Cast iron’s properties are changed by adding various alloying elements, or alloyant.. Next to carbon, silicon is the most important alloyant because it forces carbon out of solution. A low percentage of silicon allows carbon to remain in solution forming iron carbide and the production of white cast iron. A high percentage of silicon forces carbon out of solution forming graphite and the production of grey cast iron. Other alloying agents, manganese, chromium, molybdenum, titanium and vanadium counteracts silicon, promotes the retention of carbon, and the formation of those carbides. Nickel and copper increase strength, and machinability, but do not change the amount of graphite formed. The carbon in the form of graphite results in a softer iron, reduces shrinkage, lowers strength, and decreases density. Sulfur, largely a contaminant when present, forms iron sulfide, which prevents the formation of graphite and increases hardness. The problem with sulfur is that it makes molten cast iron viscous, which causes defects. To counter the effects of sulfur, manganese is added because the two form into manganese sulfide instead of iron sulfide. The manganese sulfide is lighter than the melt, so it tends to float out of the melt and into the slag. The amount of manganese required to neutralize sulfur is 1.7 × sulfur content + 0.3%. If more than this amount of manganese is added, then manganese carbide forms, which increases hardness and chilling, except in grey iron, where up to 1% of manganese increases strength and density.

Nickel is one of the most common alloying elements because it refines the pearlite and graphite structure, improves toughness, and evens out hardness differences between section thicknesses. Chromium is added in small amounts to reduce free graphite, produce chill, and because it is a powerful carbide stabilizer; nickel is often added in conjunction. A small amount of tin can be added as a substitute for 0.5% chromium. Copper is added in the ladle or in the furnace, on the order of 0.5–2.5%, to decrease chill, refine graphite, and increase fluidity. Molybdenum is added on the order of 0.3–1% to increase chill and refine the graphite and pearlite structure; it is often added in conjunction with nickel, copper, and chromium to form high strength irons. Titanium is added as a degasser and deoxidizer, but it also increases fluidity. 0.15–0.5% vanadium is added to cast iron to stabilize cementite, increase hardness, and increase resistance to wear and heat. 0.1–0.3% zirconium helps to form graphite, deoxidize, and increase fluidity

In malleable iron melts, bismuth is added, on the scale of 0.002–0.01%, to increase how much silicon can be added. In white iron, boron is added to aid in the production of malleable iron; it also reduces the coarsening effect of bismuth.

Grey cast iron

Grey cast iron is characterized by its graphitic microstructure, which causes fractures of the material to have a grey appearance. It is the most commonly used cast iron and the most widely used cast material based on weight. Most cast irons have a chemical composition of 2.5–4.0% carbon, 1–3% silicon, and the remainder iron. Grey cast iron has less tensile strength and shock resistance than steel, but its compressive strength is comparable to low- and medium-carbon steel. These mechanical properties are controlled by the size and shape of the graphite flakes present in the microstructure and can be characterised according to the guidelines given by the ASTM.[6]

White cast iron

White cast iron displays white fractured surfaces due to the presence of an iron carbide precipitate called cementite. With a lower silicon content (graphitizing agent) and faster cooling rate, the carbon in white cast iron precipitates out of the melt as the metastable phase cementite, Fe3C, rather than graphite. The cementite which precipitates from the melt forms as relatively large particles. As the iron carbide precipitates out, it withdraws carbon from the original melt, moving the mixture toward one that is closer to eutectic, and the remaining phase is the lower iron-carbon austenite (which on cooling might transform to martensite). These eutectic carbides are much too large to provide the benefit of what is called precipitation hardening (as in some steels, where much smaller cementite precipitates might inhibit plastic deformation by impeding the movement of dislocations through the pure iron ferrite matrix). Rather, they increase the bulk hardness of the cast iron simply by virtue of their own very high hardness and their substantial volume fraction, such that the bulk hardness can be approximated by a rule of mixtures. In any case, they offer hardness at the expense of toughness. Since carbide makes up a large fraction of the material, white cast iron could reasonably be classified as a cermet. White iron is too brittle for use in many structural components, but with good hardness and abrasion resistance and relatively low cost, it finds use in such applications as the wear surfaces (impeller and volute) of slurry pumps, shell liners and lifter bars in ball mills and autogenous grinding mills, balls and rings in coal pulverisers, and the teeth of a backhoe’s digging bucket (although cast medium-carbon martensitic steel is more common for this application).

It is difficult to cool thick castings fast enough to solidify the melt as white cast iron all the way through. However, rapid cooling can be used to solidify a shell of white cast iron, after which the remainder cools more slowly to form a core of grey cast iron. The resulting casting, called a chilled casting, has the benefits of a hard surface with a somewhat tougher interior.

High-chromium white iron alloys allow massive castings (for example, a 10-tonne impeller) to be sand cast, as the chromium reduces cooling rate required to produce carbides through the greater thicknesses of material. Chromium also produces carbides with impressive abrasion resistance.[citation needed] These high-chromium alloys attribute their superior hardness to the presence of chromium carbides. The main form of these carbides are the eutectic or primary M7C3 carbides, where “M” represents iron or chromium and can vary depending on the alloy’s composition. The eutectic carbides form as bundles of hollow hexagonal rods and grow perpendicular to the hexagonal basal plane. The hardness of these carbides are within the range of 1500-1800HV[7

Malleable cast iron

Malleable iron starts as a white iron casting that is then heat treated for a day or two at about 950 °C (1,740 °F) and then cooled over a day or two. As a result, the carbon in iron carbide transforms into graphite and ferrite plus carbon (austenite). The slow process allows the surface tension to form the graphite into spheroidal particles rather than flakes. Due to their lower aspect ratio, the spheroids are relatively short and far from one another, and have a lower cross section vis-a-vis a propagating crack or phonon. They also have blunt boundaries, as opposed to flakes, which alleviates the stress concentration problems found in grey cast iron. In general, the properties of malleable cast iron are more like those of mild steel. There is a limit to how large a part can be cast in malleable iron, as it is made from white cast iron.

Ductile cast iron