elements affected the graphite shape.
Increasing magnesium was not able to counteract the effect of tramp elements like Pb,
Ti, Bi etc. Rare earths were found to neutralize these elements and restore the graphite
shape to nodular form. Hence rare earths were added either with or incorporated in
master alloys. For irons treated with pure magnesium Rare Earths could be added as
mischmetal or rare earth containing inoculants.
Rare earths, as does magnesium, will combine with sulfur and oxygen. They are also
contributing, together with magnesium, in nodularizing effect.
Because of this, one must look at magnesium and rare earths content in total and not
separately in determining amounts needed for best properties.
As the rare earths are heavier than magnesium it takes 5,8 times (the atomic weights of
rare earths are about 140 and that of magnesium is 24) more rare earths than
magnesium, by weight, to combine with sulfur and oxygen (if no Mg is used).
Combination of magnesium and rare earths resulting in various shapes of graphite is

shown in figure 49 and 50. When rare earths are added with magnesium alloy the
analyzed rare earths include that portion combined with oxygen and sulfur, like
magnesium analysis.
Figure 49
RE added with the Mg-alloy
There is much information regarding the use of rare earths and its effect on the graphite
shape. A minimum amount is necessary to neutralize any residual tramp elements that
may be present in the iron. It has been shown that proper addition of rare earths
increases nodule count.
When cerium in the magnesium alloy is used in excess resulting in a residual of over
0,01%, pro-eutectoid graphite particles tend to be larger and may result in graphite
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floatation and exploded graphite, especially when the sulfur is low and the CE is on the
high side. It is also possible to create chunky graphite (depending on the flake graphite
promoting elements).
Figure 50
RE added after the
addition of FeSiMg
When rare earths are added after the magnesium treatment along with the stream
inoculant then the level of cerium that causes graphite nodule enlargement and
floatation is much lower than the 0,01%. It is closer to 0,004%.
The difference may be because the rare earths in the first case are combined with
sulfur and oxygen and most of the rare earths are non-combined in solution in the
second case. This will lead one to envision the magnesium and rare earth relationship
differently if the rare earths are added after the magnesium treatment where most of the
oxygen and sulfur are tied up with magnesium.
This may be represented in the revised areas for various shapes of graphite in figure 49
and 50.
Obviously, the levels of Mg and rare earths do not stay the same throughout the pour in
a batch system due to fading of active elements with time. From the figures 49 and 50
(above), there is no vermicular graphite shown when there are no rare earths in the
iron. Ductile iron with only magnesium will revert to grey iron without going through a
vermicular graphite form.
Remark:
The noduliser elements also form MgS and CeS. Both compounds, if ≤ 10 µm, also act
as nuclei for the graphite precipitation.
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6.4.5 TREATMENT METHODS
Many different treatment processes have evolved over the years to achieve better
quality ductile iron at the lowest cost. Many variables affected the selection of a
particular treatment process. Some of the factors are:
• Base melt quality including sulfur content

• Temperature of treatment, holding and pouring
• Delays in metal handling
• Casting section modulus
• Ease of late inoculation.
Pure magnesium injection is no longer used because of the danger of metal

splashing from the ladle, the environmental problems and the problem of getting the
magnesium into the fluid.
In the beginning years of the production of ductile iron, copper-magnesium was used.
Now it has been replaced by nickel-magnesium (15% magnesium) or by ferro-silicon-
magnesium (3 to 15% magnesium), with or without addition of rare earths.
The Open treatments (sandwich-method, pouring over, plunging) are done with
nickel-magnesium as well as ferro-silicon-magnesium. It causes a large amount of
white smoke (MgO) burdening working area and surroundings. The reproducibility is
relatively high and the possibility for correction, after analysis, is an advantage.
The Closed treatments (Tundisch cover-, Flowtret-, Sigmat-process, convertor and

mould treatment) don’t burden working area and surroundings and they are very
reproducible. But a correction after analysis (to verify residual Mg-content) is very
difficult and a higher investment costs is necessary. These closed treatments are
always done with ferro-silicon-magnesium.
Treating with “filled wire” can be done in a close or open process. The treatment
with wire has the advantage that it is less depending on the operator and it can be
combined with an inoculation after the nodulising. It has the disadvantage that it is
less usable for small quantities (< 500 kg) and high quantities, depending on the ladle
size (> 10.000 kg).
In general, it can be said that, depending on the used noduliser and method, 0,9 to
1,8 % of noduliser is added and the efficiency varies between 35 to 80 %. These are
large margins and it comes down to searching for a good combination that gives a
good nodular cast iron.
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6.4.6 PROBLEM
Problem of inconsistent result of Nodulising treatment - Nodularity
The inconsistent result of the Mg-treatment (evaluated by the nodularity of the casting
material) is due to the following factors:
1. Incorrect testing the initial S-content (spectrometer not properly calibrated).

The final S-content should be:
• > 0,005 %, preferred 0,008 – 0,012 % for thick wall castings
• Preferred 0,010 – 0,015 % for thin wall castings.
2. The incorrect weighting of the tapped amount of metal for treatment
3. The incorrect weighing of the FeSiMg addition, which depends on the

calibrated weight scale and the operator. This is less dangerous for wire
nodulising.
4. The varying amount of Mg in the FeSiMg alloy. Most alloys do have a

tolerance of ± 0,5 %, but some (cheaper ones) have a tolerance of ± 1 %. The
Mg-content differs per batch and in a badge, can be different depending on
the size (especially dust).
5. The varying amount of RE in the FeSiMgRE alloy. RE have a similar effect as

Mg for removing the oxygen and sulfur. If the alloy is ordered and delivered
without specifying the RE-content, the nodulising result will be different.
6. The inconsistent type of addition of FeSiMg. The covering of the alloy in case
of sandwich-treatment, use of oxidized treatment alloy, incorrect wire addition
due to varying speed…
7. The time between nodulising and end of pouring. During the transport
(especially for a non-covered ladle, and the pouring itself, there is also a loss
of Mg by forming MgO during contact with the air, especially if the distance
between ladle and mould is large. This extra time of transport and “less
correct” pouring can vary a lot, so the final result of nodulising does.
8. The Mgr (residual Mg-content) content is not always properly tested (with an
optimal spectrometer) and reported. This is due to the poor calibration of the
spectrometer and the fact that the tested Mg content, called Mgt is:
Mgt = Mgactive + MgMgS + MgMgO + MgMgZnO3 + MgMg2SiO4 + MgMgSiO3
Mgt total Mg-content measured (can be spectrometer)

Mgactive free Mg
MgMgS Mg-part of the MgS compound
MgMgO Mg-part of the MgO inclusion (very low)
MgMgZnO3 Mg-part of the Zn-compounds
MgMg2SiO4 Mg-part of the dross
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MgMgSiO3 Mg-part of the dross
Only Mgactive is countable / effective for the nodularity.

If the nodulising slag (MgS) is not properly removed or the sample is taken too
early after treatment, there can be a significant difference in result. And
although Mgt is correct, the Mgactive can be too low.
Equally, this can happen if the Zn-content (galvanised steel raw material) is
changing a lot.
9. During very turbulent pouring and mould filling, a lot of dross can be formed
(Mg2SiO4 and MgSiO3), which decreases again the amount of Mgactive inside
the casting. The nodularity will be less, and dross will appear.
This indicates that it is not correct to have a constant Mg-addition. Constant

means independent of the initial S-content, the ladle transport type and time,
the type of pouring and the shape and section of the casting.
An overview of the influences on the nodulising is given in next fishbone

diagram.
Liquid metal Nodulizer Fading
Type of charge material and Chemistry: Mg- RE

charging procedure content
Temperature of
S-content Chemistry: Mg-content metal
Time on high temperature:

Grain size Chemistry
above Tg (O-content)
Temperature in furnace Condition (oxidized-high Time to

compared to Tg-temperature temperature / dirt / solidification
(O-content) humidity...)
Incorrect
nodulizing
Ductile Iron
Amount of nodulizer related Type of addition /
to initial S-content metal Correctness of amount of
together with inoculant
treated metal
or not
RE-content according subversive
elements Weighed nodulizer
Grain size
Treatment temperature
Too much slag on metal Loss by adding
Amount of nodulizer related

to timing of pouring Nodulizing method Yield of treatment
Nodulizing procedure Type of addition Real addition
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6.5 INOCULATION
The main purpose of inoculation is to achieve best mechanical properties and optimum
Properties and machinability characteristics by:
1. Control of graphite structure.

2. Elimination or reduction of chill/carbide.
3. Reduction of casting section sensitivity.
In ductile iron, it will optimise the nodule shape, improve nodule count, prevent the
formation of carbides and increase the ferrite content.
Inoculation must increase the number of germs (nuclei) in the metal to that level
which will lead to the required graphite morphology.
The old rule: “spheroidise first and inoculate afterwards” is now proven to have a very
small advantage (less than 2 %). On fading, the positive advantage does not exist.
Low temperatures at the time of inoculation increase the inoculation efficiency.
Temperature °C 1325 1350 1400 1450 1500

Nodule count number/mm2 120 92 61 40 27
If the total amount is added in two parts, spread in time, the final effect will be higher
compared to a treatment that adds all at once.
The thinner the section of material, the faster the cooling will be and the higher the
risk to form carbide and decrease of the total level of free graphite. For this reason,
the inoculation should be done as late as possible, for example by mould-inoculation.
In thick sections, the effect of inoculation, at the time of metal solidification, can
already have decreased and the number of nodules will be small, the size of the
nodules big and their quality (nodularity) less.
There is a large possibility to have segregations, especially of manganese,

chromium, titanium and vanadium. These segregations also decrease the
mechanical properties.
The thicker the section, the less carbide forming, and residual elements can be
admitted. The inoculation alloy must then have a long-lasting effect.
An inoculation alloy consists mainly of silicon. For thin sections it can also include
elements as calcium, aluminium, barium, rare earths (Ce, Sr) ... These elements do
act as a catalyst for the precipitation of silicon, which will form SiO2, which are the
germs for the graphite precipitation. This type of inoculant (with lesser amounts of
Ca, Bi…) will act very quickly, but will also fade very quickly! The inoculant with Ba
addition and or Ba & Ca addition is mostly used as pre-treatment alloy in the furnace;
sometimes as first inoculator (if time between nodulising and pouring is long).
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For thick sections the best product is a pure ferro-silicon. Because of the long
reaction time, the effect will last longer, which is good for thick sections. See the
figure 51 on this page.
It is necessary to store this product in a way that no moisture pick up can happen.
This pick up will decrease the effectiveness dramatically.
The amount of inoculation product can never be adapted to the initial silicon level of the
metal! Too low or too high amounts of inoculation product will both give a bad result.
Try to use always the same quantity per tonnes of metal to get a very consistent result.
The initial level of silicon must be at least 1, 0 %.
Types and amount of inoculation:
Type Section amount disadvantage advantage
Ladle < 12 mm > 0,6 % fading effect identical per ladle

Ladle 12 – 25 mm 0,4 – 0,6 % fading effect identical per ladle
Ladle > 25 mm 0,25 - 0,4 % fading effect identical per ladle
Metal stream 0,10 – 0,20 % not continuous, identical per mould / casting
ferrosilicon inclusions
Immould 0,05 – 0,15 % ferrosilicon inclusions identical per mould / casting
Figure 51 Inoculation effect in time
Problem: inconsistent result of Inoculation treatment
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This very inconsistent result is due to the following factors:
1. Incorrect testing the initial liquid metal quality (CE-cooling curve and or
wedge test). Recalescence (undercooling) should be low: < 3 °C)
2. The incorrect weighting of the tapped amount of metal
3. The incorrect weight of the inoculant depends on the calibrated weight
scale (as well of the tapped metal as the weighed inoculant) and the
operator.
4. The varying amount of Mg in the FeSiMg alloy. Most alloys do have a
tolerance of ± 0,5 %, but some (cheaper ones) have a tolerance of ± 1 %.
5. The time between first inoculation and second (late) inoculation and the
end of pouring.
6. The grain size of the late inoculant
7. The presence of slag during the late inoculation
8. Types of inoculant of the first and second (late) inoculation.
An overview of the influences on the inoculation is given in next fishbone

diagram
Condition liquid iron:

Number of nuclei Inoculant Fading
Type of charge material and

charging procedure
Chemistry Temperature of
Preconditioned or not metal
Grain size
Time on high temperature: Chemistry
above Tg
Condition (oxidized-high Time to

Temperature in furnace temperature / dirt / solidification
compared to Tg-temperature humidity...)
Insufficient
inoculation
Ductile Iron
Amount of inoculant related Type of addition /
to initial liquid metal quality Correctness of amount of
together with nodulising
treated metal
or not
Too few MgS / CeS or too large
Grain size Weighed inoculant
No of inoculant steps
Too much slag on metal
Loss by adding
Steps related to timing
of pouring Location in metal
Inoculant procedure Type of addition Real addition
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6.6 FADING EFFECT
i. Introduction
ii. Spheroidising fading
iii. Inoculation fading
6.6.1 Introduction
It is very important to watch the fading effect of these metallurgical treatments,

because an insufficient effect will lead to:
• Vermicular (compacted, worm) flake (lamellar) graphite in case of fading of

the nodulising effect, which is not at all allowed in ductile iron
• Low nodule count in case of fading of the inoculation effect, which will lead
to the presence of carbides and shrinkage.
6.6.2 Spheroidising fading

The fading covers the decrease of Mg- and RE-content (Ce, La, Pr).
This fading is due to several factors:
1. Reaction of mainly free Mg with oxygen at the metal surface

2. Reaction of Mg and RE with combined oxygen of less stable oxides, especially
SiO2
3. Sulfides can be broken down and the sulfur will react with Mg and or RE
4. The combining of small MgS (and in a lower extend CeS) to larger particles
that float quicker to the metal surface.
The fading of the spheroidizing treatment will depend on different items as are:
1. increasing magnesium content will increase the speed of fading
2. increasing treatment temperature will increase the speed of fading
3. increasing the sulfur content will increase the speed of fading
4. use of neutral or magnesite lined ladles will decrease the speed of fading
5. a proper slagging (slag removal), 1 to 2 minutes after treatment, will decrease

the speed of fading
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6. turbulent movement of the metal:
• Ladle tilting back and forth

• Pouring into the pouring box / mould
• Filling of the pouring system and mould cavity.
7. alloying elements (Ba, Ce) in the inoculant will slow down the speed of fading
8. a protective atmosphere (example nitrogen) as can be used in a pressure pour

furnace. In this case (serial automatic pouring), the late second inoculation will
also improve the nodularity
9. continuous used ladle, not emptied after the previous pouring. The remaining
metal is cold and maybe has solidified as flake iron.
Common figures (have to be checked in every foundry) for the fading loss are:
1. 0,001 % Mg and 0,0002 % RE per minute in the pouring ladle

