24.12.2014 Views

CAST IRON INOCULATION - Elkem

CAST IRON INOCULATION - Elkem

CAST IRON INOCULATION - Elkem

SHOW MORE
SHOW LESS

You also want an ePaper? Increase the reach of your titles

YUMPU automatically turns print PDFs into web optimized ePapers that Google loves.

<strong>CAST</strong> <strong>IRON</strong><br />

INOCULAtion<br />

THE TECHNOLOGY OF GRAPHITE SHAPE CONTROL<br />

ISO 9001 ISO 14001 ISO/TS 16949


<strong>CAST</strong> <strong>IRON</strong> <strong>INOCULATION</strong><br />

THE TECHNOLOGY OF GRAPHITE SHAPE CONTROL<br />

<strong>Elkem</strong> manufactures and markets a<br />

series of high quality inoculants to treat<br />

cast iron and ensure the production of<br />

an ideal graphite shape, distribution<br />

and freedom from chill (cementite). All<br />

inoculants are available in sizes suitable<br />

for ladle or in-stream additions.<br />

This brochure describes some of the<br />

conditions in the production of cast iron<br />

that call for the addition of an inoculant<br />

to ensure the reliable production of a<br />

sound, strong, tough, machinable casting.<br />

The mechanism of inoculation and<br />

graphite nucleation in cast iron during<br />

solidification is also described.<br />

What is Inoculation of Cast Iron<br />

Inoculation is the means of controlling<br />

structures and properties of cast iron<br />

by minimizing undercooling and<br />

increasing the number of nucleation<br />

sites during solidification. An inoculant<br />

is a material added to the liquid iron<br />

just prior to casting that will provide<br />

suitable sites for nucleation of graphite<br />

during the subsequent cooling. Traditionally,<br />

inoculants have been based<br />

on graphite, ferrosilicon or calcium<br />

silicide. Almost exclusively, inoculants<br />

today are ferrosilicon based containing<br />

small quantities of active elements<br />

such as Al, Ba, Ca, Sr, Zr and RE (Rare<br />

Earth metals).<br />

The purpose of inoculation is to assist<br />

in providing sufficient nucleation sites<br />

for dissolved carbon to precipitate<br />

as graphite rather than iron carbide<br />

(cementite, Fe 3<br />

C). This is done by preventing<br />

undercooling below the metastable<br />

eutectic temperature where<br />

carbidic (white) structures are formed.<br />

The iron solidification mechanism is<br />

prone to form chilled iron structures<br />

when the inoculation is inadequate.<br />

There are several reasons why chilled<br />

structures are normally undesirable.<br />

They are hard and brittle and interfere<br />

with machining, necessitate additional<br />

heat treatment operations, resulting in<br />

nonconformance with specifications<br />

and, in general, increase the total cost<br />

of production.<br />

Inoculation changes the structure of<br />

cast iron by altering the solidification<br />

process. A look at the solidification<br />

process for hypoeutectic grey iron<br />

(iron with a carbon equivalent less<br />

than 4.3) helps in understanding the<br />

effect of inoculation.<br />

The first metal to solidify in hypoeutectic<br />

grey iron is primary austenite. As<br />

cooling continues, the remaining iron<br />

grows richer in dissolved carbon. Eventually,<br />

the liquid reaches the eutectic<br />

composition of 4.3% carbon equivalent,<br />

at which final or eutectic solidification<br />

would start under equilibrium conditions.<br />

However, equilibrium solidification does<br />

not occur under practical foundry conditions.<br />

Due to variations in chemistry,<br />

pouring temperature, solidification rate,<br />

section thickness and other conditions,<br />

the metal will cool below the eutectic<br />

temperature before the start of final<br />

solidification.<br />

If the undercooling is slight, random<br />

graphite flakes form uniformly in the<br />

iron matrix, see Figure 1. This is known<br />

as Type A graphite. As the undercooling<br />

increases, the graphite will branch,<br />

forming abnormal patterns. This is<br />

known as Types B, D and E graphite.<br />

A further increase in undercooling will<br />

suppress the formation of graphite<br />

and results in a hard white iron carbide<br />

structure.<br />

The role of the inoculant is to produce<br />

nuclei in the liquid iron melt which<br />

enhance the graphite nucleation with<br />

a low degree of undercooling. This will<br />

in turn, promote the formation of Type<br />

A graphite structures in grey iron,<br />

and a high number of small graphite<br />

nodules in ductile iron.<br />

Figure 1: Graphite type versus undercooling.<br />

1. Structure and Phases in Cast Iron<br />

The structure of cast iron has a<br />

domi nant influence on strength and<br />

machinability, and in order to obtain a<br />

machinable grey iron structure for thin<br />

sections, the addition of an inoculant<br />

to molten iron is widely practiced<br />

and often absolutely necessary. For<br />

convenience, potential difficulties with<br />

machinability can be determined by<br />

carrying out a hardness test (Brinell<br />

hardness) on iron castings and, in<br />

general, machinability improves with<br />

decreasing hardness. The cast iron<br />

structure can be influenced at two<br />

distinct stages in the production route:<br />

• during solidification<br />

• during heat treatment<br />

However, for economic reasons, the<br />

desired structure should be achieved<br />

during solidification without the necessity<br />

for heat treatment.


