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Svein Oddvar Olsen*, Torbjrn Skaland*, Cathrine Hartung*

Elkem ASA, Foundry Products Division, NORWAY

ABSTRACT The objective of this paper is to review some important aspects related to cast iron inoculation. Important conditions in the production of cast iron are described and characteristic microstructures and mechanical properties exemplify the difference between inoculated and un-inoculated irons. Principal mechanisms of inoculation and graphite nucleation in grey and ductile irons are described. The findings are based on advanced electron microscopy studies of micro-particles as heterogeneous nucleation sites for graphite. Effects of minor alloying elements such as Ca, Ba, Sr, and Al are explained as well as the critical role of oxygen and sulphur in the graphite nucleation process. (1) Finally, the mechanisms of inoculant fading are explained and some practical advises for optimized and reproducible inoculation given. Keywords: Cast iron, inoculation, graphite nucleation, fading INTRODUCTION In the production of quality cast irons the inoculation process is of vital importance. When comparing un-inoculated and inoculated irons, differences in microstructure are easily revealed, which again will strongly affect the final mechanical properties of the casting. Through inoculation the graphite nucleation

and eutectic undercooling of the iron can be controlled and this will be of crucial assistance in giving the iron its required service properties.

WHAT IS INOCULATION? Inoculation is a means to control and improve the microstructure and mechanical properties of cast iron. The inoculation process will provide sufficient nucleation sites for the dissolved carbon to precipitate as graphite rather than iron carbides (cementite). The most common inoculant is a ferrosilicon based alloy with small and defined quantities of either Ca, Ba, Sr, Zr, rare earths, and Al. Examples of un-inoculated and inoculated irons are shown in Figure 1 and the influence of inoculation on mechanical properties in Figure 2. Consequently, the effects of grey and ductile iron inoculation are improved machinability, increased strength and ductility, reduced hardness and section sensitivity and a more homogeneous microstructure. Typically, inoculation also reduces the tendency for solidification shrinkage formation.

GREY IRON INOCULATION The grey iron microstructure is normally determined by the base iron composition, the solidification cooling rate and the inoculation process. Figure 3 shows different grey iron microstructures as a function of solidification undercooling. Controlled undercooling promote the normally desired type A flake graphite, characterised by randomly distributed graphite flakes in a fully pearlitic matrix. The role of inoculation is to provide sufficient nucleation sites for graphite that is activated at low undercooling, thus promoting the formation of good type A graphite structures. Hence, inoculation is a means to change the otherwise undesired graphite forms into a more desired form. It has been found that balancing manganese and sulphur is important for the machinability of grey iron. Experiences have also resulted in a recommended ratio between manganese and sulphur in grey iron. Manganese should be adjusted to balance the residual sulphur level according to the following relationship: %Mn = %S x 1.7 + 0.3 [1]

Table 1 shows the influence of Mn:S ratio on eutectic cell count and chill tendency in un-inoculated condition. This relationship also suggests that MnS inclusions could act as nucleation sites for graphite flakes. The crystal lattice match between cubic MnS and hexagonal graphite is actually quite good. It is also known that if the sulphur content is less than about 0.03%, although balanced properly by Mn, the number of MnS inclusions will be insufficient to produce effective nucleation of good type A graphite structures.

Further, scanning electron microscope (SEM) investigations has shown that in uninoculated and inoculated irons the number of MnS inclusions are about the same, but the distribution tends to be somewhat different. In un-inoculated iron, MnS inclusions are predominantly found between the primary austenite dendrites while in inoculated iron these inclusions are found to be more randomly distributed throughout the iron matrix. This suggests that inoculation is affecting the formation sequence of MnS particles during cooling and solidification. Figure 4 shows an example of an inclusion that has acted as nuclei for graphite flake. The figure shows the distribution of relative intensity (X-ray mapping) of the different constituent elements. From this analysis it can be seen that a Mn(X)S compound with a core of Al/Ca oxides is present as graphite nucleation site. Further studies show that Ba and Sr can act the same way as Ca and Al. This means that the active elements in the inoculant, Ca-Ba-Sr-Al, primarily will form stable oxides that can act as nuclei for the Mn(X)S phase to precipitate on. The sulphide particle will again be the preferred nuclei for graphite flakes to grow from upon solidification. For the foundry it is therefore very important that the Mn:S ratio is adjusted to the right level and that some oxygen is also available for the inoculating elements to combine with in the production of grey iron. (3, 6, 7, 8)