2. 0,0006 % Mg and 0,00013 % RE per minute in closed ladle
3. 0,0003 % Mg per minute in a proper lined and covered holding furnace.
But every foundry should check this fading in its particular conditions, realising
that even different ladles (especially ratio of surface to the content) can have
different fading effect.
9.6.3 Inoculation fading
The fading of the inoculation, which mainly exist of silicon, is accepted as starting
after 4 minutes, being arrived at completely insufficient inoculation levels after 10
minutes!
For thin sections the inoculant can also include elements as aluminium, barium, rare
earths... In this case the effect will start very quickly after adding in the metal, but will
also fade quickly.
For thick sections the best product is a pure ferro-silicon. The effect starts very
slowly, but last the longest. See figure 52 (next page).
Remark
A common rule, used by foundries, is that pouring 12 minutes after the nodulising and
first inoculation will lead to serious free graphite problems.
The rule is an indication, but not correct in all situations.
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Figure 52
Required effects
for thin and thick
sections.
There are a few simple tests to quantify the fading effect for a given metal and a
consistent metallurgical treatment (desulfurising, spheroidizing, and inoculation).
The “step block” (figure 53) can be adapted to the wall thicknesses concerned.
Figure 53
Step Block
Figure 54 Eared Block
Another test bloc that can be used is the “eared block” (figure 54). This block is more
prone to carbide formation. The dimensions can be adapted to the wall thicknesses
concerned.
The fading of the spheroidizing and inoculation treatment has nearly the same
rate for most of the common techniques, knowing that the Mg-fading starts
immediately and the inoculation effect increase the first minutes (depending on
the type of inoculant) and then decrease.
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6.7 INTERESTING GUIDELINES

b. The magnesium alloy should preferably be of lower magnesium such as 4 to
5% with low rare earth content in the alloy. Steel cover may not be necessary
with low temperature and low magnesium level in the alloy.
c. Tap temperature should be kept as low as possible still maintaining a high

enough pouring temperature (above 1370 °C).
d. Post inoculation with ferrosilicon containing Ca and rare earths should be used
to neutralize detrimental elements as well as to increase nodule count.
e. If late inoculation (stream) is used then care must be taken to limit the rare
earths contributed by the inoculant as the rare earths that are not combined
with sulfur and oxygen are very potent in affecting the shape of the graphite
nodules.
f. Magnesium residual and rare earth levels should be optimized at the lowest
levels still achieving good nodularity.
g. Limit the fading time so that there will not be much difference in the magnesium
level between the first and the last mold poured.
h. Treatment size should be commensurate with mold pour weight so that the
fade time does not exceed 12 minutes for batch processing.
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7. NON-CONFORM METALLURGY
7.1.1 Incorrect shape (nodularity)

7.1.2 Incorrect size
7.1.3 Incorrect number of nodules
7.2 AMOUNT & TYPE OF GRAPHITE IN CASTING
7.2.1 Low nodularity graphite

7.2.2 Graphite flotation
7.2.3 Chunky graphite
7.2.4 Intercellular flake graphite
7.2.5 Exploded graphite
7.2.6 Deteriorated surface graphite
7.2.7 Carbides
7.2.8 Phosphide eutectic
7.2.9 Remark: Chemical analysis
7.3 STRUCTURE
7.3.1 Ferritic / pearlitic structure

7.3.2 Surface layer
7.4 INCLUSIONS
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7.1.1 Incorrect shape (lamellar, worm, vermicular)

7.1.2 Incorrect size
The graphite morphology concerns the shape and the size of the free graphite
segregation and the number of nodules present in the solidified iron.
7.1.1 Incorrect shape (lamellar, worm, vermicular)

The correct shape is obtained if the S-content and O-content is sufficiently low. But
there is practical minimum for both elements to avoid:
1. Low response to inoculation (done by S, O)

2. Inverse chilling (done by H, O).
The removal of these elements (sulfur and oxygen) is mostly done by a magnesium
and “Rare Earths” treatment. During the years of experience, it seems very confident
to judge the end-content of magnesium to be sure of the shape of the graphite.
The following figure 55 does give the result for a wall thickness of 30 to 50 mm.
If the end-magnesium content is higher as 0,035 %, the shape will be nodular, class
V and VI, on the condition that
the inoculation is properly done.
If the end-magnesium content

is around 0,025 % (and nor RE
present), more than 50 % of the
free graphite will not be
nodular.
Figure 55
Free graphite shape if no RE
is used
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If RE is present, the required amount to achieve high nodularity is lower. The next
two figures show this: first figure 56 when FeSiMgRE is used and second figure 57
when FeSiMg is used with a separate addition of RE.
Figure 56 Free graphite shape if FeSiMgRE is used
Figure 57 Free graphite shape if FeSiMg and RE are used
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The amount of the following elements (subversive elements), which tend to destroy
the free graphite shape and consequently decrease the nodularity, must be carefully
controlled by the foundry.
1. The elements lead, antimony, bismuth, boron, tellurium, arsenic and

titanium
They have a negative influence on the graphite shape. Some of them, for
example titanium and aluminium, enter the metal through the steel scrap;
others through the inoculant. The following maximum levels are suggested:
Aluminium 0,05 % antimony 0,001 % arsenic 0,02 %

Bismuth 0,002 % boron 0,002 % cadmium 0,005 %
Lead 0,002 % selenium 0,03 % tellurium 0,02 %
Titanium 0,03 % zirconium 0,10 % zinc 0,01 %
Lead is a very negative element that stimulates networks of fine lamellar graphite
(spiky-graphite). The effect (for the same nodularity) on the iron strength is high
and can be compared to the effect of a too low residual magnesium level.
The effect of these elements will decrease by adding Rare Earths (part of it is
cerium, around 40 to 50 % of the RE content). This can be done by adding only
Rare Earths or FeSiMgRE, which is ferro-silicon-magnesium with a small amount
of Rare earths).
But if too much RE is added, depending on the wall thickness of the casting and
CE (Carbon Equivalent) and residual Mg-content of the iron, the effect will be the
formation of chunky graphite (Ce, Cerium) or other deformed graphite (Y,
Yttrium).
2. Sulfur and phosphorous must be kept as low as possible.
The following indications proved to be successful:
P ≤ 0,035 %: valid for ferritic ductile iron.

P ≤ 0,030 %: valid for ferritic ductile iron for low temperatures; even preferred
it is < 0,025%.
P ≤ 0,05 %: for ductile iron used for application at room temperatures.
For sulfur, it is suggested that for all structures, S < 0,025 % before nodulising
and 0,008 < S < 0,012 % after the nodulising treatment.
These instructions, for the P- and S-levels, leads in practice to reliable results.
Too low S-levels will decrease the effect of the inoculation by reducing the
number of nuclei, which results in a lower nodule count.
The lower the sulfur content before treatment, the less magnesium is needed
and the lower the fading effect of the magnesium will be.
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Pay attention if chemical sand (catalysed with a PTSA catalyst) moulds are
used. If the degree of reclaiming the sand is high (> 75 %), a high amount of
sulfur can be present in this reclaimed sand. This sulfur can react with the
liquid metal and consequently there will be a surface layer without nodules or
with a high degree of degenerated nodules and crablike free graphite.
3. Oxygen must be low (< 50 ppm or 0,005 %), but not too low (≥ 8 ppm).
The oxygen content is mostly no problem with the production of ductile iron.
The oxygen content cannot be too low (dead burnt iron) because this will
decrease the inoculation efficiency (SiO2).
If the oxygen content is high, it will contribute to the formation of dross during
transport of the uncovered ladle, the pouring and mould filling. In practice, this
is seldom experienced.
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7.1.2 Incorrect size of graphite
This type of non-conformity, mostly too large nodule size compared to the
requirement, has only low consequences on the mechanical properties but can have
larger one on the amount of solidification shrinkage.
The incorrect size has mostly to do with the metallurgical quality of the metal and the
metallurgical treatment as well as the CE (carbon equivalent).
It is combined with the number of nodules per unit of area, because the total amount
of free graphite is decided by the C-content.
Amount of free graphite = Ccontent iron – 2,2 % - Cin carbides.

The lower the number of nodules, the larger the free graphite will be.
The number of nodules per square millimetre is depending on the metallurgical

quality of the melted iron (see ΔT in the cooling curve), as is the number of nuclei and
the effectiveness of the inoculation metallurgical treatment (number of extra nuclei).
An increasing number of nuclei will increase the number of nodules and decrease the
nodule size.
The longer the time of solidification of the metal, especially for hyper-eutectic
compositions (CE > 4,4), the larger the graphite size will be and the lesser the
amount of free graphite nodules. This appearance of large graphite happens
because for hyper-eutectic compositions, first graphite is segregating. This
segregated graphite, being a nodule, will growth extensively before the solidification
is finished. See figure 58.
Temperature
hypo-eutectic
Figure 58 hyper-eutectic
Solidification mechanism
CE
2,2
4,3
%C
eutectic
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The first segregating free graphite, also named primary graphite, will grow until a
diameter size > 100 µm (mostly between 140 – 160 µm), whereas the free graphite
segregating during the eutectic solidification (also named secondary graphite) will
have a diameter < 100 µm (mostly between 30 – 70 µm).
Next figures (59 and 60) show some examples of large nodule size.
Figure 59 Large nodule size Figure 60 Large nodule size
Causes too large nodule size:
* High carbon equivalent (CE)

* Low cooling rate
* Poor inoculation efficiency
* Small number of MgS and CeS.
Solutions:
* Adjust the chemical composition concerning CE

* Use a stronger inoculant
* Use RE, taking in account the maximum for Ce
* Use chills and or chromite sand at the location of thick sections.
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To be accountable as nodule, the diameter must be > 5 µm and or the area
involved > 20 µm2 (nodules are between 5 and 150 µm).
This type of non-conformity, dealing with as well “too low” as” too high” nodule count
number, has an important influence on the ductility of the material and a considerable
influence on the solidification shrinkage.
Several customers, knowing this potential danger, have specified a minimum nodule
count for their castings. One of the largest customers of thick wall ductile iron
castings has specified a minimum of 50, whatever the section thickness involved.
Ductile iron castings for nuclear industry even require a minimum of 100.
It is influenced by the inoculation treatment (time of the treatment, type of treatment

alloy, fading effect…) and the metallurgical quality of the molten iron and section of
the casting.
A too low nodule count (for wall thickness concerned) has negative consequences on
the mechanical properties (mostly ductility, but also increase the pearlite amount) and
shrinkage behaviour (less homogeneous matrix).
A too low nodule count can be an indication that the metal has:
• a low Ceq and or carbon content

• a low nuclei level at the time of solidifying
• a high tendency for solidification shrinkage and consequently porosity
problems.
A too high nodule count can be an indication for:
* a high tendency for mould expansion, which will increase the tendency to
porosity defects, especially in thick castings and green sand moulds
* high tendency to block the activity of risers with the consequence of primary
shrinkage below the riser.
This appearance (too high nodule count) is called “graphite flotation”. This
phenomenon is appearing if:
* the CE (carbon equivalent, Ceq) is too high compared to the section and
* it is increased if the pouring temperature is high compared to the liquidus
temperature and
* if the shape of the casting is sensitive (large vertical sections).
The following graphs (see figure 61 and 62, next page) are mostly accepted as
guideline for evaluating the nodule count, depending on the wall thickness.
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The red line indicates an accepted minimum number, minimum nodule count that has
no significant influences on the mechanical properties or shrinking behaviour of the
metal.
The blue line indicates the maximum number, maximum nodule count, above which
the appearance is called graphite flotation, with extensive mould expansion and
consequently shrinkage, with non-active risers and with lower mechanical properties
of the metal in the concerned area.
1200
1100
Nodule cdount / mm2
1000
900
800 Figure 61
700
Nodule count for
600
500 sections up to 30
400 mm
300
200
100
0
5 10 15 20 25 30
Wall thickness (mm) or M x 20
450
400
Nodule count / mm2
350
Figure 62 300
Nodule count for sections 250
> 30 mm
200
150
100
50
0
25 75 125 175
Wall thickness in mm or M x 20
Example:
The nodule count should be > 150 / mm2 and < 450 / mm2 for a section of 20 mm.
The higher the nodule count, the better the fatigue strength will be, on the condition
that it is located between the limits (blue and red limit) indicated in these figures.
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Summary:
1. Nodule count influences the pearlite content of as-cast ductile iron. Increasing
the nodule count decreases the pearlite content, decreasing strength and
increasing elongation.
2. Nodule count affects carbide content. Increasing the nodule count improves
tensile strength, ductility and machinability by reducing the volume fractions of
chill carbides, segregation carbides, and carbides associated with "inverse
chill".
3. Matrix homogeneity is influenced by nodule count. Increasing the nodule count

produces a finer and more homogeneous microstructure. This refinement of
the matrix structure reduces the segregation of harmful elements which might
produce intercellular carbides, pearlite or degenerate graphite
4. Nodule count affects graphite size and shape. Increasing nodule count results
in a decrease in nodule size which improves tensile, fatigue and fracture
properties. Inoculation practices used to improve nodule count often make the
nodules more spherical. Thus, high nodule count is generally associated with
improved nodularity.
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7.2 AMOUNT & TYPE OF GRAPHITE IN
CASTINGS
7.2.1 Low nodularity graphite

7.2.2 Graphite flotation
7.2.3 Chunky graphite
7.2.4 Intercellular flake graphite
7.2.5 Exploded graphite
7.2.6 Deteriorated surface graphite
7.2.7 Carbides
7.2.8 Phosphide eutectic
7.2.9 Remark: Chemical analysis
In certain locations of the casting or all over the casting, non-conform graphite can
occur because of the pouring, solidification time, interaction with the mould material…
The graphite morphology at other locations of the casting can be conforming to the
specifications.
In this chapter, the most common non-conformities concerning graphite appearance

will be discussed. All of them are initiated by the chemical composition, mostly by one
or two elements that are not sufficiently controlled.
None of the indicated non-conformities is accepted because they all, some

more, other less, decrease the mechanical properties of the metal.
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7.2.1 LOW NODULARITY GRAPHITE
As indicated in “chapter 4.1.1 Incorrect shape, too low nodularity”:
1. or the shape can be incorrect: worms, flakes…

2. or the “roundness of the nodules can be not very good.
The roundness or degree of nodularity is mostly set by the customer and it can be
seen that 85 % is commonly used.
How can it be that the nodularity is too low?
1. Mg content
If the Mg content is too low, the nodularity decrease, and the precipitated graphite
even shift to “worm-like” graphite (as is for compacted iron). This deformation from
nodules to worms is not suddenly happening but gradually. So, the roundness of the
nodule decreases or nodularity decreases.
Figure 63 indicates a dangerous area depending on final Mg- and S-content and is
used for a long time.
% S final
0,016
0,014 Low nodularity
0,012
0,01
target range
0,008
0,006
Carbides &
0,004 shrinkage
0,002
0,02 0,03 0,04 0,05 % Mgresidual
Figure 63 Graphite appearances depending on the residual Mg- and S-content
But normally a low residual content of Mg is required as is revealed in a study in