The microstructure of an iron casting<br />

consists of several phases, each having<br />

varying levels of carbon, iron and other<br />

elements present. Table 1 shows the<br />

analysis and specific densities of the<br />

solid and liquid phases which take<br />

part in the solidification process. When<br />

solidification is complete, the following<br />

combination of phases may be found:<br />

1) Austenite + Graphite<br />

= GREY structure<br />

2) Austenite + Graphite + Cementite<br />

= MOTTLED structure<br />

3) Austenite + Cementite<br />

= WHITE structure<br />

This review demonstrates that solidifica<br />

tion results in a minimum of two solid<br />

phases; and austenite is present in all<br />

the phase combinations. As the casting<br />

cools, the austenite subsequently transforms<br />

to pearlite and/or ferrite in solid<br />

state (eutectoid transformation).<br />

Of all the solid phases listed above,<br />

cementite has the highest hardness<br />

(~660 HB), whilst graphite is a relatively<br />

soft material of low density, which<br />

can act as a lubricant. Hardness and<br />

machinability of the as-cast structure<br />

are, therefore, influenced by the relative<br />

amounts of cementite and graphite, with<br />

austenite playing only a minor role.<br />

Table 1: Approximate analysis and<br />

specific densities of phases in the<br />

solidification range of cast iron with<br />

2.4% Si.<br />

2. Structure Stability<br />

A metastable white or mottled structure<br />

can be transformed into a stable grey<br />

structure by annealing, but the reverse<br />

transformation is not possible as the<br />

stable structure represents the lowest<br />

possible energy level (at a given<br />

temperature and composition). The<br />

graphite produced by annealing will<br />

have a different structure to that formed<br />

during solidification. Cementite,<br />

austenite and liquid iron have similar<br />

densities and all contain carbon in<br />

solution, see Table 1. No major redistribution<br />

of the atom species is required<br />

for a white structure to be produced<br />

during solidification. However, the<br />

formation of a stable grey structure<br />

containing graphite is quite different.<br />

Graphite precipitated from molten iron<br />

is virtually pure carbon, and since it<br />

has a lower specific density than the<br />

alternative phases; a major redistribution<br />

of atoms is required to develop<br />

a stable structure. A slow rate of solidification<br />

is therefore more likely to<br />

produce a grey iron structure.<br />

The precipitation of cementite, re quir ing<br />

less atom redistribution than graphite,<br />

will be more likely during rapid solidification.<br />

This can be demonstrated by<br />

examining a typical wedge test specimen.<br />

The narrow tip of the wedge solidifies<br />

at a faster rate than the thicker<br />

section at the base of the wedge, and<br />

will show a white structure whilst the<br />

area of slow cooling at the base will<br />

display a grey structure, see Figure 2.<br />

Consequently, a slow rate of solidification<br />

(slow cooling rate) and a small<br />

value of undercooling encourages the<br />

formation of a grey structure with good<br />

machinability and discourages a hard<br />

white structure.<br />

Figure 2: Chill Wedge with fast solidifying<br />

‘white’ tip and slowly cooled ‘grey’ base.<br />

3. Influence of Elements on As-Cast Structure<br />

Within the composition of cast iron,<br />

graphitizing elements will promote the<br />

carbon-carbon bond to produce graphite<br />

in the as-cast structure, whereas<br />

carbide stabilizing elements promote<br />

the carboniron bond and cementite will<br />

appear in the structure. Table 2 lists a<br />

number of such stabilizing elements.<br />

As an example, in malleable cast irons<br />

the need for the as-cast structure to<br />

solidify white determines that the silicon<br />

level is much lower than in grey irons.<br />

Also, since chromium is a carbide<br />

promoting element, it has to be kept at<br />

a low level to allow transformation to a<br />

graphitic structure during subsequent<br />

heat treatment. In normal furnace<br />

charge materials, steel and external<br />

cast iron scrap may be heterogeneous<br />

materials, especially on different deliveries,<br />

with contents of Cr, Cu, Sn, Sb, V,<br />

Mo, Ti, etc., depending on the original<br />

source and ultimately on the ability of<br />

the scrap dealer.<br />

Pig iron produced from steel scrap can<br />

also display a similar variable response<br />

to inoculation due to fluctuating trace<br />

element contents. A more consistent<br />

response to inoculation is attainable by<br />

adopting a charge containing a reasonable<br />

proportion of ore-based pig iron<br />

due to its low level of trace elements of<br />

the carbide stabilising type.<br />

Controlling the concentration of trace<br />

elements allows the foundryman a means<br />

of promoting grey as-cast structures<br />

and, also, helps in avoiding other undesirable<br />

effects of trace elements on<br />

microstructure and properties.<br />

Table 2: Graphitizing and carbide<br />

promoting elements.


