Technical Information 5 Inoculation Mechanisms

Several theories have been developed in the past to explain the mechanisms of graphite nucleation during solidification of cast iron. Most theories are based on the assumption that graphite is formed as a result of heterogeneous nucleation from non-metallic substrates during solidification and that minor elements such as Ca, Ba and Sr play an important role in the nucleation process. Ductile Iron In magnesium treated cast irons, micro-inclusions after treatment contain mainly magnesium, calcium, sulphur, silicon, and oxygen. These are primary reaction products of the magnesium treatment. The inclusions are composed of a sulphide core and a faceted outer silicate shell. The sulphide core contains both MgS and CaS, while the outer shell consists of complex magnesium silicates (e.g. MgSiO3, Mg2SiO4). These phases will not act as potent nucleation sites for graphite during solidification because of a large nucleus/graphite interfacial energy barrier. After inoculation with a Ca-containing ferrosilicon, hexagonal silicate phases of the CaSiO3 and the CaAl2Si2O8 type will form at the surface of the existing sulphide/oxide inclusions produced during nodularization. These calcium silicates will then act as very favourable sites for graphite nucleation during solidification, due to their hexagonal crystal structure which matches the graphite crystal lattice very well (i.e. low energy interface). Figure 1(a) shows a typical micro-inclusion in ductile cast iron which is formed after nodularization, while figure 1(b) gives a schematic representation of the inclusion composition after inoculation with ferrosilicon containing either Ca, Ba or Sr.
Major constituent phases:
XO SiO2 or XO Al2O3 2SiO2

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

Where X = Ca, Sr or Ba

(a) (b) Figure 1: (a) Duplex sulphide/oxide micro-inclusion in ductile cast iron, (b) Schematic representation of an inclusion after inoculation with a X-containing ferrosilicon inoculant (X denotes Ca, Ba or Sr).

The surface shell contains hexagonal calcium silicates formed during inoculant addition, while the bulk particle is a product of the nodularization treatment. Hence, the inoculation does not increase the total number of nuclei particles in the melt, but rather modifies the surface of the already existing products from nodularization.

Elkem ASA, Silicon Division

This explains the important link between magnesium treatment and inoculation, and that the basis for effective ductile iron inoculation is laid during nodularization. The resulting nodule number density will also differ greatly due to the inclusion surface modification. When inoculation is carried out with a strontium or barium containing ferrosilicon inoculant, hexagonal silicates equivalent to the calcium silicates will be formed (i.e. SrSiO3, SrAl2Si2O8, BaSiO3, BaAl2Si2O8). Grey Iron In grey iron the nucleation mechanisms differ somewhat from the situation in ductile iron, primarily due to the fact that magnesium is not added prior to inoculation. Consequently, other substrates will play the important role as sites for the Ca, Ba or Sr silicates formed during inoculation. In principal, the same types of inoculants can be used for both grey and ductile irons, and the inoculation mechanisms from hexagonal silicate phases at the surface of primary inclusions are equal for all types of irons. However, in grey cast iron the lack of primary magnesium sulphides and silicates means that other particles have to take the primary role. It is assumed that the presence of a high number of manganese sulphides (MnS) replaces the magnesium containing particles found in ductile iron. The relation between manganese and sulphur in grey cast iron should be as follows: %Mn = 1.7 x %S + 0.3 When this balance is right, the optimum conditions for the formation of small MnS particles is obtained. Furthermore, to have a highest possible number density of MnS particles as a basis for effective inoculation, the sulphur content of grey irons should be significantly higher than for ductile irons. Normally, a sulphur content between 0.05 and 0.15% is recommended. Some Important Considerations Pure ferrosilicon has no inoculation effect whatsoever. Inoculation does not increase the number of potential nucleation sites in grey and ductile iron but modifies existing sites to a beneficial form. The important consideration in effective inoculation is the formation of a high number of non-metallic micro-particles (sulphides and oxides) during magnesium treatment of ductile iron and the formation of numerous manganese sulphide particles in grey iron. Minor elements such as Ca, Ba and Sr as well as silicon in inoculants are critical for powerful effectiveness of an inoculant material. The base metal oxygen content is also critical in the formation of effective oxide substrates for graphite nucleation.