Cast Irons and Alloy Cast Irons

In Victorian times almost anything was likely to be made of cast ironstreet lamps, domestic fireplaces, railings, mock-gothic church window frames and the ornamental water fountain in the local park. Sadly many of these relics of the nineteenth century foundryman's art are no more since most fell victim to the urgent need for steel during the Second World War. Even as late as the author's childhood toy 'six-shooters' were of white cast iron, whereas to-day's children play with 'space-age' guns made of plastics materials. One important reason for the widespread use of cast iron in Victorian times was the fact that in those days not all pig iron produced was suitable for conversion into merchantable steel. In particular those pig irons high in phosphorus and sulphur were suitable only for ornamental castings which required little strength. Today cast ironis used exclusively for engineering purposes and its technology, like thatof other alloys, continues to be developed at highly sophisticated levels. 'Spheroidal graphite' cast iron and, more recently, 'compacted graphite' irons are of this type. Ordinary cast iron is very similar in composition and structure to the crude pig iron from the blast furnace. In most foundries the 'pigs' are melted, often with the addition of low-grade steel scrap, in a cupola, any necessary adjustments in composition being made during this melting process. The relative scarcity and consequent high cost of metallurgical coke has led some foundries to adopt electric melting, usually by highfrequency induction furnaces. An obvious advantage of electric melting is its chemical cleanliness and lack of sulphur contamination as compared with cupola melting where the iron is in intimate contact with the burning coke. Consequently many of the high quality grey cast irons, as well as spheroidal-graphite irons and alloy cast irons are now melted electrically. Because production costs of pig iron are relatively low as compared with other alloys, and since no expensive refining process is necessary, cast ironis a cheap metallurgical material which is particularly useful where a casting requiring rigidity, resistance to wear or high compressive strength is necessary.

Other useful properties of cast iron include: (i) good machinability when a suitable composition is selected; (ii) high fluidity and the ability to make good casting impressions; (iii) fairly low melting range (1130-1250 0 C) as compared with steel; (iv) the availability of high strengths when additional treatment is given to suitable irons, eg spheroidal-graphite iron, compacted-graphite irons or pearlitic malleable irons. The structure and physical properties of a cast iron depend upon both chemical composition and the rate at which it solidifies following casting.

The Effects of Composition on the Structure of Cast Iron

Ordinary cast iron is a complex alloy containing a total of up to 10% of the elements carbon, silicon, manganese, sulphur and phosphorus; the balance being iron. Alloy cast irons, which will be dealt with later in this chapter, contain also varying amounts of nickel, chromium, molybdenum, vanadium and copper. Carbon can exist in two forms in cast iron, namely as free graphite or combined with some of the iron to form iron carbide (cementite). These two varieties are usually referred to as graphic carbon and combined carbon respectively, and the total amount of both types in the specimen of iron as total carbon. In ordinary engineering cast iron the form in which carbon is present depends largely upon the cooling rate during solidification and upon the quantity of silicon present. In alloy cast irons those elements mentioned above will also affect the resultant structure. In fact the effects of various elements on the microstructure of cast iron is generally the sameas in steels. Cementite is a hard, white, brittle compound, so that irons which contain much of it will present a white fracture when broken, and will have a low resistance to shock. At the same time they will possess a high resistance

to wear. Such irons are called white irons. The fractured surface of a cast iron containing graphite, however, will appear grey, and the iron will be termed a grey iron. Although the form of the iron-carbon diagram is of great value to the practical metallurgist it is not a true equilibrium diagram because in fact cementite is not an 'equilibrium phase'. Cementite is said to be a metastable phase, that is, it has a natural tendency to decompose forming a mixture of iron (ferrite) and carbon (graphite). In ordinary steels this decomposition almost never occurs because in iron supersaturated with carbon the nucleation of cementite takes place much more readily than the nucleation of graphite. Once cementite has formed it is quite stable and for practical purposes can be regarded as an equilibrium phase. In a simple iron-carbon alloy containing, say, 3% carbon, solidification would begin with the formation of primary austenite and at 1131C