4. Influence of Nuclei on Solidfication Structure<br />

When crystallisation of eutectic cast<br />

iron in chilled specimens is studied,<br />

a gradual advance of the solidification<br />

front is revealed. Transformation does not<br />

take place instantaneously or uniformly<br />

over a cross section. Initial solidification<br />

occurs at the surface from distinct<br />

crystallization centres and after some<br />

time a solid/liquid interface forms. Other<br />

isolated crystallisation centres are<br />

active in the remaining melt and initiate<br />

the formation of solid, see Figures 3<br />

and 4. These isolated areas are called<br />

eutectic cells.<br />

Eventually, cells grow at the expense<br />

of the liquid, and a solid cast structure<br />

develops. Each eutectic cell consists of<br />

graphite and austenite with graphite as<br />

the primary phase.<br />

Precipitation is initiated by randomly<br />

distributed crystallisation centres, called<br />

nuclei. These nuclei offer favourable sites<br />

for the deposition of carbon atoms and,<br />

subsequently, precipitation of graphite<br />

and austenite onto existing graphite<br />

continues. The morphology of these cells<br />

for grey iron shows a marked difference<br />

with that for nodular iron, as can be<br />

seen from Figure 3.<br />

• Grey iron: graphite lamellae start<br />

growing from a common centre and<br />

stays in contact with the melt as austenite<br />

fills the spaces between<br />

the lamellae.<br />

• Nodular iron: a graphite nodule forms<br />

first and is surrounded by austenite at<br />

a later stage.<br />

In eutectic nodular iron, the nodule<br />

number is virtually identical with the<br />

number of eutectic cells.<br />

The mechanism described is for eutectic<br />

solidification and is not influenced by<br />

the presence of kish (primary) graphite<br />

or austenite dendrites.<br />

Austenite<br />

Graphite<br />

Austenite<br />

Graphite<br />

Figure 3: Eutetic cells: lamellar (top),<br />

nodular (bottom) graphite .<br />

The nuclei substances can be more easily<br />

observed in nodular graphite iron than<br />

in grey iron, since it is easy to locate the<br />

centre of a graphite spheroid. Measurements<br />

have shown that the nuclei are<br />

between 0.5 to 2.0 microns in diameter,<br />

with a bulk chemical composition of<br />

magnesium sulphide and magnesium<br />

silicate. A similar investigation of nuclei<br />

composition for grey iron has shown that<br />

the nucleus has a core of a complex<br />

aluminium-X-oxide where X can be<br />

Ca, Ba, Sr, Ce, Zr surrounded by the<br />

manganese sulphide.<br />

Figure 4: Solidification of near eutetic<br />

iron 2 .<br />

5. Prerequisites for Successful Inoculation<br />

5.1 Number of Nuclei<br />

About 2.4wt% graphite and 97.6wt%<br />

austenite are formed during the crystallization<br />

of eutectic (nodular) cast iron,<br />

which corresponds to approximately<br />

8 vol% graphite and 92 vol% austenite.<br />

The mean diameter of graphite nodules<br />

is usually between 10 – 80 microns,<br />

although lower and higher values are<br />

possible. This leads to about 3000 to<br />

30,000 nodules per cubic millimetre<br />

depending on the section size (cooling<br />

rate) of the casting. The total number of<br />

possible nuclei for graphite (inclusions)<br />

will be at least one order of magnitude<br />

larger than this graphite nodule density.<br />

This means that the number of inclusions<br />

or possible nuclei for graphite is at least<br />

100,000 per cubic millimetre and that<br />

only a small fraction of these nuclei<br />

actually nucleates graphite during<br />

solidification 1 . Table 3 gives examples<br />

of number densities and mean particle<br />

sizes for nuclei and graphite nodules in<br />

ductile cast iron under various inoculation<br />

conditions. As can be seen from<br />

the table, the number and mean size of<br />

nuclei particles are unaffected by the<br />

inoculant addition, although the nodule<br />

characteristics obtained after solidification<br />

are strongly dependent on the<br />

type of inoculant used. These findings<br />

will be discussed below.<br />

The calculations used to generate these<br />

figures contain certain assumptions,<br />

but one can safely conclude that:<br />

• The number of nuclei per volume of<br />

melt is extremely high, and approximately<br />

one order of magnitude larger<br />

than the number of graphite nodules<br />

actually nucleated;<br />

• The ability of the particles to nucleate<br />

graphite is strongly affected by the<br />

inoculant addition.<br />

In order to obtain a nucleation event, a<br />

certain degree of undercooling during<br />

solidification is required. But since<br />

different nuclei phases initiate graphite<br />

nucleation at different undercooling<br />

levels, it is preferable to have a large<br />

number of nuclei particles which can<br />

initiate nucleation at very small undercooling.<br />

This is achieved by the addition<br />

of an inoculant to the melt just prior to<br />

casting.