Germany. The old graph (see graph in chapter 4.1.1 Incorrect graphite shape) is now
replaced by the new graphs (figure 64 and 65) as indicated next.
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Figure 64 Graphite shape depending on % Mg and RE if the nodulising is done

by FeSiMgRE.
Figure 65 Graphite shape depending on % Mg and RE if the nodulising is done

by FeSiMg and later addition of pure RE.
It is clear that RE plays a significant role.
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2. RE (Rare Earths)
The RE do play a key role in forming nodules because they are even more powerful
as noduliser than Mg, they have a higher tendency to bound S and O.
The other advantage is that they mostly form very small compounds of sulphides
(CeS) and oxides (CeO), which act as nuclei. In this way they increase the nodule
count very much.
But they also tend to destroy the good nodules if their content is too high compared
to the wall thickness.
So, it is very well possible that certain types and amounts of RE do give a good result
in thin and medium size castings but not in thick wall castings!
Most of the RE’s are mainly containing Ce (cerium), between 40 to 50 %. The

combination of RE and Mg decides about the graphite shape, nodularity. Cerium is
used to compensate the presence of the harming (mostly flake promoting elements)
elements like Ti, Bi, Sb…
When using RE with Ce, it is known that the cerium may not be too high, depending
on the wall thickness (solidification time of the metal) of the casting. If it is too high, it
will initiate chunky graphite, which will be discussed in chapter “4.2.3 Chunky
graphite”.
This shifting from correct nodules to chunky graphite is not happening suddenly, but
gradually. So, an amount of Ce, allowable to avoid chunky graphite, can anyhow
decrease the nodularity.
If the RE is containing Yt (Ytrium), it seems to have a very good result concerning

nodule count in thin castings, which are quickly solidifying.
Very few is known about the result in thick wall castings, because it is seldom used in
Europe and USA, but it is very well possible that, like Ce and may be even more
active, deforms the nodules.
Some results are shown with nodules that are “strange”, in a foundry using nodulisers
with RE (Yt) in thick castings. See figure 66, 67 and 68. Depending on the amount of
RE, and the presence of Cu (> 0,75 %), the nodularity went down as percentage RE
increased.
Figure 66 Unusual nodules
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Figure 67
Unusual
nodules
Figure 68 Increasing
amount of element Yt in
thick wall castings (>
150 mm)
It seems to be clear that as well Mg as RE, including Yt can have a beneficial

effect to produce ductile iron with a high nodularity and nodule count. But
once it is used in thick wall castings, strange graphite appears.
Lanthanum (La) is another RE-element. Several literatures tell that they improve the
shrinkage behaviour by promoting the non-axial solidification (less dendritic). This is
not yet accepted by all researchers and the effect is very few in thick wall castings
(do not solidify dendritic at all).
Pay attention that the spectrometer is properly calibrated because these

elements are present in low contents and their activity change quickly from
positive to negative effects on the graphite shape.
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7.2.2 GRAPHITE FLOTATION
7.2.1.1 Definition
Graphite flotation (GF) is the concentration of graphite at the top of the casting and
below cores.
The carbon concentration in this area is often as high as 5,0 to 6,0 %, whereas the
nominal content is around 3,6 %.
7.2.1.2 Appearance
The figure 69 a, b and c show the appearance of the graphite nodules in the GF
area. The nodules are so concentrated that they can sometimes be in physical
contact one with another.
Figure 69 a, b and c Graphite flotation
When these castings concerned are broken, an area displaying a black fracture can
be seen.
The carbon concentration in the black fractures is often as high as 5,0 to 6,0 %,
whereas the nominal content is around 3,6 %.
If it is located in the area of the riser(s), there are 2 possibilities:
1. If the riser is properly designed, the riser neck will solidify early, and the
graphite location is under the riser
2. If the riser is too large, the riser neck will stay open long time. The floating
graphite will partly disappear inside the riser and it is possible that there is no
graphite flotation just under the riser.
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7.2.1.3 Mechanism
During solidification, the graphite is precipitating from the liquid metal; the time that it
does that is depending on the carbon equivalent.
Hypo-eutectic iron is first solidifying by dendrites of iron to increase the carbon

equivalent of the liquid metal to the eutectic one (CEeutectic = 4,33).
From the moment this eutectic composition is achieved, also free carbon is
appearing. This carbon is restricted in growth by the already existing metal dendrites
and will have a brief time to form. They will mostly not float up in the casting.
Hyper-eutectic iron is first releasing free graphite to align the liquid chemical
composition with the eutectic one (CEeutectic = 4,33). The free carbon is continuously
growing until the material is completely solidified. See figure 70.
Temperature
hypo-eutectic
hyper-eutectic
Figure 70
Solidification of iron
CE
2,2
4,3
%C
eutectic
Graphite is significantly less dense than iron, so it has the tendency to float when it
precipitates in the liquid iron. The tendency is larger if the graphite nodule is larger.
When this flotation occurs prior to the complete solidification of the metal, a
concentration of graphite nodules occurs at the cope surface (top part of the mould)
and immediately under cored surfaces.
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7.2.1.4 Influencing factors
The three most crucial factors associated with the presence of graphite flotation are:
• Carbon equivalent (CE)
• Casting section size and shape
• Size of the graphite
• Solidification rate
• Pouring temperature and metal temperature in casting.
Carbon Equivalent
Graphite flotation may occur in all hypereutectic irons (CE > 4,33), but is mostly
present in ductile iron with a carbon equivalent (CE) that exceeds 4,5%. The nodule
size will mostly be large, and they can float up quickly.
Carbon equivalent is defined by the expression:
CE = %C + (%Si/3) + (%P/3)
For alloyed irons, sometimes the following formula is used:
CE = %C + (%Si/3) + (%P/3) + 0,076 (%Cu) + 0,051 (%Ni) + 0,4 (%S) – 0,028 (%Mn)
The extent of flotation is small when irons are just hypereutectic (i.e., their CE values
just exceed 4,33, depending on the wall thickness).
The higher the liquidus temperature, the more the difference of this temperature with
the eutectic temperature, the longer the metal will form nodules in liquid metal and
the more the nodules will growth and float to the top.
Approximate calculation:
C Si P CE Tl-Teu
Tl (hypereutectic iron) in °C: % % % °C
3,55 2,37 0,03 4,35 -6
-505,8 + 389,1*(%C + 0,31 %Si) 3,6 2,37 0,03 4,4 14
3,6 2,67 0,03 4,5 49
Tl (hypereutectic iron) in °C: 3,7 2,67 0,03 4,6 87
3,8 2,67 0,03 4,7 126
1154,6 + 5,2*(%Si)
Casting section size and shape
The concentration of graphite can only happen if the nodules float up in the liquid.
This requires a long solidification time, which means heavy section. Therefore,
flotation effects are confined mainly to heavier sections and the area below a riser.
The shape is also important because if this is very complex, the graphite will never
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reach the top. If this is straight up, it is very easy to float up.
If the casting and especially the top of the casting is thick, the graphite flotation will
be more pronounced.
Size of the graphite
The larger the graphite nodule size, the higher the float up speed will be.
The float speed can be calculated by Stokes law:
V = 2 * (δmetal – δgraphite) * r² / g * η
δmetal density of metal

δgraphite density of graphite segregation
r radius of graphite nodule
g gravity factor: 9,81 m/s²
η viscosity of liquid metal: g.s / cm³
The lower the NC (nodule count), the larger the nodules will be. Few nodules will be
present if the inoculation is poor, the S-content too low and the Ce-content low.
Solidification rate
If the solidification rate of the metal is increased by chills (or another tool), the metal
will completely solidify much quicker and the time for floating up will be much lesser.
So, the effect will be less.
Pouring temperature and metal temperature in the casting
If the pouring temperature is high, the mould material will heat more, which leads to a
longer solidification time of the metal because the heat will be removed more slowly.
An increase of 10 °C is equal to an addition of 0,01 % C (or 0,03 % Si).
If the pouring system is concentrated and the pouring time short, there will be area
with a high metal temperature. As an example: if the ingating is in the bottom and the
pouring time long, the metal temperature on the top will be low and the nodules will
float less.
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7.2.1.5 Consequences
Mechanical properties, particularly tensile strength, elongation and impact strength,

can deteriorate significantly in the graphite flotation zone.
Observers have reported:
1. 25 % reduction in tensile strength,

2. over 80 % reduction in percent elongation, and
3. over 50 % reduction in impact strength
4. fatigue strength will decrease a lot (mostly > 25 %)...
The yield strength is very few influenced.
Graphite flotation is dangerous because it appears near to the surface, which in most
real stress situations is the highest stressed area.
The volume shrinkage will be totally different in the graphite flotation zone
compared to the other zones. Because the other zones lost more graphite, the
graphite expansion will be less, and it is likely that shrinkage appears.
The high carbon top zone has a large graphite expansion and the metal will be
pushed to the other area, which it cannot reach if the section is long. Than the mould
wall movement will be large, or the metal is pushed into the riser, which cannot work
properly anymore. The metal in the risers mostly also contains graphite flotation and
the expected feeding behaviour is lost.
The fluidity of the hyper-eutectic metal is also less than for the eutectic one. This is
not due to the graphite flotation (there is during the filling not yet free graphite), but
appears mostly at the same time due to the common factor (CE > 4,5).
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7.2.1.6 Solutions
Chemical composition, CE
Control of the base iron composition (especially the CE) before magnesium treatment
and inoculation is a practical and effective way to prevent flotation.
The effect of carbon and silicon on graphite flotation is like the effect on the liquidus
arrest temperature, as described by the carbon equivalent liquidus (CEL)
relationship:
CEL = %C + (%Si/4) + (%P/2)
To prevent flotation, it is important not to exceed the maximum CEL values for ductile
iron castings of different section sizes. In most literature, indications are given
depending on the structure, as cast.
The first indication is given by ASM Specialty Handbook, “Cast Iron”, issued 1996.
Recommended carbon content to minimize graphite flotation

In ferritic ductile irons containing 2,5 % Si
Maximum wall thickness

in inch 1/8 1/4 1/2 1 2 3 >4
in mm 3,5 6,3 12,5 25 50 75 > 100
Total carbon content
in % 4,35 4,05 3,85 3,55 3,40 3,35 3,30
The next table is another table mentioned in ASM Specialty Handbook, “Cast Iron”,
issued 1996.
The table after that, is found in “Ductile Iron I Production”, issued in 1992 by QIT –
Fer et Titane Inc.
It is accepted that the tables of QIT are very strict and the indicated value can
be passed mostly without problems. The ASM table is more realistic and
should not be passed.
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Table: Carbon, silicon and Carbon equivalent to avoid graphite flotation
Source ASM Specialty Handbook Cast Iron
As cast structure
Wall thickness pearlitic Ferritic
Min Max C Si CE C Si CE
mm mm % % % %
3 3 3,85 2,85 4,82 4,25 2,85 5,22

6 3,80 2,85 4,77 4,00 2,85 4,97
12 3,75 2,75 4,68 3,90 2,85 4,87
25 3,70 2,75 4,63 3,80 2,85 4,77
50 3,60 2,75 4,53 3,65 2,85 4,62
75 3,40 2,75 4,33 3,50 2,85 4,47
> 100 3,25 2,75 4,18 3,45 2,85 4,42
6 6 3,85 2,80 4,80 3,95 2,85 4,92
12 3,80 2,80 4,75 3,90 2,85 4,87
25 3,75 2,80 4,70 3,85 2,85 4,82
50 3,70 2,80 4,65 3,80 2,85 4,77
75 3,65 2,70 4,57 3,70 2,85 4,67
> 100 3,60 2,70 4,52 3,60 2,85 4,57
12 12 3,80 2,75 4,73 3,85 2,80 4,80
25 3,75 2,75 4,68 3,80 2,80 4,75
50 3,65 2,75 4,58 3,75 2,80 4,70
75 3,60 2,65 4,50 3,70 2,80 4,65
> 100 3,55 2,65 4,45 3,65 2,80 4,60
25 25 3,60 2,55 4,45 3,75 2,70 4,67
50 3,55 2,55 4,35 3,65 2,70 4,57
75 3,50 2,55 4,30 3,60 2,65 4,50
> 100 3,40 2,40 4,22 3,55 2,65 4,45
50 50 3,55 2,25 4,32 3,55 2,45 4,38
75 3,40 2,20 4,15 3,50 2,45 4,33
> 100 3,40 2,20 4,15 3,45 2,45 4,28
75 75 3,40 2,15 4,13 3,40 2,45 4,23
> 100 3,40 2,15 4,13 3,40 2,45 4,23
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Table: Carbon, silicon and Carbon equivalent to avoid graphite flotation
Source Ductile Iron I Production, QIT – Far et Titane Inc.
As cast structure
Wall thickness Pearlitic Ferritic
Min Max C Si CE C Si CE
Mm mm % % % %
3 3 3,90 2,90 4,87 3,90 2,95 4,88

6 3,85 2,85 4,80 3,85 2,95 4,83
12 3,80 2,80 4,73 3,80 2,90 4,77
18 3,75 2,70 4,65 3,75 2,85 4,70
6 6 3,85 2,65 4,73 3,85 2,85 4,80
12 3,75 2,60 4,62 3,75 2,75 4,67
25 3,65 2,55 4,50 3,65 2,70 4,55
37 3,55 2,45 4,32 3,60 2,65 4,48
12 12 3,70 2,45 4,52 3,70 2,60 4,57
25 3,60 2,40 4,40 3,60 2,55 4,45
50 3,50 2,40 4,30 3,50 2,50 4,33
62,5 3,50 2,35 4,28 3,45 2,50 4,28
25 25 3,60 2,35 4,28 3,55 2,50 4,38
50 3,50 2,35 4,28 3,45 2,50 4,28
75 3,50 2,25 4,25 3,45 2,40 4,25
50 50 3,45 2,20 4,18 3,40 2,35 4,18
75 3,40 2,20 4,13 3,40 2,35 4,18
100 3,40 2,15 4,12 3,35 2,25 4,10
75 75 3,40 2,20 4,13 3,35 2,35 4,13
100 3,40 2,15 4,13 3,35 2,25 4,10
> 100 3,40 2,15 4,12 3,35 2,25 4,10
Pouring temperature
Do not use high pouring temperatures but compare them to the TL or liquidus
temperature.
Maximum CEL (= %C + %Si/4 + %P/2) depending on section / pouring

temperature
Section Pouring temperature °C

mm 1315 1340 1370 1400 1425 1455
20 4,56 4,53 4,50 4,47 4,45 4,42

30 4,52 4,49 4,46 4,43 4,40 4,37
50 4,44 4,41 4,38 4,35 4,32 4,29
80 4,31 4,27 4,24 4,21 4,19 4,15
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Cooling rate
Use chills if possible because they will decrease the temperature quickly, lead to a
higher cooling rate, which means a lower real modulus.
Shape
It is impossible to change the shape, but it mostly helps if the largest sections are not
put on top of the mould.
Risers
Avoid large and heavy risers, especially hot type risers.
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7.2.3 CHUNKY GRAPHITE
7.2.3.1 Definition
Chunky graphite is graphite nucleated in cells with interconnected graphite
branches.
See the difference in free graphite types in figure 71.
Chunky graphite starts in a ball-shaped cell, and growths as a strong branching in

slightly isolated colonies; sometimes also described as a “cell-type accumulation of
compacted-flake graphite. The graphite is inter-crystalline eutectic graphite.
Chunky graphite is sometimes called “grouped vermicular graphite”.
Chunky graphite is not a broken graphite nodule. More information in the book
“Chunky Graphite”.
Examination with scanning electron microscope (SEM) shows that all the graphite is
within a cell interconnected. The average size of a chunky graphite cell is much
larger than the normal spheroid cells. It is often located along the austenite dendrite
arms and Mg-Ca-Si-S-O inclusions act mostly as nucleus.
Intercellular flake graphite is located at the cell boundaries, initiated by the

segregation of elements to these boundaries. Chunky graphite is located inside the
cells.
Figure 71
Difference in free graphite
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7.2.3.2 Appearance
The chunky graphite appearance shows large interconnected graphite cells, possibly
with nodules at intercellular boundaries. It appears mostly together with intercellular
flake graphite. See figure 72.
It is mostly connected to heavy sections (> 75 mm) and slow cooling. The RE, mainly
Ce and La will segregate and increase their content in the last solidifying metal. The
larger the section, the higher the Ce- and La-content.
Chunky graphite appears very often at the connection of riser-casting and can be
detected as a dark area with low strength and poor ductility. It will be promoted by
(too) high cerium content.
Figure 72 Appearance of chunky graphite
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7.2.3.3 Mechanism
The mechanism is not very well understood, and the researchers are still arguing with
each other. See book “Chunky Graphite”.
7.2.3.4 Influences
Up to now, no chunky graphite is found if there was no Ce present. So, this indicates
that chunky graphite formation requests a Ce-content.
The elements, which do promote chunky type of graphite, will mostly bloc the
formation of intercellular flake graphite and reverse. Here is the descriptive list:
Promoting chunky graphite in decreasing order: Ce, Ca, Si, Ni