DUCTILE IRON INOCULATION Figures 5 shows examples of microstructure in inoculated and un-inoculated ductile irons. The extensive chill (carbides) in un-inoculated condition will destroy the mechanical properties of this iron and make it very difficult to machine such castings. Hence, inoculation is a crucial requirement for most ductile iron processes simply to make machinable castings. In ductile iron the nodularising treatment will influence inoculation efficiency and therefore it is important to select the correct treatment process and magnesium bearing material. Formation of a high number of small micro-inclusions during magnesium treatment is an advantage, and Figure 6 shows how nodularising provides the basis for an effective subsequent inoculation. Also, Figure 7 shows how investigations of micro-inclusions at different magnifications have led to the discovery of the nucleation site for graphite in ductile iron. During nodularising, numerous inclusions are formed with a sulphide core and an outer shell containing complex magnesium silicates. Such micro-inclusions will however not provide effective nucleation of graphite because the crystal lattice structure of magnesium silicates does not match well with the lattice structure of graphite. However, after inoculation with a ferrosilicon alloy containing Ca, Ba or Sr, the surface of the magnesium silicate micro-particles will be modified and other complex Ca, Sr, or Ba silicate layers will be produced (see Figure 8). Such silicates have the same hexagonal crystal lattice structure as graphite, and due to very good lattice mach will therefore act as effective nucleation sites for graphite nodules to grow from during solidification. (1)

FADING OF INOCULATION EFFECT The gradual loss of inoculation effect during liquid metal holding is well known to the foundry people, and this fading of inoculation will eventually result in carbide formation and poor graphite structures if the iron is held for prolonged times before pouring. The reason for this fading loss is coarsening and growth of micro-inclusions, also called the Ostwald Ripening Effect. The driving force for this coarsening is a reduction in the specific surface area of inclusions, thus reducing the total energy of the system. The volume fraction of non-metallic inclusions will however remain unchanged due to the high particle phase stability. (10) This fading effect is very fast just after inoculation when distances between micro-particles are short, and is much more severe to the iron quality than fading losses of residual magnesium. Figures 9 and 10 show this inoculation fading effect by particle coarsening and a reduction in the number density of potential nucleation sites during time. The fading rate of inoculation is directly related to the diffusion rate of reactive elements through the liquid metal.

INOCULATION METHODS The required addition rate of an inoculant to liquid iron is very much depending on where and when it is to be introduced. Figure 11 shows an example of substantial reductions in addition rate when going from an early addition to the transfer ladle to a late addition to the metal stream. At transfer, the required inoculant addition rate may be as high as 1 wt%, while the alternative late instream inoculation may require only 0.1 wt% addition still providing sufficient or even better inoculation effectiveness. This is primarily due to the late addition giving much less time available for particle coarsening and fading effects. (2, 4, 5)

INOCULATION ELEMENTS The main finding from studies of micro-inclusions as nucleation sites for graphite is that the key nucleating elements in the inoculant are Ca, Ba, Sr and Al. The ferrosilicon alloy itself is only the carrier material of these critical active elements, but is also needed in order to give these minor elements the right concentration and solubility for an optimum inoculation performance.

COMPARISON OF ACTIVE MICRO-INCLUSIONS In grey iron it is found that small oxide particles will acts as the nuclei for Mn(X)S that again will be the decisive nuclei for graphite flakes to grow from at small undercoolings. In ductile iron however, a stable sulphide core is found to be the nuclei for complex silicates that again will be modified by the active elements in the inoculant before it can act as a potent nuclei for graphite. However, the

same specialty ferrosilicon inoculant materials are still being used for both grey and ductile irons and the main reason is that key elements are highly reactive and can form various types of micro-inclusions, some of them being favourable sites for graphite to grow from during solidification.

SUMMARY The principal inoculation mechanisms are quite different in grey and ductile irons. In grey iron, a stable oxide will be the primary nuclei for manganese sulphide precipitation that again will nucleate graphite flakes of good type A form. In ductile iron, a sulphide is the nuclei for complex silicates that again will nucleate a high number of graphite nodules. The same inoculant materials can however be used successfully in both type of irons, since the reactive elements such as Ca, Ba, Sr and Al are all strong oxide, sulphide and silicates formers in both grey or ductile irons. The inoculant fading effect is connected to diffusion rate, growth and coarsening, and a general reduction in the number density of micro-inclusions as nucleation sites for graphite. In order to obtain a sound and reproducible iron production process some critical inoculation factors will have to be controlled properly. For grey iron one should pay special attention to the following factors: 1) The Mn:S ratio should be maintained at the same level every time and sulphur should preferentially be kept at minimum 0.05%. 2) Aluminium is found to be an important part of the nucleus core and should be adjusted and kept at controlled levels every time. Recommended residual Allevel in grey iron is 0.005% - 0.01% for optimum inoculation effectiveness. 3) There should be a certain oxygen level in the base iron from fresh metal processing. The use of some rusty raw materials may assist in providing a good oxygen potential. 4) Pouring time after inoculation should be minimized in order to keep fading losses under control. 5) Use an inoculant with defined chemical composition and sizing. For ductile iron, the following factors must be controlled: 1) The magnesium treatment process reactivity should be controlled and minimized. A violent treatment process will provide less potential nucleation sites and more difficult conditions for powerful inoculation effectiveness.

2) There should be a certain oxygen level in the base iron from fresh metal processing. The use of some rusty raw materials may assist in providing a good oxygen potential. 3) The sulphur content should be kept low and constant. Preferential range for ductile iron is 0.005 to 0.015% base iron sulphur content. 4) Pouring time after inoculation should be minimized in order to keep fading losses under control. 5) Use an inoculant with defined chemical composition and sizing.