5.2 Constituents of an inoculant<br />

Most of the inoculant material is socalled<br />

‘carrier’ material that is doped<br />

with a minor additive (“nucleant”),<br />

which produces nucleating particles<br />

in the iron melt. These particles will, in<br />

turn, initiate the crystallization of graphite.<br />

The carrier (e.g. silicon and iron<br />

combined as ferrosilicon) should have<br />

the following characteristics:<br />

• provide fast and homogeneous distri -<br />

bution of the nucleant in the melt<br />

• have a composition that is compat ible<br />

to the analysis of the melt<br />

• form an alloy between the nucleant<br />

and the carrier<br />

• be cost efficient<br />

Trials using very pure ferrosilicon as an<br />

inoculant have demonstrated that it<br />

does not have any nucleating effect for<br />

graphite 1,3,4 as shown in Table 3.<br />

The nucleant, e.g. Ca, Sr, Ba or Al only<br />

needs a limited presence and it is<br />

beneficial if the nucleant forms an alloy<br />

with the carrier. Also, the nucleant must<br />

have a limited solubility in cast iron,<br />

and form stable compounds with the<br />

other elements forming the nuclei particles<br />

(e.g. sulphur and oxygen). Good<br />

nucleation effect may be achieved if<br />

the ferrosilicon contains small but controlled<br />

amounts of calcium, strontium or<br />

barium in the range of 0.6 to 2.0%.<br />

Table 3: Example of nuclei and nodule<br />

number densities, average<br />

diameters and volume fractions 1 .<br />

5.3 Composition of the Nuclei<br />

in Ductile Iron<br />

Laboratory test results are used in this<br />

section to explain the role of calcium<br />

as an example of a trace element<br />

behaving as the nucleant in ferrosilicon.<br />

Calcium will occur in ferrosilicon as a<br />

silicide (CaSi 2<br />

). Calcium has virtually no<br />

solubility in iron, and reacts with components<br />

in the melt to form sulphides<br />

and oxides.<br />

In magnesium treated cast irons, the<br />

inclusions contain mainly magnesium,<br />

calcium, sulphur, silicon and oxygen.<br />

These are primary reaction products<br />

of the magnesium treatment. The<br />

inclusions are composed of a sulphide<br />

core and a faceted outer silicate shell.<br />

The sulphide core contains both MgS<br />

and CaS, while the outer shell consists<br />

of complex magnesium silicates<br />

(e.g. MgO•SiO 2<br />

, 2MgO•SiO 2<br />

). These<br />

phases will not act as potent nucleation<br />

sites for graphite during solidification<br />

because of a large nucleus/ graphite<br />

interfacial energy barrier. The interfacial<br />

energy barrier is the controlling factor in<br />

heterogeneous nucleation behaviour.<br />

Figure 5: Transmission electron<br />

micrograph of duplex sulphide/oxide<br />

inclusion in ductile iron (left).<br />

Schematic representation of an inclusion<br />

after inoculation by a calcium<br />

containing ferrosilicon. The surface<br />

layer of calcium silicate is the effective<br />

phase for graphite nucleation (right). 1


After inoculation with a Ca-containing<br />

ferrosilicon, hexagonal silicate phases of<br />

the CaO•SiO 2<br />

and the CaO•Al 2<br />

O 3<br />

• 2SiO 2<br />

type will form at the surface of the existing<br />

oxide inclusions produced during<br />

nodularisation. These silicates will act<br />

as very favourable nucleation sites for<br />

graphite during solidification, due to<br />

their hexagonal crystal structure, which<br />

matches the graphite crystal lattice<br />

very well (i.e. low energy interface).<br />

Figure 5 shows a typical inclusion in<br />

ductile cast iron which is formed after<br />

nodularisation (left), and a schematic<br />

representation of the inclusion composition<br />

after inoculation (right). The surface<br />

shell contains hexagonal calcium<br />

silicates formed during inoculant addition,<br />

while the bulk particle is a product<br />

of the nodularisation treatment. Hence,<br />

the inoculation does not increase the<br />

total number of nuclei particles in the<br />

melt, but rather modifies the surface of<br />

the already existing products from nodularisation.<br />

This explains why the number<br />

density of particles in uninoculated<br />

and inoculated ductile iron melts are<br />

the same (Table 3), while the resulting<br />

nodule numbers will differ greatly due<br />

to the inclusion surface modification.<br />

When inoculation is carried out with<br />

a strontium or barium containing ferrosilicon<br />

inoculating hexagonal silicates<br />

equivalent to the calcium silicates<br />

(CaO•SiO 2<br />

and CaO•Al 2<br />

O 3<br />

•2SiO 2<br />

) will<br />

be formed (i.e. SrO•SiO 2<br />

, SrO•Al 2<br />

O 3<br />

•2SiO, BaO•SiO 2<br />

and BaO•Al 2<br />

O 3<br />

•2SiO 2<br />

)<br />

5.4 Composition of nuclei in grey iron<br />

Recent research results have identified<br />

a three step nucleation process for<br />

generating graphite flakes in grey iron.<br />

By means of electron microscope investigations,<br />

it has been revealed that<br />

a nucleus for a graphite flake consists<br />