Promoting flake graphite in decreasing order: Bi, Pb, Sb, As, Cd, Al, Sn, Cu.
Also, aluminium is promoting the appearance of flake graphite.
So, to eliminate both defects, a balanced addition of elements of both groups must
be added, or no of them at all.
If no other element is added, the balance between silicon (Si) and tin (Sn) must be
according to the figure 73.
CHUNKY GRAPHITE
3,5
3,3
Figure 73
3,1
Balance of Si & Sn and
chunky graphite
% Silicium (Si)
2,9 CHUNKY GRAPHITE

2,7 appearance
2,5
2,3
2,1
NO CHUNKY GRAPHITE
1,9
1,7
1,5
0 0,02 0,04 0,06 0,08 0,1
% Tin (Sn)
The elements Zr, Zn and Se are promoting intercellular flake graphite, but their effect
on chunky graphite is unknown or proven.
Titanium is a very special element. It is known for promoting flake graphite and can
be balanced by cerium:
0,01 % Ce balances 0,07 % Ti
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Titanium also interacts with magnesium (see figure 74).
Remark:
But titanium also combines with nitrogen (N), which can be present in the
metal. If the foundry is using a mould material, containing nitrogen like furan,
and does reclaiming of the sand, the nitrogen can interact with the metal in the
metal surface layer and cause pinholes and deterioration of graphite.
AREA OF GOOD NODULES
Figure 74 0,12
Influence on nodularity % Mg (Magnesium) 0,1
of Mg & Ti
0,08
AREA OF REGULAR NODULES
0,06
0,04
0,02
0
0 0,02 0,04 0,06 0,08 0,1
% Ti (Titanium)
A decreasing nodule count and an increasing magnesium level will increase the
amount of chunky graphite. An increasing cerium level will increase the amount of
chunky graphite, especially in thick sections (< 0,030 % or < 0,035 % for Ce + Li).
High CE (carbon equivalents) will also promote the formation of chunky graphite. For
the chemical composition of the metal after the nodulising treatment, take in account
that 0,05 to 0,15 % C is lost during this metallurgical treatment.
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Static mechanical properties
The static stresses are mostly tested by a tensile test.
The test results on specimen with chunky graphite are, in case of ferritic ductile iron,
indicating a:
1. medium decrease in tensile strength (depending on the amount of chunky

graphite)
2. equal yield strength
3. decrease in elongation: from over 18 % to 3 - 6 % for ferritic ductile iron
4. equal hardness (HB).
These above-mentioned effects will be less for pearlitic ductile iron.
If chunky graphite is present, the elongation decrease depending on the ratio of the
infected area to the total test bar area (it can decrease to very low values as < 5 %).
Some very common figures for ferritic ductile iron are:
Property Without chunky With chunky graphite
Tensile 390 MPa 295 MPa

Yield 280 MPa 275 MPa
Elongation 22 % 3–5%
Yield/tensile 0,72 0,93
The ratio between yield and tensile can give a clear indication, as seen above and in
the table below. The higher the ratio value, the more the chance for chunky graphite
or other non-conformities.
Tensile E0,2 % standard E0,2 / T
350 220 22 EN 0,629

400 250 18 EN 0,625
400 270 18 ASTM 0,675
450 310 10 EN 0,689
500 320 7 EN 0,640
600 370 3 EN 0,617
Pay attention, a high ratio yield / tensile strength can also indicate micro porosity or
inclusions in the test bar, which have nothing to do with chunky graphite.
This scattering in results for the elongation is due to the difference in ratio of the
section with chunky graphite, compared to the total section of the test bar.
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Dynamic stresses
Some of the largest German ductile iron foundries did order a study about defects in
large castings. This study is done by the “Froner Institut”.
The following results are found.
The fatigue strength seems to be decreased by some 30 to 50 %.
This decrease seems to be very

Defect Rel. Fatigue
high. But if we compare this
Endurance
decrease with the effect of other
types of non-conformities, then None 1.00
we can find that a CC1 (X-ray) Dross 0,54
defect has the same fatigue
strength decrease! This type of Micro shrinkage. 0,73
defect (CC1) is nearly all the time
and by 90 % of the customers Macro shrinkage 0,50
allowed.
Chunk graph. 0,75
Anomalies 0,83
Crack propagation
The rate of growth of a crack in the section with chunky graphite is increased a lot.
This is, according to German literature, some:
• 45 % decrease in crack sensitivity fracture

• 10 x higher crack propagation speed.
The critical crack size is shifted to very small values.
Machinability
Chunky graphite will increase the machinability, especially if it is combined with

graphite flotation. In this case, the hardness can decrease by some 20 HB.
But the surface quality will be less (higher roughness), due to the tearing off the
surface material.
The appearance will always be black (or dark grey) and rough (graphite is pulled out
by the tool).
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7.2.3.6 Solutions
So, the action of cerium is depending on the wall thickness and number of hazardous
elements, taken in account that the proper magnesium content is present. The
following rule can give an indication for the maximum cerium content.
Wall thickness < 25 mm Ce 0,020 – 0,015 %

25 – 50 mm Ce 0,015 – 0,010 %
50 – 100 mm Ce 0,010 – 0,005 %
100 – 250 mm Ce 0,005 – 0,002 %
> 250 mm Ce 0,002 – 0,000 %
If the actual Ce-content is too high, compared to the above given contents, an
addition of Sb can be made to compensate the too high Ce-content. This should only
be used in case of unexpected high Ce-content and not as standard procedure.
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7.2.4 INTERCELLULAR FLAKE GRAPHITE
7.2.4.1 Definition
This is about small free flake (lamellar) graphite, located on the grain boundaries.
7.2.4.2 Appearance
The chunky graphite appearance shows large interconnected graphite cells, possibly
with nodules at intercellular boundaries. It appears mostly together with intercellular
flake graphite. It is also more present in thick sections due to the segregation effect of
some of the flake graphite promoting elements. See figure 75 a, b and c.
A special appearance of the intercellular graphite (more small carbides) is also called
“Chinese script”.
Figure 75 a, b and c Appearance of intercellular

flake graphite
7.2.4.3 Mechanism
The flake graphite promoting elements are mostly segregating to the centre of thick
walls and their concentration on the grain boundaries will be sufficiently high for
forming small flake graphite.
Pay attention, this also happens in thin wall castings if the content of the flake
promoting elements is high and not compensated by Ce or another element.
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7.2.4.4 Influences
The elements, which do promote chunky graphite, do mostly bloc the formation of
intercellular flake graphite and reverse. Here is the descriptive list:
Promoting chunky graphite in decreasing order: Ce, Ca, Si, Ni

Promoting flake graphite in decreasing order: Bi, Pb, Sb, As, Cd, Al, Sn, Cu.
Also, aluminium is promoting the appearance of flake graphite.
So, to eliminate both defects, a balanced addition of elements of both groups must
be added, or none at all.
The elements Zr, Zn and Se are promoting intercellular flake graphite, but their effect
on chunky graphite is not known and not proven.
Titanium is a very special element. It is known for promoting flake graphite and can
be balanced by cerium:
0, 01 % Ce balances 0,07 % Ti
Titanium also interacts with magnesium.
But titanium combines with nitrogen (N), which is present in the iron.
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If the foundry is using a mould material, containing nitrogen like furan, and does
reclaiming of the sand, the nitrogen can interact with the metal in the metal surface
layer and cause pinholes and deterioration of graphite.
The main consequence is that the ductility decrease. The elongation of the tensile
test decrease and especially the high value Charpy V test result decrease and the
transition temperature increase.
7.2.4.6 Solution
1. Do not use too much steel in the charge, especially not:
• Galvanised steel
• High machinability steel with Pb, Se…
• Titanium killed steel
2. Control the subversive element content and compensate eventually with Ce.
Once formed and present in the solidified metal, it cannot be removed or

decreased anymore!
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7.2.5 EXPLODED GRAPHITE
7.2.5.1 Definition
This type of non-conform free graphite appears if the Mg (> 0,07 %) and or Mg + RE
content is high, especially if it is combined with a high CE (Carbon Equivalent).
It is especially appearing in thick section castings.
7.2.5.2 Appearance
The graphite can appear as a nodule that is cracked (starting phase) or even as a
splashed nodule (very pronounced effect). See figure 76, 77 and 78.
Figure 76 Exploded graphite
It is many times combined with graphite flotation.
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7.2.5.3 Mechanism
The mechanism is not very well known but it has surely to do with the high Mg-
content and the long cooling time in thick sections, section crossings or below risers.
7.2.5.4 Influences
The following factors play a role:
1. High carbon equivalent (CE > 4,33)

2. Too high cerium (also lanthanum, neodymium, praseodymium is working in
such way) content (compared to content of trace elements and wall
thickness), mostly > 0,02 %
3. Low cooling rate from pouring temperature to complete solidification
4. Too high magnesium content (Mg > 0,08 %)
The consequences are mostly very similar to graphite floatation, with which it mostly
appears together.
Mechanical properties, particularly tensile strength, elongation and impact strength,

can deteriorate significantly in the graphite flotation zone.
Observers have reported:
1. 25 % reduction in tensile strength,

2. over 80 % reduction in percent elongation, and
3. over 50 % reduction in impact strength
4. fatigue strength will decrease a lot (mostly > 25 %)...
The yield strength is very few influenced.
Graphite flotation is dangerous because it appears near to the surface, which in most
real stress situations is the highest stressed area.
The volume shrinkage will be totally different in the graphite flotation zone
compared to the other zones. Because the other zones lost more graphite, the
graphite expansion will be less, and it is likely that shrinkage appears.
The high carbon top zone has a large graphite expansion and the metal will be
pushed to the other area, which it cannot reach if the section is long. Than the mould
wall movement will be large, or the metal is pushed into the riser, which cannot work
properly anymore. The metal in the risers mostly also contains graphite flotation and
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the expected feeding behaviour is lost.
The fluidity of the hyper-eutectic metal is also less than for the eutectic one. This is
not due to the graphite flotation (there is during the filling not yet free graphite), but
appears mostly at the same time due to the common factor (CE > 4,5).
7.2.5.6 Solutions
1. calculate the proper Mg-addition (during nodulising), taken in account that RE

also will benefit the spheroidising
2. Decrease the CE according to the rules depending on the wall thickness
3. Decrease the pouring temperature
4. Use chilling for quicker solidification
5. Locate risers on an as small as possible section.
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7.2.6 DETERIORATED SURFACE GRAPHITE
7.2.6.1 Introduction
7.2.6.2 Types
The surface is influenced by:
1. Mould material and

2. Non-metallic inclusions at the upper side of the casting and below cores
3. Non-metallic or other inclusions at side walls of the mould.
This initiates reactions and forms inclusions, which are mostly composed of reaction
products on the base of sulfur MnS, MgS) or magnesium (MgS, Mg2SiO3, MgSiO4) or
other elements (MnS, MnO), which will influence the material at that location,
concerning graphite morphology and structure. These inclusions will have a
degenerating influence on the free graphite in the area concerned and will form slag,
dross, pin holes and other gas inclusions...
There are several types of deteriorated surface graphite: chunky graphite combined
with intercellular flake graphite, flake graphite, worm graphite (compacted) …
The chunky graphite, possibly combined with intercellular graphite, is discussed in

previous chapter. The effect at the surface will be initiated by the presence of sulfur
and or nitrogen in the mould material.
In this chapter, only the non-metallic inclusions that have an influence on the free
graphite will be discussed. The non-metallic inclusions are of the following nature:
1. sulphides
2. magnesium-sulphides and magnesium-silicates
3. magnesium-manganese-iron-silicates
4. magnesium-aluminium-iron-silicates
5. magnesium-calcium-silicates
6. silica-oxides (slag)
7. ferro-silicon
8. pin holes.
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7.2.6.2 Types
1. Sulfides
This is not common, but can happen if the mould material (sand) is poorly reclaimed
and the mould coating is not strong. Besides the MgS inclusions, there will also be
flake graphite on this location.
By poorly reclaiming of sand the sulfur content can increase. If the applied coating is
not tight or the coating does blister during pouring, the metal can come in contact
with the mould material and absorb sulfur. Mostly there will be a reaction with
magnesium (see next item: magnesium-silicates), unless the amount of magnesium
is locally to low.
Anyhow the graphite morphology (lamellar) will be disturbed, as shown on the

picture, figure 79.
Figure 79
Sulfides and flake graphite
A coating with zircon-magnesite-silicates will prevent a large sulfur pick up from the
sand in thin sections. In thick sections and section connections, no coating will be
that strong that it can prevent this sulphide formation from happening.
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2. Magnesium-sulfides and magnesium-silicates
This is the typical ductile iron “dross” type inclusion.
Dross is a reaction product formed by magnesium during the magnesium-treatment

and the subsequent re-oxidation of magnesium and the reaction with Si, rejected
from the molten metal. It is, present as a surface layer, always accompanied by flake
graphite!
Dross:
1. MgS: few present because removed after the nodulising
2. MgO: present but mostly on top of the metal in the ladle or inside the mould
in case of turbulent filling
3. Mg2SiO3, MgSiO4, 2MgO.SiO2: most dangerous dross type, formed by
turbulent filling and due to the reaction of Mg and the Si of the mould.
Appearance is given in pictures 80 to 84.
The reaction of magnesium with sulfur, oxygen and silicon are “continuously”. The
reaction product is lighter as the iron and will drift up to the surface. It will also be
located under the cores and at the sidewalls, where it sticks if it touches them.
It can form strong stringers instead of concentrated slag like area. A string like shape
will decrease the fatigue strength and the impact strength (like a crack).
If this effect is very well shown in the surface, it is called “elephant skin”.
Figure 80 Dross and flake graphite Figure 81 Dross
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Figure 82
Dross layer with flake graphite
Figure 83 Detailed dross inclusion
Figure 84 Elephant skin on a casting
This reaction cannot be avoided completely because ductile iron needs

nodules and therefore Mg will be present. It can only be minimalized!
Because the magnesium is primarily in the dross, in the surrounding of dross the
graphite will be deteriorated to vermicular and even flake graphite. Sometimes there
is also a graphite layer around the dross-defect.
The reaction involved will be:
Si + O2  SiO2
SiO2 + 2C  Si + 2CO
2 Mg + O2  2MgO
Mg2Si + O2  2MgO + Si
SiO2 + 2Mg  2MgO + Si
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MgO + SiO2  MgO.SiO2 (enstatite)
2MgO + SiO2  2MgO.SiO2
MgO.SiO2 + MgO  2MgO.SiO2 (forsterite)
The dross formation can be minimised by (sometimes conflicting rules):
1. keep the Mg content as low as possible for forming less MgS, MgO and
MgSiO4 and Mg2SiO3.
2. keep the Mg content sufficiently high to avoid flake and vermicular graphite
3. keep the CE (carbon equivalent) as low as possible because it leads to