REFERENCES 1) T.SKALAND A model for graphite formation in ductile iron. Ph.D Thesis 1992 : 33, The Norwegian Institute of Technology, Norway (1992) 2) R.ELLIOTT Cast Iron Technology, 1988, London, UK, Butterworths 3) I.RIPOSAN, M.CHISAMERA, S.STAN, T.SKALAND, M.ONSOIEN Analysis of possible nucleation sites in Ca/Sr over-inoculated grey irons. AFS Transactions vol. 109, 2001, pp. 1151-1162 4) S.I.KARSAY Ductile Iron Production, QIT, 1976 5) Elkem Technical Information Sheets No. 1 34 6) I.RIPOSAN, M.CHISAMERA, S.STAN, T.SKALAND Graphite nucleants (micro-inclusions) characterization in Ca/Sr inoculated grey irons. SPCI 7 Science and Processing of Cast Iron International Conference, Barcelona, Spain, 2002 7) J.K.SOLBERG, M.ONSOIEN Nuclei for heterogeneous formation of graphite spheroids in ductile cast iron. Material Science and Technology, vol 17, October 2001, pp. 1238 8) F.NEUMANN Theorien ber das Impfen. Giesserei, No.14, July 1996, pp. 9) ASM Metals Handbook, vol 1, tenth edition, 1990, pp. 6 10) J.D.VERHOEVEN, Fundamentals of Physical Metallurgy, Chapter 8 and 10, John Wiley & Son, Inc, 1975

Grey Iron



Ductile Iron

Figure 1: Examples of structures in un-inoculated and inoculated irons. (5)

Un-inoculated Un-inoculated
Example: Tensile: 200 MPa Elongation: 0 % Hardness: 700 HB

Example: Tensile: 450 MPa Elongation: 10 % Hardness: 180 HB

Control of structure and properties by minimizing undercooling and providing nucleation of graphite during solidification

Figure 2: Effects of inoculation on typical mechanical properties of ductile iron. (5)

Figure 3: Graphite structures as a function of eutectic undercooling in grey iron.

Table 1: Experimental results showing effects of Mn and S contents and Mn:S ratio on eutectic cell count and chill level in grey iron. % Mn 0.8 1.0 0.8 0.3 %S 0.012 0.022 0.065 0.20 Mn:S 67 46 12 1.5 Cell Count [mm] 15 15 21 69 Chill [mm] 13 10 7 23

a) SEM micrograph of (Mn,X)S compound and graphite flake

b) Distribution of Carbon

c) Distribution of Manganese

d) Distribution of Sulphur

e) Distribution of Aluminium

f) Distribution of Calcium

g) Chemical composition along a cross line through the (Mn,X)S compound. Figure 4: X-ray mapping showing composition of micro-inclusion as nuclei for graphite flake in grey iron. (3, 6)

Poor Inoculated


Good Inoculation

Improved Recovery

Reduced Mg-Addition
P ro p erty P r o o f S t r e n g th T e n s i l e S tr e n g t h E lo n g a tio n B r in e l l H a r d n e s s N o d u le C o u n t M ic r o s t r u c t u r e R p 0 .2 Rm A5 HB 1 0 m m s e c tio n ASTM C l a s s i f ic a t io n U n in o c u la t e d N ot d e tected < 300 M P a N ot d e tected > 600 < 5 0 p er m m 2 C a rb id ic I n o c u la te d 200 - 400 M P a 350 - 800 M P a 3 - 30 % 140 - 300 > 1 5 0 p er m m 2 F e r r i t ic a n d / o r P e a r lit i c

Figure 5: Examples of microstructure and mechanical properties in un-inoculated and inoculated ductile irons. (5)



Treatm ent Reactivity

5 m Size Distribution
Figure 6: Schematic representation of size distribution of inclusions as micronuclei and slag in treated ductile iron.


a) 100x (optical)

b) 1,000x (SEM)

XO SiO 2 or XO Al 2O 3 2SiO 2

Where X = Ca, Sr or Ba

c) 70,000x (TEM)

d) Schematic composition

Figure 7: Ductile iron micro-inclusions at different magnifications and the schematic composition of nucleation sites for graphite. (1)

Major constituent phases:


Shell: MgO SiO2 2MgO 2SiO2 Core: MgS CaS

XO SiO2 or XO Al2O3 2SiO2

Where X = Ca, Sr or Ba

Figure 8: Schematic representation of micro-inclusion composition in treated ductile iron before and after inoculation. (1)


Time Nucleation Sites Fading of Inoculation = Coarsening of Inclusions

Ostwald - Ripening - Effect

Figure 9: Fading of inoculation described as a coarsening phenomenon causing reduction in the number density of potential nucleation sites.

Figure 10: Calculated reduction in number density of micro-inclusions as a function of holding time after inoculation. (1)
Transfer Ladle Pouring Ladle In-stream

1 1 2 2

3 3

4 4
Examples: Examples:

Position Addition rate [wt%] Sizing [mm]

1 0.3 1.0 0.5 15

0.3 0.5 0.05 0.2 0.04 0.2 0.5 10 0.2 1 0.5 5

Figure 11: Schematic representation of different methods for inoculant addition to the transfer ladle, pouring ladle or mould.