of a particle with a body of manganeseand<br />

calcium-sulphide surrounding a<br />

nucleus core of complex Al 2<br />

O 3<br />

–XO<br />

oxides, see Figure 6. The core oxide<br />

contains elements such as calcium,<br />

barium, strontium, zirconium, and rare<br />

earth elements. Towards the surface<br />

of the manganese/calcium-sulphide<br />

body, even more complex compounds<br />

have been observed on which the<br />

graphite has grown.<br />

The hypothesis is that the oxides form<br />

as stable elements in the iron melt first.<br />

Secondly, manganese and calcium<br />

sulphides grow on these oxides until<br />

a desired size and a more complex<br />

faceted compound appears on the surface.<br />

The third step is that the graphite<br />

starts to grow on this faceted surface<br />

and grows along its base planes of<br />

hexagonal structure.<br />

One interesting observation was that<br />

aluminium seems to play a key role in<br />

the nucleation process in conjunction<br />

with other elements. Testing of iron with<br />

very low levels of aluminium showed<br />

poorer performance than iron with a<br />

certain level of aluminium. It can be<br />

concluded that final content of aluminium<br />

in grey iron should be between<br />

0.005 and 0.010% in order to maximise<br />

eutectic cell count in grey iron. This<br />

aluminium content range is and has to<br />

be less than the 0.015 – 0.25% Al, as<br />

this range for pin-hole susceptibility<br />

influenced by aluminium.<br />

As a result of these observations, <strong>Elkem</strong><br />

has invented the Preseed preconditioner<br />

that contains zirconium and<br />

aluminium, to be added to the iron melt<br />

in the furnace or well ahead of inoculation,<br />

in order to increase the potency<br />

of the melt for inoculation<br />

Figure 6: Transmission electron micrographs of complex sulphide/oxide inclusion in grey iron and profile of chemical<br />

composition through the nucleus.


5.5 Specification of Inoculants<br />

The chemical composition and reliability<br />

of the analysis from lot to lot is important<br />

if a ferroalloy is to be considered as a<br />

good and consistent inoculant. Many<br />

foundrymen insist on silicon and phosphorus<br />

analyses in pig iron, but pay little<br />

attention to the analysis of the inoculant,<br />

or vice versa. The preceding paragraphs<br />

indicate quite clearly that the minor<br />

constituents in ferroalloys, not the major<br />

constituents (usually sili con), are critical<br />

for the performance as inoculants. All the<br />

<strong>Elkem</strong> inoculants are alloys that have<br />

been smelted and alloyed to the quoted<br />

specifications, and with the exception<br />

of Ultraseed ® inoculant, no further additions<br />

have to be mechanically blended<br />

with the alloy. The analysis guaranteed<br />

by the specification ensures consistent<br />

inoculant properties from lot to lot. The<br />

inoculants listed in Table 4 differ by<br />

analysis, price and application. The<br />

foundry experts of <strong>Elkem</strong> can give<br />

detailed information on each inoculant<br />

and its individual features, and also<br />

suggestions as to the most suitable alloy<br />

for a specific foundry condition.<br />

5.6 Addition Technique<br />

Chemical considerations alone will not<br />

ensure satisfactory results since equal<br />

attention must be paid to addition technique.<br />

For ladle inoculation this means<br />

a continuous addition of inoculant to the<br />

stream of iron (normally added between<br />

one third and two thirds of ladle filling)<br />

so that the high turbulence encourages<br />

fast and homogeneous distribution of<br />

the alloy. Stream inoculation may be<br />

practised, in conjunction with automatic<br />

pouring furnaces, using finer sized<br />

grades of the above inoculants at lower<br />

addition rates. Similarly, inoculant fade<br />

can be overcome by reducing the time<br />

interval between the inoculant addition<br />

and solidification by placing the inoculant<br />

piece, or insert, into the gating<br />

system. The reaction with liquid iron<br />

occurs within the mould and this is<br />

known as in-mould inoculation.<br />

Fading is the reduction in inoculation<br />

effect with increasing time taken to pour<br />

inoculated iron. <strong>Elkem</strong> inoculants have<br />

been assessed against untreated reference<br />

melts and even after 10 minutes<br />

the inoculation effect of the treated melt<br />

proved to be good. Provided ladle inoculation<br />

has been carried out in a satisfactory<br />

way and the ladle is not delayed<br />

for an excessive period before pouring,<br />

the need for mould inoculation can be<br />

avoided in most cases.<br />

Table 4: <strong>Elkem</strong> preconditioner, inoculants and inserts for grey and ductile irons.<br />

Alinoc ® , Barinoc ® , Elcast ® , Foundrisil ® ,Reseed ® , SMZ ® , Superseed ® , Ultraseed ® , Vaxon ® and Zircinoc ®<br />

are registered trademarks owned by <strong>Elkem</strong> AS. Preseed is a trademark of <strong>Elkem</strong> AS.