graphite flotation and this condition increase the dross formation.
4. Keep the silicon content as low as possible (more SiO2, due to the reaction 2Si
+ O2  SiO2), especially when also Ni is used
5. Avoid over-inoculation because most inoculants are promoting the dross

formation due to the presence of SiO2, Al, Ce…
6. Decrease the pouring time and increase the pouring temperature. Low
temperatures will increase the dross formation (there will be much more SiO2,
due to the reaction 2Si + O2  SiO2) and prevent the floating up. Therefore,
particular care must be taken for heavy wall castings, where silicon can
oxidise and react with Mg being a long time with magnesium.
7. Avoid turbulence during pouring and mould filling. Oxygen will be pulled in the
metal (2 Mg + O2  2MgO). Therefore, it is preferred to fill a mould bottom up
at an as low speed as possible.
8. Perform a proper slag removal of the ladle before pouring.
With the use of nickel-magnesium in niresist irons (containing from 15 to 35 % of

nickel), the problem (dross formation) will be much larger.
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3. Magnesium-manganese-iron-silicates
This is a complicated dross inclusion (see previous item), see figure 85.
It is stringer like, rather thick and long. It will deteriorate the graphite nodules near to
it, although less as the previous inclusions (magnesium-sulphides and magnesium-
silicates that formed flakes).
The difference is that this will happen, producing a ferritic ductile iron with a too high
magnesium and or silicon and manganese content.
Figure 85 Mg-Mn-Fe-Si inclusions
Especially the manganese will try to

react with sulfur, which is very low
levelled in ductile iron. Then the
manganese will segregate to the last
solidifying area, which is mostly the
riser and the area just below the riser
and hot spots and center of thick
sections.
In these locations, a magnesium-manganese-iron-silicate can be formed.
To avoid this type of slag, the

magnesium and silicon level must
be as low as possible. But also, the
manganese content must be set
according to the indication in the
figure 86.
Figure 86
Relation Si-Mn (avoid dross).
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4. Magnesium-aluminium-iron-silicates
This is another complicated dross inclusion (see previous item); see figure 87.
It is a stringer like inclusion, rather thick and long and these strings contain graphite.
It will deteriorate the graphite nodules, although less as the previous inclusions
(magnesium-sulphides and magnesium-silicates and magnesium-manganese-iron-
silicates).
Figure 87
Mg-Al-Fe-Si dross
The difference is that this will happen, producing a ferritic ductile iron with a too high
magnesium and or silicon and aluminium content.
The aluminium is coming partly from the raw material (steel scrap), but mostly from
the inoculant. Several inoculants have high aluminium content. If this is combined
with a high magnesium and silicon content, this type of dross can be formed.
The appearance will be strong, long and thick stringer-like. The influence on the
graphite deterioration is not very high, as can seen in figure 69.
Aluminium is mostly present in the range of 0,003 to 0,05 % and does promote
pinholing and the appearance of vermicular (wormlike) graphite. It is accepted that
the maximum content should be 0,05 % combined with a low Mg- and Si-content!
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5. Magnesium-calcium-silicates
This is another type of dross like inclusion. See figure 88.
The inclusion is massive and at the borders a small area of degenerated graphite is
present. If calcium is not part of the dross, it will form a very fluid slag.
If the inoculant contains Ba, also this element, together with Ca, will be present in this
type of dross.
It appears if the magnesium, silicon and calcium-content are high.
The calcium will mainly come from a previous desulfurising treatment. It is also
present in some inoculants.
Figure 88
Mg-Ca-Si or Mg-Ca-Ba-Si
dross
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6. Silica-oxides (slag)
This inclusion will appear as a cluster. See figure 89.
It is mostly part of the refractory lining of the furnace and or the ladle.
It has nothing to do with the chemical composition of the metal.
It forms an agglomerate and can have a small influence on the graphite morphology
at its borders. The graphite can appear in nids and be very small sized.
The influence on the nodules and on the properties, is very small.
Figure 89
Silicon oxide inclusions
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7. Ferro-silicon
It is also called: “shiny inclusions”. It is mostly surrounded by very fine graphite

nodules. See figures 90 to 93.
This inclusion is probably the least harmful of all. It is ferrosilicon, mostly inoculant,
which did not solve in the liquid metal. It is frequently observed for thin wall castings,
which are immould inoculated.
To avoid this, it is preferred to inoculate with fine grained inoculant and at an

elevated temperature, depending on the time from the inoculation to the solidification
of the metal. Improving the pouring system, to avoid entering of this ferrosilicon to the
mould, is a safety measure.
Figure 90 Ferro-silicon inclusion Figure 91 Ferro-silicon inclusion
Figure 92 Ferro-silicon inclusion
Figure 93 Ferro-silicon inclusion
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8. Pinholes
Pinholes are a defect in the material, mostly gas like bubble (hydrogen gas) just
below the casting surface.
The gas holes are spherical, or egg shaped, have a diameter less than 3 mm (< 3
mm) and do have shiny smooth walls, mostly with a crystalline graphite film inside.
The metal around this defect is mostly slightly decarburized and sometimes a ferrite
ring with vermicular or lamellar free graphite.
The open pinholes are mostly a combination of pin hole and dross.
See figure 94 to 96.
Figure 94 Closed pin hole
Figure 95 Detail of closed pin hole
Figure 96 Open dross pinhole
It is a defect, lack of material, which also influence the carbon at its borders, but only
in a very small area around the pin hole. The hole can be internally coated by a
graphite layer (mostly for the closed defects) and by deteriorated graphite (mostly for
an open defect) in the surrounding area.
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It is the hydrogen content, which will cause pinholing. Some of them have an opening
to the surface, some not. The defect is catalysed by the presence of nitrogen and
depends on the hydrogen content.
The main source is humidity, moisture, and water from the:
* air
* reaction products due to the slag
* rust and humidity on ferro-alloys, scrap, returns...
* wet refractory lining of the furnace or ladle
* mould and or core material, especially green sand moulds
* water coating.
Aluminium is increasing the solvability of hydrogen at elevated temperature but will

also catalyze the splitting of water, as also does magnesium and manganese.
Mg + H2O ---> MgO + 2 H

2 Al + 3 H2O ---> Al2O3 + 6 H
Mn + H2O  MnO + 2 H
Ti will increase the effect of aluminium (Al). Therefore, the following rules are
preferred:
* Al < 0,01 %, which can be a problem for ductile iron due to the necessary
high amount of inoculation.
* Ti < 0,02 % if combined with aluminium.
To avoid this defect, the following actions are preferred:
1. The hydrogen content must be decreased. The hydrogen can come from
rusted raw material, but mostly from the moisture in the mould and the air.
Therefore, dry the mould (especially for green sand moulds) and use
mould material with low water content and low nitrogen content (furan and
catalyst in chemical bounded sand).
2. Do ingate at thin sections and increase pouring temperature.
3. Manganese will promote the hydrogen pickup. Decrease the manganese
content.
4. Keep the Mg content low
5. Use inoculants with low aluminium content
6. Add 0,05 % Te.
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7.2.7 CARBIDES & PHOSPHIDE EUTECTIC
7.2.7.2 Cementite
7.2.7.3 Carbides due to spheroidizers
7.2.7.4 Alloyed carbides
7.2.7.5 Inverse chilling
The carbides are combinations of carbon with another element and they do influence
graphite morphology because they do take carbon from the metal, consequently
there is less graphite available for the free graphite segregation.
The carbides have a high hardness; do decrease the ductility and Charpy V value
and the machinability. Also, the shrinkage tendency will increase.
Carbide content has both direct and indirect effects on the properties of ductile iron
castings. Next figures 97 and 98 show that increasing the volume per cent of hard,
brittle carbide increases the yield strength, but reduces the tensile strength. This
convergence of yield and tensile strengths produces a decrease in elongation with
increasing carbide content.
Figure 97
Effect of carbides on yield strength
Figure 98
Effect of carbides on tensile strength
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The presence of carbides in a ductile iron matrix also increases the dynamic elastic
modulus and significantly reduces machinability.
The formation of eutectic carbide during solidification affects the volume fraction of
graphite produced because carbide and graphite compete for the carbon contained in
the liquid iron. Fifteen volume per cent of carbide would require 1 per cent carbon,
reducing the carbon available for graphite by approximately one third. The formation
of carbide thus increases the likelihood of internal casting porosity by reducing the
expansion effects produced by the formation of graphite during solidification.
To minimize the detrimental effects on properties and machinability, maximum

carbide levels of less than 5 % are normally specified. These levels can usually be
achieved as-cast by reducing the levels of carbide forming elements using high purity
pig iron in the furnace charge and by increasing the nodule count through the
application of good inoculation practices.
When required, heat treatment can be used to eliminate carbides. This can reduce
the effect on the properties and machinability but the effect on the porosity will still
exist because it happened during the solidification.
The iron carbides, called cementite (Fe3C), are composed of iron and carbon. The
other carbides are alloyed with an element as can be: manganese, chromium… But
also trace elements as titanium can form carbides; especially if an excess of cerium
is present (> 0,03 %).
There are four types of carbides: cementite, carbides from spheroidizers, carbides
from alloying elements and inverse chilling.
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7.2.7.2 Cementite
This iron-carbide (Fe3C) is also called “chill carbide” and can be present in any
ductile iron (mostly formed due to quick cooling). The appearance can be seen in
figures 99 to 102.
It forms a continuous phase due to an improper metallurgical condition of the metal

for the given cooling rate.
It will decrease the ductility (as well on room temperature as lower temperatures) and
machinability and increase the hardness and shrinkage tendency of the material.
They are mostly combined with small pearlite area in a ferritic structure.
To avoid this type of carbide formation, the chemical composition (concerning carbon
and silicon) must be balanced to the wall thickness and the cooling rate.
It is necessary to decrease manganese as much as possible due to its segregation

effect, especially in thick wall castings. The trace elements as are chromium and
titanium must be as low as possible, because they will increase the effect of
manganese.
Decreasing the wall thickness will increase the tendency to form cementite.
The higher the cooling rate, the higher the tendency to form cementite
The only remedy, if the chemical composition is set, is an efficient inoculation, which
depends on the type of inoculant, the amount of inoculant and the time of addition,
which should be as close as possible to the solidification.
Figure 99
Cementite in non-inoculated iron
Figure 100 Cementite in pearlite structure
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Figure 101 Cementite in ferritic structure
Figure 102 Cementite
The tendency to form cementite can be evaluated by the graphitising factor K (the
lower the factor, the higher the tendency to form cementite):
K = %C * {%Si – 0,2 *(%Mn – 1,7 * %S – 0,3) – 1,2 * %Cr – 0,4 * %Mo – 2 * %V

– 8 * %Mg + 0,1 * %P + 0,4 * %Ni + 0,5 * %Al + 0,4 * %Ti + 0,2 * %Cu}
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7.2.7.3 Carbides due to spheroidizers
These are needle-like carbides as can be seen in the microstructure picture (figure
103). As a matter of fact, they are plate shaped.
They mostly appear in case that there is too high magnesium content, or other rare
earth elements, used as spheroidizer, like Ce…
They will certainly appear if the silicon content of the iron is low (problem in low
temperature application ductile iron).
Decreasing the amount of magnesium and or rare earths and increasing the silicon
content will decrease the amount of this type of carbides.
Figure 103
Carbides due to too high
Mg-content
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7.2.7.4 Alloyed carbides
These are carbides formed by carbon and another element, not being iron (Fe) or Mg
or RE (Rare Earths).
Manganese carbides
In the unalloyed ductile iron (only C, Si, Mn, P, S and Mg and RE are intentionally
added and present), the alloyed carbides can only be manganese-carbides. See
figures 104 and 105.
It appears depending on the silicon content and cooling rate and section size.
Up to a section of 37,5 mm (1,5 inch), the manganese content can be balanced by
silicon. For larger section, this is not possible anymore. They will appear in these
thick sections, due to the segregation of manganese (see segregation tendency).
In a thick section, the cooling to the solidification is that slow that for instance a 0,35
% Mn will increase up to 2,5 % in the last freezing metal (thermal center). The silicon
cannot help anymore because this segregates in the first freezing metal.
Manganese will react, especially if there is very few sulfur, with carbon to form
carbides. These carbides are the least harmful alloyed carbides.
Sulfur can decrease the amount of manganese carbides if the amount is about 0,008
% or higher. This sulfur content is a minimum content for ductile iron.
Figure 104
Manganese carbides Figure 105 Manganese content on
micro-scale
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Other carbides
If there is some chromium present, mostly from the steel scrap, this can form carbide,
definitely if the amount is over 0,5 % (See figure 106). If the amount is less, it can
combine with manganese in the complex manganese-chromium-carbide. This leads
to the rule to never combine high Mn and Cr. See figure 107.
Figure 106
Chromium-manganese carbides
Figure 107 General alloyed carbides
The elements vanadium (V) and molybdenum (Mo) can also form carbides, mostly at
the grain boundaries, which decrease the ductility very much.
The trace elements are also important. Especially titanium is a strong carbide
promoter (max Ti < 0,07 % to avoid carbides). These carbides are cubic and are
situated at the grain boundaries. Besides forming carbides, titanium does promote
vermicular graphite. See figure 108 to 110.
Titanium carbides do decrease the ductility, especially at low temperatures.
Figure 108 Cubic titanium carbides

Figure 109 Detail cubic titanium carbides
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Figure 110 Anchor shaped titanium

carbides
List of carbide promoting elements in alphabetic ranking is:
B, Ce, Cr, H, Mg, Mn, Mo, Se, Te, Ti and V.
General rule for these elements:
Cr < 0,05 % (not alloyed)

Cr < 0,50 % (if combined with Mo)
V < 0,03 %
B < 0,002 %
Mo < 0,05 %
Mo < 0,30 % (alloyed)
Ti < 0,04 %
Te < 0,003 %
Mn < 0,35 % for pearlitic structure, section > 12,5 mm
Mn < 0,60 % for pearlitic structure, section < 12,5 mm
Mn < 0,25 % for ferritic structure, section > 12,5 mm.
The carbides are also present in thick sections, in the center, due to segregation!
Especially Mn and Mo are very prone to it.
Alloyed carbides are difficult to dissolve by heat treatment; require a very long
dwelling time on elevated temperature.
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7.2.7.5 Inversed chilling
This deals about large area of carbides in the center of a section. See figure 111 and
112.
Due to very low oxygen content after spheroidizing, the initially freezing material is
graphitic, but the last freezing metal will contain too few nuclei and the structure will
become increasingly white (more carbides).
Another reason can be the inoculation, which depending on the efficiency of it, will
have the following consequences:
• too few efficiency: no or insufficient nuclei

• too much inoculant: first freezing metal takes all oxygen.
Figure 111 Inverse chilling Figure 112 Detail inverse chilling
To avoid this inverse chilling presence, the following rules must be followed:
• avoid high melting temperatures

• avoid long dwelling time on elevated temperature
• decrease the magnesium-content
• reduce the amount of carbide promoting elements
• improve inoculation: amount and time of inoculation.
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7.2.8 PHOSPHIDE EUTECTIC
Phosphide eutectica are compounds, which are very rich in phosphor content. See
figures 113 and 114.
Phosphorus is practically insoluble in iron at room temperature. The formed

phosphide eutectic (Fe3P) is rejected from the last iron to freeze and will be located
at the grain boundaries.
Due to this segregation effect of P, the content in the last freezing metal will be:
2 x % P in thin sections (< 10 mm)

5 - 10 x % P in thick sections (> 25 mm).
Each 0,01 % P can form 0,064 % of Fe3P.
These eutectica are frequently combined with small pearlite area and carbides.
Figure 113 Phosphide eutectic
Figure 114 Detail of Phosphide eutectic
They do decrease the mechanical properties at higher temperatures. They always do

decrease the ductility very much.
A phosphorus content increase of 0,03 to0,06 % can decrease the elongation with 50
%. The dynamic strength is lowered a lot, because these phosphides, located at the
grain boundaries, will easy a crack growth and decreases the Charpy V value as well
as increase the transition temperature.
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Phosphide eutectica have few influence on the graphite shape, promotes pearlite and
forms intercellular carbide network. This is shown in the figures 115 to 117.
Figure 115 Phosphide eutectic
Figure 116 Phosphide eutectic and

degenerated graphite
Figure 117 Phosphide eutectic and

carbides
Phosphide eutectica do increase the tendency to form porosity during solidification.

