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Cast iron usually refers to Gray iron, but also identifies a large group of ferrous alloys, which solidify with a eutectic. The color of a fractured surface can be used to identify an alloy. White cast iron is named after its white surface when fractured due to its carbide impurities which allow cracks to pass straight through. Grey cast iron is named after its grey fractured surface, which occurs because the graphitic flakes deflect a passing crack and initiate countless new cracks as the material breaks.

Iron (Fe) accounts for more than 95% by weight (wt%) of the alloy material, while the main alloying elements are carbon (C) and silicon (Si). The amount of carbon in cast irons is 2.1 to 4 wt%. Cast irons contain appreciable amounts of silicon, normally 1 to 3 wt%, and consequently these alloys should be considered ternary Fe-C-Si alloys. Despite this, the principles of cast iron solidification are understood from the binary iron-carbon phase diagram, where the eutectic point lies at 1154 °C and 4.3 wt% carbon. Since cast iron has nearly this composition, its melting temperature of 1150 to 1200 °C is about 300 °C lower than the melting point of pure iron.

Cast iron tends to be brittle, except for malleable cast irons. With its low melting point, good fluidity, castability, excellent machinability, resistance to deformation, and wear resistance, cast irons have become an engineering material with a wide range of applications, including pipes, machine and car parts, such as cylinder heads, blocks, and gearbox cases. It is resistant to destruction and weakening by oxidization (rust).

Silicon is essential to making grey cast iron as opposed to white cast iron. When silicon is alloyed with ferrite and carbon in amounts of about 2 percent, the carbide of iron becomes unstable. Silicon causes the carbon to rapidly come out of solution as graphite, leaving a matrix of relatively pure, soft iron. Weak bonding between planes of graphite lead to a high activation energy for growth in that direction, resulting in thin, round flakes. This structure has several useful properties.

The metal expands slightly on solidifying as the graphite precipitates, resulting in sharp castings. The graphite content also offers good corrosion resistance.

Graphite acts as a lubricant, improving wear resistance. The exceptionally high speed of sound in graphite gives cast iron a much higher thermal conductivity[citation needed].. Since ferrite is so different in this respect (having heavier atoms, bonded much less tightly) phonons tend to scatter at the interface between the two materials. In practical terms, this means that cast iron tends to “damp” mechanical vibrations (including sound), which can help machinery to run more smoothly.

All of the properties listed in the paragraph above ease the machining of grey cast iron. The sharp edges of graphite flakes also tend to concentrate stress, allowing cracks to form much more easily, so that material can be removed much more efficiently.

Easier initiation of cracks can be a drawback once an item is finished, however: grey cast iron has less tensile strength and shock resistance than steel. It is also difficult to weld. However, compressive strength can be almost as high as for some mild steels.

Grey cast iron's high thermal conductivity and specific heat capacity are often exploited to make cast iron cookware and disc brake rotors.

With a lower silicon content and faster cooling, 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, usually in a eutectic mixture where the other phase is austenite (which on cooling might transform to martensite). These eutectic carbides are much too large to provide precipitation hardening (as in some steels, where cementite precipitates might inhibit plastic deformation by impeding the movement of dislocations through the 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 (conceivably?) balls for rolling-element bearings and the teeth of a backhoe's digging bucket (although the latter two applications would normally use high quality wrought high-carbon martensitic steels and cast medium-carbon martensitic steels respectively).

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 and a somewhat tougher interior.

White cast iron can also be made by using a high percentage of chromium in the iron; Cr is a strong carbide-forming element, so at high enough percentages of chrome, the precipitation of graphite out of the iron is suppressed. High-chrome white iron alloys allow massive castings (for example, a 10-tonne impeller) to be sand cast, i.e., a high cooling rate is not required, as well as providing impressive abrasion resistance.

Malleable iron starts as a white iron casting, that is then heat treated at about 900 °C. Graphite separates out much more slowly in this case, so that surface tension has time to form it into spheroidal particles rather than flakes. Due to their lower aspect ratio, 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 faced by grey cast iron. In general, the properties of malleable cast iron are more like mild steel. There is a limit to how large a part can be cast in malleable iron, since it is made from white cast iron.

A more recent development is nodular or ductile cast iron. Tiny amounts of magnesium or cerium added to these alloys slow down the growth of graphite precipitates by bonding to the edges of the graphite planes. Along with careful control of other elements and timing, this allows the carbon to separate as spheroidal particles as the material solidifies. The properties are similar to malleable iron but parts can be cast with larger sections.

Cast iron is melted in furnaces usually in half ton measures[citation needed]. The metal melted usually consists of discs and drums[citation needed] and its properties are changed by adding an inoculant. This alters the characteristics of the metal to various grades and between grey and SG iron.