6. Control of Inoculation<br />

Although nuclei cannot be observed<br />

directly at solidification temperatures,<br />

they have an effect on some properties<br />

which can be measured by:<br />

• recording cooling curves<br />

• measuring depth of chill in chill<br />

wedges<br />

• counting the number of eutectic cells<br />

• counting the number of graphite<br />

nodules<br />

6.1 Cooling Curves<br />

Cooling curves record the changes<br />

in temperature with time as a consequence<br />

of a change of energy within<br />

the system. A deviation from normal<br />

cooling indicates the occurrence of a<br />

source of heat such as the heat of<br />

crystallization released by a precipitating<br />

phase. The location of the inversion<br />

points on the generally S-shaped<br />

cooling curve in the region of eutectic<br />

crystallization indicates the tendency<br />

of the melt to solidify “grey” or “white”.<br />

A high level of nucleation promotes a<br />

higher arrest temperature which, by<br />

avoiding the white eutectic, will result<br />

in less risk of carbide formation.<br />

Conversely, when the inversion point is<br />

at a low level on the cooling curve, there<br />

will be a tendency for cementite to<br />

precipitate instead of graphite giving a<br />

“white” structure. An increased cooling<br />

rate, as found in thin sections, will increase<br />

the degree of undercooling that<br />

must be balanced by an increased<br />

number of active nuclei to avoid the<br />

formation of white iron. In the iron-carbon<br />

system there is only a 7 ºC interval<br />

between “grey” solidification and sufficient<br />

undercooling to cause “white”<br />

solidification. In Figure 7 the cooling<br />

curve for an uni noculated reference<br />

melt is compared with a curve from a<br />

melt inoculated with 0.25% inoculant<br />

addition.<br />

The uninoculated melt shows inversion<br />

at 1145 ºC whereas inversion occurs<br />

at 1162 ºC for the inoculated melt. This<br />

means that the uninoculated melt is<br />

undercooled by 20 ºC and the inoculated<br />

melt by 3 ºC, which gives “white” and<br />

“grey” solidification, respectively.<br />

Figure 7: Solidfication curves for<br />

uninoculated ductile iron (a), and<br />

inoculated ductile cast iron (b)<br />

(30 mm section size).<br />

6.2 Chill Testing<br />

The traditional method to determine the<br />

tendency of a melt to solidify “grey” or<br />

“white” is by examining chill wedges.<br />

The larger the zone of white iron, the<br />

fewer the number of nuclei that were<br />

active in initiating a “grey” solidification.<br />

Figure 8 shows chill wedges from a<br />

foundry which had an average 11.2 mm<br />

of chill for a period of two week on uninoculated<br />

cupola iron. By adding 0.2%<br />

FeSi (85% Si), the average chill depth<br />

was reduced and with 0.125% Superseed<br />

® inoculant addition, the chill depth<br />

was reduced even further.<br />

6.3 Eutectic Cell Count<br />

The number of eutectic cells in grey iron<br />

can be determined on etched microspecimens.<br />

If an effective inoculant has<br />

been added to the melt, there will be a<br />

large number of active nuclei to promote<br />

graphite precipitation at low undercooling<br />

during solidification. This will<br />

be represented on the micro-specimen<br />

by a high cell count for grey iron and<br />

a high nodule count for ductile iron.<br />

Table 5 shows the result of cell counts<br />

after inoculation. The eutectic cell<br />

number increases as the inoculant<br />

addition to the base melt is increased.<br />

Other factors, such as over-inoculation<br />

leading to shrinkage proprensity, will influence<br />

the optimum inoculant addition.