They also decrease the weldability, which is normally already low for ductile iron.
The effect can be decreased by a “full annealing” of the material (austenitizing and
very slow cooling), but can never be removed!
To avoid these eutectica, the following rules should be fulfilled:
1. P < 0,03 % before nodulising, should definitely < 0,035 % final analysis
for ferritic ductile iron, which will be used at low temperatures.
2. P < 0,05 % for ductile iron used for application at room temperatures.
3. P < < 0,1 % before nodulising and in the final analysis is preferred < 0,05 %
for pearlitic ductile iron.
The phosphorus content should be about 0,02 % to avoid the effect completely.
Another rule: % P + % Si < 2,53 % for P < 0,03 % and Si < 2,50 %.
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7.2.9 REMARK: CHEMICAL ANALYSIS
All the effects, discussed in this chapter, are the consequence of very small changes
in chemical composition and or the presence of elements in very small quantities.
To evaluate the effect and find solutions, it is required to have a correct chemical
analysis!
If performed by the spectrometer, some of the elements will be difficult to measure

because the testing tolerance can be of the equal magnitude as the result.
Secondly, the spectrometer must be calibrated with the proper samples, containing at
least a sample with a lower content and a sample with a higher content. This for all
elements involved.
If the elements are not properly measured, please do not use the result for further
evaluation and action!
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7.3 STRUCTURE
7.3.1 Introduction
7.3.2 Chemical composition
7.3.2.1 Elements without influence
7.3.2.2 Elements promoting ferrite
7.3.2.3 Elements promoting pearlite
7.3.3 Cooling rate
7.3.4 Surface layer
7.3.1 INTRODUCTION
The most common structures in the “as cast” castings are ferritic and pearlitic or a
combination of both.
The other structures as are bainitic and martensitic are mostly present after a heat
treatment, mostly quenching and tempering or austempering or martempering.
The austenitic structure can exist if the material is alloyed with a sufficient amount of
nickel.
The as cast structure will depend on the chemical composition and the cooling rate in
the mould; the structure after heat treatment depends on the chemical composition
and cooling after austenitising.
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7.3.2 CHEMICAL COMPOSITION
As already mentioned, the chemical composition is chosen in a way that there are no
carbides, the correct graphite morphology is present, and the structure is achieved in
the “as cast” condition.
A low nodule count will favour the pearlite structure.
We deal in this chapter with the structure and its dependency of the chemical
composition. There are elements, which do:
1. not influence the structure

2. promote ferrite
3. promote pearlite.
7.3.1 Elements without an influence

Carbon has no influence on the structure. Be aware that the spheroidizing treatment
will decrease the carbon content by 0,05 % with few stirring and 0,20 % with violent
stirring (stirring dependant mainly on the Mg-content of the FeSiMg). The lost carbon
will enter the slag or disappear as CO.
The spheroidizing active elements (mainly Mg but also Ce, La, Y…) have no
influence on structure, although they can form carbides if their amount is too high.
Sulfur, determined as final sulfur content after the spheroidizing treatment, has no
influence on the structure. But there is literature mentioning that, depending on the
ratio to the manganese content, there can be a different amount of ferrite.
For a silicon content of 2,5 %, if Mn / S = 15 to 17, the ferrite content will be
maximised. This means that for S = 0,010 %, manganese should be 0,15 to 0,17 %.
7.3.2 Elements promoting ferrite

Silicon is the most powerful ferrite-promoter.
But it does increase the strength and the hardness of the ferrite, does decrease the
impact test energy and thermal conductivity, does increase the transition temperature
(Charpy V testing) for brittle fracture.
For material with very low silicon, it is possible that the yield strength is too
low. To avoid this, sometimes the material is alloyed with 0,2 to 0,5 % of
nickel. This can be introduced by a spheroidizing with nickel-magnesium.
But by adding Ni, a heat treatment is required if the ductile iron is of Type EN-
GJS-400-18 or EN-GJS-350-22, to assure a complete ferritic structure.
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Some figures concerning the increase of transition temperature:
Silicon 30,0 °C per 1 % in the range from 1,0 to 2,0 % silicon

Silicon 45,0 °C in the range from 2,0 to 3,0 % silicon
Silicon 60 – 100 °C (other literature)
Nickel 10 – 22,0 °C
Manganese 55,0 °C
Phosphorus 280 - 300 °C
It has also a strong influence on the graphite morphology (nodule count if Si is added
as inoculant) and can cause graphite flotation (if the CE is high compared to the
section) as well as promote the formation of dross (magnesium-silicon- sulfur
products).
For the appearance of graphite flotation, see chapter 7.2.2 GRAPHITE FLOTATION.
It is important to know the structure because it is the most important item for the
strength and toughness. The ferrite content can be calculated, although not all
literature gives equal formula. Never forget that the structure is also depending on the
cooling rate after pouring; these formulas suppose that the casting could be cooled in
the mould until a temperature below 400 °C.
Formula 1
% ferrite = 92,3 – 96,2 (%Mn) – 211 (%Cu) – 1427 (%Pb) – 2815 (%Sb)
Formula 2
% ferrite = 40,7 + 12,2 (%Si * Sc) –239,2 (%Mn)

+ 75,4 (%Si * Sc) * (nodules/mm2)
+ 0,089 (nodules/mm2) * (% inoculation)
Sc = % C / {4,3 – (%Si)/3 – (%P)/3}
(Sc : see calculation graph on next page)
Formula 3
% ferrite = 66 (%Si) + 721 (%P) + 226 (%Mo) – 29 (%Mn) – 100 (%Cu)

- 30 (% Cr) -16,5 (%Ni) – 234 (%Mo * %Ni)
– 113 (%Cu * %Mo) – 86
The first formula is non-complex but does emphasize the trace elements like lead too
much. The result cannot be very accurate (difficulty to measure Pb-content). Also, the
influence of copper seems to be too high.
The second formula does take in account the chemical composition as well as the
metallurgical quality of the metal (nodule count and inoculation). As such it is not
taken in account the alloying elements as are copper, nickel…
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The formula is meant to be able to calculate the expected ferrite content, based on
the chemical composition and standard cooling rate. The problem is that it is very
difficult, or it requires a lot of statistical research, to predict the nodule count, which is
used in the formula.
The third formula is very complete concerning all the common alloying elements. It is
easy to use for every foundry but requires a very high process control concerning
nodule count and inoculation.
The hardness of the ferrite is increased according to the following formula:
HVferrite = 29,12 x (% Si) + 110,63
These formulae cannot be used for pearlitic iron, which means type EN-GJS-600-3
and higher.
Figure 118 Calculation Sc and Tl-temperature
There is also a special guideline for the Mn-content.

Above 70 mm, the maximum Mn-content should be 0,20 % (segregation effect).
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With lower wall thickness, the Mn-contents can partly be compensated by the Si-
content as indicated in next figure 119.
Figure 119
Preferred maximum
Mn-content
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7.3.3 Elements promoting pearlite
There are two mechanisms for the pearlite promotion:
1. segregating of elements to the last solidifying liquid
The ranking, segregation factor, is as follows, stating that a figure < 1,00
indicates an element that goes to the “first freezing” liquid and a figure >
1,00 indicates an element that segregates to the “last freezing” liquid.
Element Mo Ti V Cr Mn P
Factor 25,3 25,0 13,2 11,6 1,7 – 3,5 2,0
Element Si Co Ni Cu
Factor 0,7 0,4 0,3 0,1
The higher the segregation factor, the more important the cooling time
will be. A slow cooling (up to solidification), will increase the
segregation.
2. retarding the diffusion of carbon to the ferrite and stabilising

cementite
These are the carbide promoting elements, as an example Mn.

The ranking for the “pearlite promoting” effect is as follows:
Element Sn Mo P Cu Ti Mn Ni Cr
Effectiveness 39 7,9 5,6 4,9 4,4 0,44 0,37 0,37
In practice, the following must be taken in account:
1. Manganese is never used for structure purpose, but will be limited to avoid
carbides (depending on Si-content)
2. Phosphorus is never used for promoting pearlite because of its effect as is:
decreasing ductility and weldability, increasing the formation of porosity and
phosphide-eutectic
3. Titanium is never used for pearlite promotion because of its negative effect on
graphite morphology and tendency to form carbides
4. Chromium is seldom used for pearlite promotion because its strong tendency
to form carbides
5. Molybdenum is seldom used for pearlite promotion because it’s excessive cost
and tendency to form cell boundary carbides. It is used if the material is
applied in the service temperature range of 400 to 550 °C (because of its
increasing effect on creep resistance)
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6. Nickel is seldom used for pearlite promotion because of its cost. It can be used
if the silicon content must be very low and the spheroidizing is done by nickel-
magnesium
7. The most economic and frequently used combination is: Cu and or Sn.
Both will decrease the elongation of the tensile test.
The following combination assures 99 % of pearlite (2,5 % silicon)
Cu % 1,5 1,0 0,5 0,25 0,00

Sn % 0,00 0,03 0,07 0,15 0,24
But these elements do have an influence on the graphite morphology:
Only Sn, and Sn > 0,17 % intercellular flake graphite
0,07 % Sn + 1,0 % Cu intercellular flake graphite
0,10 % Sn + 1,5 % Cu nodular graphite
Proposal: Sn from 0,075 to 0,15 % or

Cu from 1,00 to 1,75 % or
Sn 0,10 % combined with 1,0 % Cu.
An example of the influence of copper on pearlite content is indicated in figure 120a.
PEARLITE ACCORDING TO % Cu
100
% PEARLITE
80
60
40
20
0
0 0,25 0,5 0,75 1
% Cu
Figure 120a Influence of Cu on pearlite formation
Remark:
An addition of < 0,30 % of Cu has nearly no effect on the properties. See figure
120b.
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Figure 120b Influence of Cu on properties of ductile iron
Remark:
Antimony (Sb) is a very strong pearlite promoter, a lot more than tin (Sn). It is
sometimes introduced by inoculants. Pay attention for it!
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7.3.3 COOLING RATE
7.3.3.2 Calculation method 1
7.3.3.4 Influence of chills
The cooling rate (after pouring) is important in the temperature range of 800 down to
400 °C. Below the temperature of 400 °C, the structure is not changed anymore in
unalloyed or low alloyed ductile iron. The cooling rate after heat treatment can lead to
martensite at lower temperatures, but this is not considered in this text.
A quick cooling will promote pearlite.
The cooling rate after pouring is depending on the mould concept (especially the ratio
of sand to iron and the sand thickness between the casting and the mould box), the
use of chills and the shakeout time.
A mould with high sand to metal ratio will have a very low cooling rate. This will
promote ferrite formation.
The cooling rate is important in the temperature zone of 800 to 400 °C (figure 121).
It is depending on the mould concept, the use of chills and the shakeout time.
A rapid cooling will promote pearlite.
A mould with high sand to metal ratio will have a very low cooling rate. This will
promote ferrite formation.
For a green sand mould with a sand / metal ratio of 2 / 1, containing a flat casting
without cores, the following figure can be used as a guideline for cooling from 1400
°C to 660 °C. This temperature is too high for ferritic castings and high complex
castings. The residual stresses build up by this removing from the mould at 660 °C
will create too much residual stresses. The cooling to 315 °C, which is preferred for
ferritic ductile iron castings and complex shape castings, takes double time.
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Figure 121 Cooling from 1400 to 660 °C in green sand moulds
The time, read on the scale, must be multiplied by it selves.
If the casting has a complicated shape, and especially a lot of cores (core
sand will heat up the metal or slow its cooling) and heavy sections in the
center of the casting / mould, and or low residual stresses, this time can be
multiplied by
1,5 for complicated shapes

2,0 for casting with cores and required low residual stress
3,0 for casting with lot of cores, heavy sections /low residual stress.
This new result will be multiplied by

2 for a sand / metal ratio of 4
2,5 for a sand / metal ratio of 6.
If the casting is produced in chemical bounded sand, the result times,
calculated for green sand, must be multiplied by another 1,75 x.
Therefore the full day (24 hours) per 50 mm of section is a good rule for
ferritic ductile iron castings in chemical bounded sand mould.
Example for green sand
The dotted line gives an example (in green sand) for a maximum section with
5,05 cm modulus (about 100 mm wall thickness) and simple shape, targeting
for a ferritic structure but shaken out at 660 °C, indicating 20. This means that
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the preferred shake out time is 20 x 20 = 400 minutes or 6 hours and 40
minutes.
Allowing the casting to be until 315 °C in the mould (for having low residual
stresses), will double the time, which means 800 minutes or 13 hours and 20
minutes.
If the mould has a sand/metal ratio of 4, the time will be 1600 minutes or 26
hours and 40 minutes.
Example for chemical bounded sand
If there is the same situation as for green sand concerning casting and mould,
we must multiply the green sand figure by 1,75; which mean 2800 minutes or
46 hours and 40 minutes. This is 1 day 22 hours and 40 minutes, which fits
good with the rule indicated above (24 hours per 50 mm wall thickness).
SUMMARY
For a green sand mould with a sand / metal ratio of 2/1, containing a flat
casting without cores, the following figure can be used as a guideline for
cooling from 1400 °C to 660 °C.
Dimensional Pearlite Ferrite

Wall
Modulus Minutes Hours Minutes Hours
thickness
cm mm min h min h
result A result A result B result B
1 20 4 5
2 40 35 65 1h5min
3 60 65 1h5min 120 2h
4 80 120 2h 255 4h15min
5 100 225 3h45min 400 6h40min
6 120 290 4h50min 530 8h50min
7 140 400 6h40min 785 13h5min
8 160 530 8h50min 1025 17h5min
9 180 730 12h10min 1295 21h35min
10 200 840 14h 1600 26h40min
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Multiplication factors, applicable on table
Green sand Chemical bounded sand

Pearlite Ferrite Pearlite Ferrite
Extra 660 °C 315 °C 660 °C 315 °C 660 °C 315 °C 660 °C 315 °C
result result result result result result result result

Ax Ax Bx Bx Ax Ax Bx Bx
Simple shape 1,00 2,00 1,00 2,00 1,75 3,50 1,75 3,50
Complicated shape
Sand/metal: 2 1,50 3,00 1,50 3,00 2,60 5,25 2,60 5,25
Sand/metal: 4 3,00 6,00 3,00 6,00 5,20 10,5 5,20 10,5
Sand/metal: 6 3,75 7,50 3,75 7,50 6,50 13,1 6,50 13,1
Cores/ low residual

stress
Sand/metal: 2 2,00 4,00 2,00 4,00 3,50 7,00 3,50 7,00
Sand/metal: 4 4,00 8,00 4,00 8,00 7,00 14,00 7,00 14,00
Sand/metal: 6 5,00 10,0 5,00 10,0 8,75 17,5 8,75 17,5
Cores/ heavy section /

low residual stress
Sand/metal: 2 3,00 6,00 3,00 6,00 5,25 21,0 5,25 21,0
Sand/metal: 4 6,00 12,0 6,00 12,0 10,5 42,0 10,5 42,0
Sand/metal: 6 7,50 15,0 7,50 15,0 13,1 52,5 13,1 52,5
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QIT suggests the following graph, shown in figure 122, of which the result comes
close to the previous method.
Figure 122 Preferred shake out time for ductile iron castings
The literature around this method is not mentioning any condition concerning sand to
metal ratio, or conditions concerning the number of cores or the complexity of the
shape. It is supposed that similar correction factors can be applied as for method 1.
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7.3.3.4 Influence of chills
The effect of the chills on the casting is more than just speed up the solidification at
the chill area.
The chill absorbs heat from the casting and consequently will increase its
temperature. The temperature of the chill, at the end of the solidification, will depend
on the volume of the chill, its heat density and heat conductibility.
A thin chill will heat to a higher temperature than a thick one.

