It should first be pointed out that the normal equilibrium diagram really represents the metastable equilibrium between iron and iron carbide (cementite). Cementite is metastable, and the true equilibrium should be between iron and graphite. Although graphite occurs extensively in cast irons (2-4 wt % C), it is usually difficult to obtain this equilibrium phase in steels (0.03-1.5 wt %C). Therefore, the metastable equilibrium between iron and iron carbide should be considered, because it is relevant to the behavior of most steels in practice.
The much larger phase field of γ-iron (austenite) compared with that of α-iron (ferrite) reflects the much greater solubility of carbon in γ-iron, with a maximum value of just over 2 wt % at 1147°C (E, Fig.1). This high solubility of carbon in γ-iron is of extreme importance in heat treatment, when solution treatment in the γ-region followed by rapid quenching to room temperature allows a supersaturated solid solution of carbon in iron to be formed.
The α-iron phase field is severely restricted, with a maximum carbon solubility of 0.02 wt% at 723°C (P), so over the carbon range encountered in steels from 0.05 to 1.5 wt%, α-iron is normally associated with iron carbide in one form or another. Similarly, the δ-phase field is very restricted between 1390 and 1534°C and disappears completely when the carbon content reaches 0.5 wt% (B).
There are several temperatures or critical points in the diagram, which are important, both from the basic and from the practical point of view.
The eutectoid temperature is 723°C while the eutectoid composition is 0.80% C(s). On cooling alloys containing less than 0,80% C slowly, hypo-eutectoid ferrite is formed from austenite in the range 910-723°C with enrichment of the residual austenite in carbon, until at 723°C the remaining austenite, now containing 0.8% carbon transforms to pearlite, a lamellar mixture of ferrite and iron carbide (cementite). In austenite with 0,80 to 2,06% carbon, on cooling slowly in the temperature interval 1147°C to 723°C, cementite first forms progressively depleting the austenite in carbon, until at 723°C, the austenite contains 0.8% carbon and transforms to pearlite.
Steels with less than about 0.8% carbon are thus hypo-eutectoid alloys with ferrite and pearlite as the prime constituents, the relative volume fractions being determined by the lever rule which states that as the carbon content is increased, the volume percentage of pearlite increases, until it is 100% at the eutectoid composition. Above 0.8% C, cementite becomes the hyper-eutectoid phase, and a similar variation in volume fraction of cementite and pearlite occurs on this side of the eutectoid composition.
The three phases, ferrite, cementite and pearlite are thus the principle constituents of the infrastructure of plain carbon steels, provided they have been subjected to relatively slow cooling rates to avoid the formation of metastable phases.
However, by quenching from the austenitic state to temperatures below the eutectoid temperature Ae1, ferrite can be formed down to temperatures as low as 600°C. There are pronounced morphological changes as the transformation temperature is lowered, which it should be emphasized apply in general to hypo-and hyper-eutectoid phases, although in each case there will be variations due to the precise crystallography of the phases involved. For example, the same principles apply to the formation of cementite from austenite, but it is not difficult to distinguish ferrite from cementite morphologically.
As in the case of ferrite, most of the side plates originate from grain boundary allotriomorphs, but in the cementite reaction more side plates nucleate at twin boundaries in austenite.
Pearlite is a very common constituent of a wide variety of steels, where it provides a substantial contribution to strength. Lamellar eutectoid structures of this type are widespread in metallurgy, and frequently pearlite is used as a generic term to describe them.
These structures have much in common with the cellular precipitation reactions. Both types of reaction occur by nucleation and growth, and are, therefore, diffusion controlled. Pearlite nuclei occur on austenite grain boundaries, but it is clear that they can also be associated with both pro-eutectoid ferrite and cementite. In commercial steels, pearlite nodules can nucleate on inclusions.