Table 5: Eutectic cell count (30 mm round bars).<br />

Figure 8: Cupola melted grey iron; no<br />

inoculation (left), inoculated with 0.2%<br />

FeSi85% (centre), and inoculated with<br />

0.125% Superseed ® inoculant (right).<br />

7. Fading of Inoculation<br />

7.1 Principle Effects<br />

The effects of inoculation are at a maximum<br />

immediately after the addition of the<br />

inoculant. The rate of inoculant fading,<br />

which depends upon the composition<br />

of the inoculant and the condition of the<br />

iron to which it is added, may be very<br />

rapid and much of the inoculating effect<br />

may be lost in the first few minutes after<br />

the addition. The principal effects of<br />

fading are:<br />

• to cause greater undercooling to take<br />

place during eutectic solidification<br />

and to lead to a greater tendency to<br />

chilling in grey and ductile cast irons,<br />

particularly in thin sections;<br />

• to reduce the number of nodules<br />

formed in ductile iron and to cause a<br />

deterioration in their shape. If suffic ient<br />

ly severe, the deterioration in shape<br />

may affect the mechanical properties<br />

of the casting;<br />

• to reduce the number of eutectic cells<br />

growing in flake graphite irons result<br />

ing in a less uniform size distribution<br />

of graphite in the casting and a<br />

reduction in mechanical properties.<br />

There are some well established facts<br />

concerning fading which are of practical<br />

significance:<br />

• all inoculants fade;<br />

• there is no period after inoculation<br />

during which fading does not occur.<br />

To obtain the maximum effect, metal<br />

should be cast as soon as possible<br />

after the addition of inoculant;<br />

• some inoculants fade more slowly<br />

than others;<br />

• inoculating effects vary according to<br />

inoculant composition. It is desirable<br />

that foundries should carry out tests<br />

to determine which is the most suit<br />

able inoculant for their purpose.


7.2 Coarsening of Inclusions<br />

It has previously been discussed that<br />

graphite nucleation occurs from nonmetallic<br />

inclusions in the melt. A significant<br />

coarsening of these inclusions<br />

occurs within the time interval between<br />

inoculation and solidification of the cast<br />

iron. This coarsening of inclusions will<br />

result in a reduction in the inclusion<br />

number density, consequently reducing<br />

the graphite nucleation frequency.<br />

Hence, the fading of inoculation can<br />

be explained by this coarsening of the<br />

inclusion population with time. Due to<br />

the coarsening, the total number of<br />

possible nucleation sites for graphite<br />

during solidification is reduced.<br />

Figure 9 shows a plot of the number<br />

density of inclusions in cast iron as a<br />

function of holding time after inocu lation.<br />

7.3 Effects of Various Inclusions<br />

Inoculants lose their ability to reduce<br />

chill and nucleate graphite if the metal<br />

is held for extended periods before<br />

casting. However, inoculants have<br />

different fading characteristics. The<br />

barium-based Barinoc ® inoculant<br />

produces a high initial number of<br />

nucleation sites throughout the holding<br />

period, thus making it an excellent<br />

inoculant for ladle treatments.<br />

Foundrisil ® inoculant is an effective<br />

chill reducer for both low and high<br />

sulphur grey iron as well as ductile<br />

iron. Another effective inoculant that<br />

maintains the inoculation effect is the<br />

strontium-containing Superseed ®<br />

inoculant. Figure 10 shows the fading<br />

characteristics of some inoculants in<br />

cast iron.<br />

Figure 9: Coarsening behaviour of<br />

inclusions in liquid cast iron during<br />

holding.<br />

Figure 10: Fading characteristics for<br />

various inoculants in cast iron.<br />

8. Inoculation and Cast Iron Properties<br />

8.1 Inoculation and Strength<br />

Inoculation increases the number of<br />

eutectic cells (or nodules) which leads<br />

to a finer structure of the iron, and in<br />

particular, this will cause an increase in<br />

tensile strength in hypoeutectic irons.<br />

Figure 11 shows the increase in tensile<br />

strength by adding an inoculant.<br />

8.2 Inoculation and Machinability<br />

Inoculation increases the number of<br />

potent nuclei that will promote graphite<br />

nucleation at low undercooling. Improved<br />

machinability is achieved by<br />

inoculation suppressing the formation<br />

of hard un-machinable white iron<br />

structures. Inoculation also reduces<br />

section sensitivity. While uninoculated<br />

irons will show a wide variation in<br />

hardness, inoculated grey or nodular<br />

cast irons will show more consistent<br />

hardness values over a wide range of<br />

sections, Figure 12.<br />

Figure 12: The wall thickness sensitivity<br />

of (Brinell) hardness can be<br />

reduced by an inoculant (partly calculated<br />

from Rockwell -B* and -C**).<br />

Figure 11: Increasing inoculant<br />

additions improve tensile strength.<br />

The final analyses of these trial melts<br />

are identical after inoculation.