An iron chill can absorb more heat than a graphite chill, but a graphite chill can
conduct its heat much better to the surrounding sand; so mostly the final
temperature of a graphite chill will be lower than from an iron chill.
When the metal passes the Ac3 temperature and the austenite transforms to pearlite
or ferrite, the casting cooling rate slows down because the chill also must cool (which
acts as a much thicker casting wall). The following happens:
1. Transforming to ferrite: the cooling rate slows down and the ferrite
transformation is favoured, which is targeted.
2. Transforming to pearlite due to the chemical composition (alloying

elements): the cooling rate slows down and the material can pass through
the ferrite zone in the CCT diagram. But even if it is still pearlite, the time in
the temperature range of 680 to 600 °C is that long that pearlite dissolves
into ferrite and graphite. The ferrite and graphite have a lower strength and
hardness.
When the casting is chilled over a large area and especially when the distance
between the chills is large compared to the thickness, there will be pearlite area (in
between the chills) and ferrite area (at the chill contact).
So, the result will be a mixture of pearlite area and ferrite area, clearly separated from
each other and consequently also a mixture of area with different hardness and
strength. See figure 101 for the principle. If the chills are close to each other, the
outer surface can be all over ferrite and nothing can be seen in the as cast condition.
Anyhow, if the machining is done, the area will be clearly visible until the machining
has removed all the material that was influenced by the chills. See figure 123 and
124.
The amount of influenced depth can be influenced by the thickness of the chill
compared to the thickness of the casting, but be aware that this can lead to chills that
do not have the required effect on the solidification modulus of the casting section
involved.
Chilling in small section (< 25 mm) will tend to the formation of pearlite and probably
cementite or carbides. The chills do take a lot of heat from the metal and can
transport this heat without becoming an elevated temperature.
There will be a very high nodule count, especially if no carbides are formed.
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Chilling very thick sections (> 75 mm) will lead to a quick freezing of the metal. This
metal will have a high nodule count. But now the chills are heated up a lot (to 700 °C
for iron or steel chills). The cooling of the metal will be very slow, and ferrite will be
formed in the area under the chills. The rest of the metal can be pearlitic.
Never chill a heavy wall casting in ductile iron for increasing the hardness!
This effect can only be removed by a heat treatment, using a temperature above Ac3
(to assure that all material will have the austenitic temperature) and then cooling at
the proper rate to assure the pearlitic structure.
Figure 123
Effect of chilling on pearlitic ductile
iron (principle)
Pearlite-ferrite mixture
Pearlite
Figure 124
Effect of chilling on pearlitic ductile
iron after machining
The casting wall thickness is 150 mm, chill thickness 80 mm. After machining 8 mm,
the hardness difference was 175 HB (under the chill) and 252 HB (in between the
chills).
Pay attention for cases where the casting is close to the mould box, which create a
situation that the flask (mould box) can act as a chill. This can, in case that the flask
is heavy walled, have a chilling effect on that casting area and influence the structure
as mentioned above.
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7.3.4 SURFACE LAYER
It is possible that, at the surface of a casting, a different structure will be present.
It is known already for the graphite shape, which can be different due to the reaction
of the metal with elements coming from the mould material. An example for this is the
flake graphite due to the reaction of Mg from the metal with S from the chemical
bounded sand, to such extends that flake (or vermicular) graphite is formed.
But also, due to segregation effects and flotation of free graphite and dross (to a
lesser extend of slag), the chemical composition can be locally changed so that a
different structure is formed. This will mostly be on top of the casting (as is located in
the mould) but does not happen very often. See figure 125 and 126.
It is also possible, especially for thin castings, to change the surface structure by
using a special coating.
Figure 125 Ferritic surface layer Figure 126 Normal surface layer
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7.4 INCLUSIONS
The inclusions, due to the metallurgy, can be:
1. Carbides
2. Nitrides
3. Dross
4. Slag.
Carbides are dealt with in previous chapter.
Nitrides are seldom present in ductile iron, and id present it will be in such a small
quantity that they can be ignored.
The dross is already discussed in the previous chapter if it is present in the surface.
But dross can be all over in the casting.
The dross is a Mg-compound from the following composition: Mg2SiO3, MgSiO4,

2MgO.SiO2.
As can be seen, it requires a lot of free Mg (not MgS) and oxygen. The oxygen can
be introduced during the pouring, the filling of the pouring system (especially with
high sprue’s) and the mould cavity (high metal speed in the ingates, > 0,5 m/s).
The free Mg can be estimated by the following formula:
Mgfree = Mgspectrometer – 0,75 x Sspectrometer.
It is said that the metal temperature plays a role, and this is correct because a low
metal temperature will decrease the floating speed of the dross. This floating speed is
already low (small size of the dross) and the dross will be located all over the casting
section. It is also possible, at elevated temperatures (which are mostly not present in
the ladle or pouring box, that the dross split again in its basic elements.
The slag can be based on Ca, which creates a very liquid, difficult to remove slag.
The Ca is mostly introduced by the inoculant and for this reason, it is important to
control the Ca-content of the second / late inoculation.
There is a foundry saying: melt cold and pour hot.

This is to avoid that the elevated temperature in the furnace will decrease the nuclei
too much. It is accepted that for most ductile irons, a temperature of 1510 °C and
higher, will increase the tendency for inverse chilling very much.
Elevated temperatures in the furnace will also increase the furnace lining wear.
The most common materials have a melting temperature compared to the equilibrium
temperature as indicated in next figure 127.
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Figure 127 Equilibrium diagram
This diagram gives the temperature above which SiO2 + 2 C  Si + 2 CO.
This means that nuclei (SiO2) decrease and C decrease by creating the CO-gas.
The formula behind it is:
lg (Si / C2) = -27486 / T + 15,47 T in °K (also named Tg)
The reaction needs a driver, which is the higher temperature (Tc), given by the next
formula:
Tc = 0,7866 x Tg + 362 (in °C).
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8. CONCLUSION
The metallurgy of ductile iron is a complex subject because the structure, which is in
the picture for all types of cast metal, there is also the free graphite.
The section of the casting has, in case of ductile iron, less influence on the structure
than in case of grey iron; identical concerning mechanical properties. But the
international standards do give different values depending on the section, when the
test bars are attached.
The significant difference is that the effect on the graphite shape is very high and
most problems appear in very thin (< 10 mm) and very thick (> 75 mm) castings. This
effect even results in the use of different techniques and alloys for the metallurgical
treatments depending on the wall thickness.
For this reason, whatever literature, brochure or procedure is read, check

always for which casting or test bar section it is written!
The free graphite has concerning shape a considerable influence on the mechanical
and even physical properties of the iron. It should be perfect, and it is poor to be
satisfied with the minimum 80 or 85 % requirement that some customers have set.
There are several techniques (concerning type of nodulisers, type of addition…) to
perform the nodulising, each of them with its strength and weak items, but the most
important is to control it to a high extend.
On top of this, several new techniques using new elements (La, Y…) come on the
market but lack extensive experience and historical result data. The suppliers are
promising very high quality, but this is not always achieved and or not in all cases
achieved.
Another very important feature of ductile iron is that it is a “living” material due to the
presence of magnesium. Magnesium is so high reactive with oxygen that it will
continuously react and by doing this, the chemical composition (concerning Mg) is
changing and reaction products (MgO and dross) enter the casting.
This effect makes it extremely difficult to monitor and control the quality of heavy wall
ductile iron castings due to the long time between nodulising and pouring, the mostly
turbulent filling of the mould and the long solidification time after pouring.
A lot of foundries deliver ductile iron castings. Most of them meet the mechanical
properties (tensile test and hardness) according to the standard. When the Charpy V
test at low temperatures is required, a lot of them cannot deliver conform to the
standard. But the biggest problems appear if the casting is specified with NDT testing
and quality levels. Very few foundries can deliver consistently castings according to
level 2 (EN standards for XT, UT, MT and PT).
The applying of “process control”, which seems to be normally accepted by everyone

but few applied, is a condition sine qua non for delivering ductile iron castings.
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ATTACHMENT: EFFECT OF
MELTING ON THE CHEMISTRY
ROLE OF OXYGEN
The solvability of oxygen in pure iron (Fe) is increasing with increasing temperature
as can be seen in the following data:
0,16 % at 1523 °C and

0,23 % at 1600 °C.
The more alloying elements, the lower the solvability as can be seen for an iron with
3,5 % C and 2,0 % Si:
0,0040 % at 1300 °C (40 ppm).
The most common reaction during melting of iron is the following (reaction with air
and furnace lining):
Si + 2 O  SiO2 {1} extra nuclei
SiO2 + 2 C  Si + 2 CO {2} Si content increases
SiO2 + 2 Mn  Si + 2 (MnO) {3} slag
During the solidification in the mould, carbon can also react with metal-oxides as
follows:
MeO2 + 2 C  Me + 2 (CO) {4} gas bubbles
Reaction {2} is depending on the temperature as indicated in following formula:
Log KSi,C = log (Si/C2) = {- 27486 / T} + 15,47 (T in °K)
This proves that oxygen is the drive behind any reaction and can be positive
(formation of nuclei) as well negative (dissolving of nuclei, slag and gas bubble
formation).
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ROLE OF TEMPERATURE
The temperature above which SiO2 + 2 C  Si + 2 CO is the equilibrium temperature
(Tg). Above this temperature, the number of nuclei (SiO2) decrease and C decrease
by creating the CO-gas. The formation of SiO2 is basic for the metallurgical quality of
the liquid metal. The formula behind it is:
lg (Si / C2) = -27486 / T + 15,47 T in °K (also named Tg)
Tg is the temperature above which the SiO2 is splitting to Si and O (reaction {2} in
previous chapter); it is called the “Si equilibrium” temperature. This means that above
it, the number of nuclei will decrease and the content of C in the metal will increase.
Tg = (- 27486 / {log (Si / C2) – 15,47}) – 273 in °C

Tg is for steel in the range of 1500 – 1600 °C and for iron of 1350 - 1470 °C.
Next figures give this equilibrium temperature.

Tg - temperature °C
Figure 127 a Equilibrium Si-C in general
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Figure 127b Equilibrium diagram for types of iron
The reaction (above the equilibrium line) needs a driver, which is the higher
temperature (Tc), given by the next formula:
Tc is the temperature above which an extensive amount of CO will be formed; it is

called the “gas formation equilibrium” temperature (sometimes also called the C
equilibrium or cooking temperature). The Si content in the metal will increase and the
carbon content decrease.
Tc = 0,7866 x Tg + 362 °C acid lined furnace
A graph for quick estimating the Tc-temperature is given in figure 127c.
This Tg- and Tc-temperature calculations are not valid for ductile iron melted in
a furnace with neutral (Al2O3) or basic (MgO) lining! See attachment.
Figure 128 indicates the safe zone for nuclei (below Tg-temperature) and the
dangerous zone (loss of nuclei and carbon) above the Tc-temperature.
In between these temperatures, there is a weak reaction.
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Figure 127 c
Relation Tc - Tg
Tc is mostly about 50 °C above the Tg

temperature.
% Si Tc temperature
Figure 128 Tc-
and Tg-
SiO2 + 2 C --> Si + 2 CO
temperature MeO2 + 2 C --> Me + 2 (CO)
SiO2 + 2 Mn --> Si + 2 (MnO)
Tg temperature
Si + 2 O --> SiO2
%C
On next page, there is a table with an inventory of these temperatures, Tg and Tc, for
acid lined furnaces including the liquidus temperature (P is taken as 0,03 %).
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Chemical composition
%C % Si TL (°C) Tg (°C) Tc (°C)
2,9 1,0 1260 1404 1466

2,9 1,2 1254 1412 1472
2,9 1,4 1249 1419 1478
2,9 1,6 1244 1425 1483
2,9 1,8 1238 1430 1487
2,9 2,0 1233 1435 1491
2,9 2,2 1228 1439 1494
2,9 2,4 1222 1443 1497
2,9 2,6 1217 1447 1500
3,0 1,0 1247 1401 1464

3,0 1,2 1242 1409 1470
3,0 1,4 1237 1416 1475
3,0 1,6 1231 1422 1480
3,0 1,8 1226 1427 1484
3,0 2,0 1220 1432 1488
3,0 2,2 1215 1436 1492
3,0 2,4 1210 1440 1495
3,0 2,6 1204 1444 1498
3,1 1,0 1235 1398 1461

3,1 1,2 1229 1406 1468
3,1 1,4 1224 1413 1473
3,1 1,6 1219 1419 1478
3,1 1,8 1213 1424 1482
3,1 2,0 1208 1429 1486
3,1 2,2 1203 1433 1489
3,1 2,4 1197 1437 1492
3,1 2,6 1192 1441 1495
3,2 1,0 1222 1395 1459

3,2 1,2 1217 1403 1465
3,2 1,4 1212 1410 1471
3,2 1,6 1206 1416 1476
3,2 1,8 1201 1421 1480
3,2 2,0 1196 1426 1484
3,2 2,2 1190 1430 1487
3,2 2,4 1185 1434 1490
3,2 2,6 1180 1438 1493
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%C % Si TL (°C) Tg (°C) Tc (°C)
3,3 1,0 1210 1392 1457

3,3 1,2 1205 1400 1463
3,3 1,4 1200 1407 1469
3,3 1,6 1195 1413 1473
3,3 1,8 1189 1418 1478
3,3 2,0 1185 1423 1481
3,3 2,2 1178 1427 1485
3,3 2,4 1173 1431 1488
3,3 2,6 1168 1435 1491
3,4 1,0 1198 1389 1455

3,4 1,2 1193 1397 1461
3,4 1,4 1187 1404 1467
3,4 1,6 1182 1410 1471
3,4 1,8 1177 1416 1475
3,4 2,0 1171 1420 1479
3,4 2,2 1166 1425 1483
3,4 2,4 1160 1429 1486
3,4 2,6 1155 1432 1489
3,5 1,0 1186 1387 1453

3,5 1,2 1180 1395 1459
3,5 1,4 1175 1402 1465
3,5 1,6 1169 1408 1469
3,5 1,8 1164 1413 1473
3,5 2,0 1159 1418 1477
3,5 2,2 1154 1422 1481
3,5 2,4 1148 1426 1484
3,5 2,6 1143 1430 1487
3,55 1,0 1179 1386 1452