Fig(1)

eutectic consisting of austenite and cementite would form. However, engineering cast irons contain sufficient silicon to increase the instability ofcementite to the point where graphite is precipitated from solution instead. Therefore primary austenite will separate out first until the eutectic temperature (1131C) is reached, but at that temperature the eutectic which forms consists of austenite and graphite. This eutectic develops from nuclei

and is in the form of approximately spherical particles known as eutectic cells. The layers of austenite and graphite develop in roughly radial form, both being deposited directly from the liquid phase graphite appears to be in the form of separate flakes, but in fact the eutectic cells are threedimensional and roughly sphericalin shape so that the graphite layers can be regarded as something like those shown That is, rather like a cluster of potato crisps growing out from a central nucleus. As in the case of the eutectoid point in steels the eutectic point in cast irons may be displaced to the left by the presence of other elements, notably silicon. Thus, a cast iron containing less than 4.3% carbon may be hyper-eutectic in composition and so deposit primary graphite (instead of cementite) before the eutectic cells start to form. This primary graphite is generally coarse and was known as 'kish'.Rapid cooling, which produces a greater degree of under cooling, initiates the formation of a greater number of eutectic cells and also more frequent branching in the eutectic graphite 'leaves', giving much fine graphite flakes. The smaller the eutectic cells, the finer the graphite flake sand hence the better the mechanical properties. The presence of graphite gives a softer iron which machines well because of the effect of the graphite flakes in forming chip cracks in advance of the edge of the cutting tool). Moreover, since graphite occupies a greater volume in the solid structure than does carbon in solution in the liquid iron, it tends to counteract the effects of shrinkage during solidification.

Fig(2)

Silicon :
dissolves in the ferrite of a cast iron and is the element which has the predominant effect on the relative amounts of graphite and cementite which are present. Silicon tends to increase the instability of cementite (13.12) so that it decomposes, producing graphite and hence, a grey iron. The higher the silicon content, the greater the degree of decomposition of the cementite, and the coarser the flakes of graphite produced. Thus, whilst silicon actually strengthens the ferrite by dissolving in it, at the same time it produces softness by causing the cementite to break down to graphite. When, however, silicon is present in amounts in excess of that necessary to complete the decomposition of all the cementite, it will again cause hardness and brittleness to increase. Both the direct and indirect effects of silicon must therefore be considered. The presence of silicon in a cast iron is beneficial in so far as it increases the fluidity of the molten iron, and so improves its casting properties.

Sulphur:
The possible effect of the silicon present in an iron cannot be completely estimated without some reference to the sulphur content, since sulphur has the opposite effect, in that it tends to stabilise cementite. Sulphur, then, inhibits graphitisation and so helps to produce a hard, brittle, white iron. Moreover, its presence as the sulphide FeS in cast iron will also increase the tendency to brittleness. During the melting of cast iron in the cupola there is a tendency for some silicon to be oxidised and lost in the slag. At the same time some sulphur will always be absorbed from the coke in the cupola. Both of these changes in composition tend to make the iron more 'white' as they are opposed to the formation of graphite. The foundryman therefore makes allowances for these changes during melting in the cupola.

Manganese
The effect of sulphur is governed, in turn, by the amount of manganese present. Manganese combines with sulphur to form manganese sulphide, MnS, which, unlike iron(II) sulphide, is insoluble in the molten iron and floats to the top to join the slag. The indirect effect

of manganese, therefore, is to promote graphitisation because of the reduction of the sulphur content which it causes. Manganese has a stabilizing effect on carbides, however, so that this offsets the effect of sulphur reduction in promoting graphitisation. The more direct effects of manganese include the hardening of the iron, the refinement of grain and an increase in strength.

Phosphorus
is present in cast iron as the phosphide Fe3P, which forms a eutectic with the ferrite in grey irons, and with ferrite and cementite in white irons. These eutectics melt at about 950 C, so that high-phosphorus irons have great fluidity. Cast irons containing 1% phosphorus are, therefore, very suitable for the production of castings of thin section. High phosphorus contents should be avoided in heavy sections however, since Fe3P is brittle and lowers strength considerably. Its presence tends to promote increased shrinkage. Phosphorus has a negligible effect on the stability of cementite, but its direct effect is to promote hardness and brittleness due to the large volume of phosphide eutectic which a comparatively small amount of phosphorus will produce. Phosphorus must therefore be kept low in castings where shock-resistance is important.