9. Inoculation and Shrinkage<br />

The solidification of grey iron is characterized<br />

by the formation of a skin type<br />

array of eutectic cells at the mould/metal<br />

interface, followed by the development<br />

of eutectic cells ahead of the advancing<br />

solidification front. Newly formed graphite<br />

compensates partly or fully for the liquid<br />

iron contraction, provided it precipitates<br />

within a relatively rigid “skin”, which is<br />

charac teristic of uninoculated grey iron.<br />

How ever, if the mode of solidification is<br />

changed, the good shrinkage characteristics<br />

can be jeopardized, especially if<br />

a rigid skin cannot be developed at the<br />

mould/metal interface leaving the mould<br />

directly exposed to ferrostatic pressure.<br />

Eventually, the mould may yield under the<br />

ferrostatic pressure from the remaining<br />

liquid, and the increased volume of the<br />

mould cavity becomes too high for compensation<br />

by graphite precipitation at the<br />

end of solidification. Some shrinkage may<br />

occur as a result of excessive dilation of<br />

the mould although mould geometry<br />

will have an influence.<br />

Unfortunately, inoculation changes the<br />

mode of solidification in such a way that<br />

the rigidity of the “skin” is decreased.<br />

Inoculant additions should not become<br />

excessive to avoid shrinkage and yet the<br />

addition should be adequate to ensure<br />

“grey” solidification. Test specimens,<br />

Figure 13, show that for an equivalent<br />

chill depth, the eutectic cell count will be<br />

lower when using Superseed ® inoculant<br />

in place of foundry grade ferrosilicon.<br />

The lower cell count reduces the ferrostatic<br />

pressure on the mould and improves<br />

the tendency to avoid shrinkage<br />

defects.<br />

Since the eutectic cell count for nodular<br />

cast iron is much higher than for grey iron,<br />

one would expect a greater shrinkage<br />

tendency, and it is interesting to see<br />

that the solidification pattern is in fact<br />

similar to over-inoculated grey iron.<br />

Ultraseed ® inoculant has proven highly<br />

successful in providing fresh nucleation<br />

sites to ductile irons of long holding time<br />

where the base iron or magnesium<br />

treated iron have been held for prolonged<br />

times before addition of the<br />

post inoculant. Such long hold times<br />

are well known to reduce the overall<br />

capabilities of the iron prior to inoculation<br />

resulting in so-called “dead” iron.<br />

Ultraseed ® inoculant will thus reinstall<br />

good nucleation effectiveness from<br />

reactions with its sulphur and oxygen<br />

content forming new nucleation sites.<br />

Due to the powerful effects of Ultraseed ®<br />

inoculant on raising nodule count and<br />

improving chill protection, it has been<br />

found that the tendency to shrinkage<br />

formation is also reduced with this inoculant.<br />

Especially, the type of shrinkage<br />

that often occurs as small porosities in<br />

hot-spot sections of the complex castings;<br />

appear to be effec tively reduced<br />

or even eliminated by Ultraseed ® inoculant.<br />

Figure 14 shows an example of<br />

microshrinkage porosity that has been<br />

minimized by the use of Ultraseed ®<br />

inoculant.<br />

Figure 13: Comparison of the eutectic<br />

cell count in 5 mm sections at about<br />

equal chill depth (from BCIRA).<br />

Figure 14: Example of micro-shrinkage prorosity in ductile iron part that has been<br />

minimized by Ultraseed ® inoculant (left), compared to manganese-zirconium<br />

containing inoculant (right).


10. Product Development<br />

Based on a comprehensive under standing<br />

of the mechanisms of ino culation<br />

described in this brochure, <strong>Elkem</strong> has,<br />

over the years, evaluated many alternative<br />

alloy analyses to develop the current<br />

range of inoculants which includes the<br />

well established Superseed ® ,Ultraseed ® ,<br />

Reseed ® and Alinoc ® inoculants.<br />

Development of new improved alloys<br />

goes on continuously.<br />

Recently, Preseed preconditioner<br />

has been added to the portfolio as a<br />

novel preconditioner to enhance inoculation<br />

effect.<br />

For further information on <strong>Elkem</strong>’s<br />

extensive range of inoculants, please<br />

contact your local representative. The<br />

success of <strong>Elkem</strong> products worldwide<br />

justifies their elaborate development<br />

and provides a sound base for the<br />

foundryman to select the appropriate<br />

inoculant for his foundry’s particular<br />

requirements.<br />

References:<br />

1) Skaland, T.: Ph.D Thesis, The Norwegian Inst. of Tech., 1992<br />

2) Engler, S.: Giesserei, techn.-wiss.Beih., 17(1965), p 169/202<br />

3) Moore, A.: Brit.Foundrym. 68 (1974) March, p59/69 Patterson, V.H; Foundry 100 (1972) June, p 68/71<br />

4) Riposan et al: Investigation of the Effect of Residual Aluminium on Solidification Characteristics of Un-inoculated Ca/Sr-Inoculated Gray Irons. AFS 2004<br />

<strong>Elkem</strong> AS<br />

Foundry Products<br />

Hoffsveien 65B<br />

P.O. Box 5211<br />

Majorstuen<br />

N-0303, Oslo, Norway<br />

Telephone : +47 22 45 01 00<br />

Telefax : +47 22 45 01 52<br />

www.foundry.elkem.com<br />

Revised April 2012 © Copyright <strong>Elkem</strong> AS

Hooray! Your file is uploaded and ready to be published.

Saved successfully!

Ooh no, something went wrong!