3,55 1,2 1174 1394 1458
3,55 1,4 1169 1401 1464
3,55 1,6 1163 1407 1468
3,55 1,8 1158 1412 1472
3,55 2,0 1152 1417 1476
3,55 2,2 1147 1421 1480
3,55 2,4 1142 1425 1483
3,55 2,6 1137 1428 1486
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%C % Si TL (°C) Tg (°C) Tc (°C)
3,6 1,0 1173 1385 1451

3,6 1,2 1167 1392 1457
3,6 1,4 1162 1399 1463
3,6 1,6 1157 1405 1467
3,6 1,8 1152 1410 1471
3,6 2,0 1146 1415 1475
3,6 2,2 1141 1419 1479
3,6 2,4 1134 1423 1482
3,6 2,6 1130 1427 1485
3,65 1,0 1167 1383 1450

3,65 1,2 1161 1390 1456
3,65 1,4 1156 1398 1462
3,65 1,6 1151 1404 1466
3,65 1,8 1146 1409 1470
3,65 2,0 1140 1414 1474
3,65 2,2 1135 1418 1478
3,65 2,4 1129 1422 1481
3,65 2,6 1124 1426 1484
3,7 1,0 1161 1382 1449

3,7 1,2 1156 1390 1455
3,7 1,4 1150 1397 1461
3,7 1,6 1145 1403 1465
3,7 1,8 1139 1408 1470
3,7 2,0 1134 1413 1474
3,7 2,2 1129 1417 1477
3,7 2,4 1124 1421 1480
3,7 2,6 1118 1425 1483
3,75 1,0 1154 1381 1448

3,75 1,2 1149 1389 1454
3,75 1,4 1144 1396 1460
3,75 1,6 1138 1401 1465
3,75 1,8 1133 1407 1469
3,75 2,0 1127 1412 1473
3,75 2,2 1122 1416 1477
3,75 2,4 1117 1420 1480
3,75 2,6 1112 1423 1482
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%C % Si TL (°C) Tg (°C) Tc (°C)
3,8 0,80 1153 1370 1440

3,8 0,90 1150 1375 1444
3,8 1,00 1148 1380 1447
3,8 1,10 1145 1384 1451
3,8 1,20 1142 1388 1454
3,8 1,30 1140 1391 1456
3,8 1,40 1137 1394 1459
3,8 1,50 1134 1398 1461
3,8 1,60 1132 1400 1464
3,85 0,80 1147 1369 1439

3,85 0,90 1144 1374 1443
3,85 1,00 1141 1379 1446
3,85 1,10 1139 1383 1450
3,85 1,20 1136 1387 1453
3,85 1,30 1133 1390 1455
3,85 1,40 1131 1393 1458
3,85 1,50 1128 1396 1460
3,85 1,60 1125 1399 1463
3,90 0,80 1140 1368 1438

3,90 0,90 1138 1373 1442
3,90 1,00 1135 1378 1446
3,90 1,10 1132 1382 1449
3,90 1,20 1130 1385 1452
3,90 1,30 1127 1389 1455
3,90 1,40 1124 1392 1457
3,90 1,50 1122 1395 1459
3,90 1,60 1119 1398 1462
3,95 0,80 1134 1367 1437

3,95 0,90 1132 1372 1441
3,95 1,00 1129 1377 1445
3,95 1,10 1126 1381 1448
3,95 1,20 1124 1384 1451
3,95 1,30 1121 1388 1454
3,95 1,40 1118 1391 1456
3,95 1,50 1116 1394 1459
3,95 1,60 1113 1397 1461
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%C % Si TL (°C) Tg (°C) Tc (°C)
4,0 0,80 1128 1366 1436

4,0 0,90 1125 1371 1440
4,0 1,00 1123 1375 1444
4,0 1,10 1120 1380 1447
4,0 1,20 1117 1383 1450
4,0 1,30 1115 1387 1453
4,0 1,40 1112 1390 1455
4,0 1,50 1109 1393 1458
4,0 1,60 1107 1396 1460
4,05 0,80 1122 1365 1436

4,05 0,90 1119 1370 1440
4,05 1,00 1116 1374 1443
4,05 1,10 1114 1378 1446
4,05 1,20 1111 1382 1449
4,05 1,30 1108 1386 1452
4,05 1,40 1106 1389 1455
4,05 1,50 1103 1392 1457
4,05 1,60 1100 1395 1459
4,10 0,80 1116 1364 1435

4,10 0,90 1113 1369 1439
4,10 1,00 1110 1373 1442
4,10 1,10 1108 1377 1445
4,10 1,20 1105 1381 1448
4,10 1,30 1102 1385 1451
4,10 1,40 1100 1388 1454
4,10 1,50 1097 1391 1456
4,10 1,60 1094 1394 1458
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CONCLUSION
There are 3 temperature zones:
1. Below and around Tg
The oxygen content in the metal stays equal or decrease slightly. The
de-oxidizing is done by the silicon. When the power of the melting
furnace is shut down, a small oxide layer will appear on top of the liquid
metal. The involved reaction is:
Si + 2 O  SiO2 {1} extra nuclei
2. Between Tg and Tc
The oxygen content in the metal increase. The closer the temperature is
to the Tc temperature; the more oxygen will be absorbed. When the
power of the melting furnace is shut down, slag will appear on top of the
liquid metal. The FeO and MnO slag are formed and they are
dangerous because they will, if not removed, increase the CO defects
during solidification in the mould.
SiO2 + 2 Mn  Si + 2 (MnO) {3} slag
If the next formula “(Tb – Tg)2 x t” is below 6800, there will be no

problem with gas and or slag.
If the result of the formula is larger than 6800, than late de-oxidizing
(can be FeSi or another one, just before tapping) or increasing the
temperature above Tc is required. See the reactions in temperature
zone 3 (above Tc).
(Tb – Tg)2 x t > 6.800 in min.(°C)2 {4}
Tb is bath temperature (liquid metal)

Tg is equilibrium temperature
t is dwelling time in minutes.
3. Above Tc temperature
The oxygen content will decrease quickly (due to the CO formation) and
the metal is “cleaned”. Oxides and slag will segregate and float to the
metal surface.
If this is going on too long time, the oxygen (and nuclei) will become
very low and the metal is “killed”, which will lead to a poor activity of any
inoculant added later.
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SiO2 + 2 C  Si + 2 CO {2} loss of C
MeO2 + 2 C  Me + 2 (CO) {5} slag, gas bubbles
The minimum time to clean the metal is sometimes indicated as follows:
(Tb2 – Tc) x t2 ≥ {(Tb1 – Tg)2 x t1 - 6.800}/218 {6}
or
(Tb1 – Tg)2 - 6.800 ≤ 218 x (Tb2 – Tc) x t2 {6}
Tb1 is bath temperature of the stay between Tc and Tg

Tb2 is bath temperature (liquid metal) of the stay above Tc
Tc is the cooking temperature (SiO2 --˃ Si + 2O)
Tg is equilibrium temperature (Si + 2O --˃ SiO2)
t1 is dwelling time between Tc and Tg in minutes
t2 is dwelling time above Tc in minutes.
But a too long dwelling time will remove too much oxygen (iron is
“killed”) and this will lead to a very ineffective inoculation effect.
For ductile iron, a somewhat higher oxygen content is not that bad because of the
addition of FeSiMgRE. The magnesium and the cerium (from the RE) will react with
the oxygen and remove it. This leads anyhow to a lower efficiency of the nodulising
treatment because part of the Mg / Ce is used for oxygen removal.
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ATTACHMENT: EFFECT OF THE
METALLURGICAL TREATMENTS
ON THE NUCLEI
The number of nuclei, being important for every ductile iron, will decide
about the nodule count. The higher the nodule count, the fewer problems
will appear concerning intergranular inclusions and carbides as well as
shrinkage tendency.
The first step is melting. Figure 129 indicates relatively the evolution of
nuclei number.
Figure 129 Nuclei depending on operation
Number of
nuclei MELTING
Pig iron: high

number of nuclei
SiO2 --> Si + 2O
Si + 2O --> SiO2 C + O --> CO
Returns: different
number of nuclei
Steel: no nuclei
Tl Tg Tc Ttap
Temperature
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The second step (see figure 130) is the preconditioning, which is done to
boost the number of nuclei before tapping.
METALLURGICAL TREATMENT
PRECONDITIONING
SiO2 + BaO from
Number of FeSiBa
nuclei
SiO2 of Pig Iron
SiC + 2O --> SiO2 + C
SiO2 --> Si + 2O
C + O --> CO
Tg Tc Ttap
Temperature
Figure 130 Nuclei evolution
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The third step is nodulising (see figure 131), which must assure the presence of
sufficient Mg (and RE) for achieving a high nodularity, but which also does decrease
the nuclei count a lot.
NODULISING
Number
of nuclei
Mg + S
2 Mg + SiO2 +
O2 --> Mg2SiO4
or Mg2SiO3
Tc Ttap
Temperature
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The fourth step is inoculation (see figure 132), which is mostly done in 2 steps: one
during nodulising or directly after nodulising, and a second one in the pouring box or
metal stream during pouring. Especially the last one has a large effect on the nuclei
count.
INOCULATION & TRANSPORT & INOCULATION & POURING
Number
of nuclei
Transport
Inoculation Inoculation
Pouring
Si + O2 --> SiO2
Si + O2 --> SiO2
2 Mg + SiO2 + 2 Mg + SiO2 +
O2 --> Mg2SiO4 O2 --> Mg2SiO4
or Mg2SiO3 or Mg2SiO3
MgS --> slag MgS --> slag
Ttap Temperature
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ATTACHMENT: MELTING IN
NEUTRAL & BASIC LINED
FURNACES
In acid lined furnaces (SiO2), the combination of Si and C is very important because it
decides about the formation of SiO2-nuclei and about the C-removal (CO formation).
The temperature involved are Tg- and Tc-temperature (as described previously).
The Si-C equilibrium will never be reached in a neural or basic lined furnace. This is
because:
* Al (from neutral lining) will react quicker with O2 than Si

* Mg (from basic lining) will react quicker with O2 than Si.
This is proven by the free energy diagram.
The Al2O3 line is meeting the CO line at 1950 °C (SiO2-line at 1450 to 1500 °C),
which temperature will never be present in melting liquid iron.
The MgO line could have met the CO-line at 1800 °C, but it was already gas above
1150 °C.
So, it will be impossible to decrease the C-content by melting at elevated

temperature.
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There will be very few SiO2 nuclei in the liquid metal. This indicates that inoculation
will be very important.
But with this type of furnaces, there can be a slag formation of Al2O3 (from the neutral
lining) and Si from the liquid metal as well as SiO2 from added oxidised ferro-silicon
and the inoculation and MgO from the nodulizing or basic lining.
If a lot of returns are melted (especially as first charge), there will be Mg and a high Si
present.
The potential types of slag can have a high (for iron) melting point (1595 °C) for Al-Si
slag, but a lower one ( > 1400 °C) for Al-Si-Mg and for Al-Si-FeO – Fe2O3 slag) and a
very low one (> 1200 °C) for Al-Si-FeO slag.
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For this reason, it is important to remove the Al2O3 (combined with FeO if rusted
material is charged) containing slag before nodulizing and inoculation.
The amount of required Mg-addition will be lower compared to the metal in an acid
lined furnace because there will be less free oxygen (especially if the Al-containing
slag is removed).
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The amount of slag formation will depend on the combination of next factors:
1. Type and quantity of elements that react with lining material

2. Type and quantity of elements that react with each other
3. Furnace surface (side and bottom) compared to the content:
Fs/Fc in dm2 / dm3 or dm-1
4. Stirring effect of liquid metal
Depending on the 1/frequency
5. Depth of liquid metal, setting the ferrostatic pressure
6. Liquid metal temperature
7. Time that liquid metal is in contact with lining.
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UNIVERSITY DEGREE IN 1970, LEUVEN
WORKING WITH CASTINGS AS USERS AND PRODUCER

SINCE 1970
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DUCTILE

5. INFLUENCE OF CHEMICAL COMPOSITION

6. INFLUENCE OF METALLURGICAL TREATMENTS

ATTACHMENT: EFFECT OF MELTING ON THE CHEMISTRY

ATTACHMENT: EFFECT OF THE METALLURGICAL TREATMENTS

ATTACHMENT: MELTING IN NEUTRAL & BASIC LINED FURNACES

No data from this book can be used without verification; the

Nothing from this book may be copied without specific approval of

Then the graphite appearance is described. The free graphite is important

The non-conformities as well in graphite appearance as in structure will be described

The influence of the chemical composition is discussed separately. The range of

At latest, the influence of the metallurgical treatments, which are desulfurising,

Two other comments should be made to understand the next text:

2. A distinction should be made between subversive and tramp elements:

* Tramp elements influence the matrix structure and hence the

* Subversive elements impact graphite structure and hence the

EN 1563 Founding – Spheroidal graphite cast irons

ISO 1083 Spheroidal graphite cast irons - Classification

ASTM A536 Standard Specification for Ductile Iron Castings

2.1 GENERAL NOTION

Despite significant advances in electron microscopy, the use of the optical

Photomicroscopy and modern video techniques are important metallographic tools as

Figure 1 Light microscope Figure 2 stereo microscope

The scanning electron microscope has many advantages over traditional

Figure 4 Beam scheme

Figure 5 Schematic view microscopes

The SEM is an instrument that produces a largely magnified image by using

A beam of electrons is produced at the top of the microscope by an electron gun.

3.1 FREE GRAPHITE

3.1 FREE GRAPHITE

1. German VDG-Merkblatt P441 (august 1962)

2. European standard (DIN) EN ISO 945-1994

3. American ASTM-standard A 247-67 (Reapproved 1998).

Shape I is the “flake (lamellar) shape”,

Shape II is a “special shape”, seldom

Shape III is the “vermicular or worm

Shape IV is the “shape of aggregates”

Shapes V and VI are the “nodular or

Figure 8 Graphite shape acc EN

The above-mentioned classification is the appearing in the European EN ISO 945

Figure 9 Graphite shape acc to ASTM

EN ISO 945 kind of graphite ASTM A 247 Kind of graphite

I flake graphite, lamellar VII flakes, lamellar

Figure 10 Irregular graphite shapes

Figure 11 Example of nodularity

The most common requirement is a minimum nodularity of 85 %. For special

Figure 12 Graphite shape factor

Table Review of Graphite size

DIN and ISO 945-1994 ASTM A 247

Figure 13 Graphite size

• Matrix homogeneity is influenced by nodule count. Increasing the nodule count

Series 2: combination of diameter of nodules and nodule count

Figure 15 Nodule count and size

Figure 16 a and b Nodule count and size Wall thickness 10 mm

Figure 17 a and b Nodule count and size Wall thickness 30 mm

Figure 18 a and b Nodule count and size Wall thickness 50 mm

3.1.5.1 Type of free graphite

But an amount of flake or intercellular flake graphite > 5 % is not accepted,

3.1.5.2 Nodularity & size

Figure 20 Influence nodularity on

These results indicate that non-spherical graphite initiates fatigue failure in

3.1.5.3 Degenerated graphite

3.1.5.4 Influence of elements

Cmax = 1,30 % + 0,00257 * T (°C) – 0,31(% Si) – 0,33(% P)