The Iron Carbon Phase Diagram

There is more to the iron-carbon phase diagram than related in the backbone. In
particular, there is some nomenclature that I avoided in the main text but that is
important for understanding other writings about iron and steel. So let's start with a
phase diagram that contains maximal information:

Iron-carbon Phase Diagram

Source: Arabic Internet site

The important boundaries (the lines) separating phases have some universally
used abbreviations:

• A1: The upper limit of the ferrite / cementite phase field (horizontal line
going through the eutectoid point).
 • A2: The temperature where iron looses its magnetism (so-
called Curie temperature). Note that for pure iron this is still in the 〈-
phase.
• A3: The boundary between the  austenite and the austenite/ ferrite field.
• A4: The point in this case where 〈 changes to  at high temperatures.
• ACM: The boundary between the  austenite and the austenite / cementite
field.

Why would anybody abbreviate a temperature with the letter "A"? Well, it stands
for "arrest", something that happens in the slope of dilatometric or thermal curves
recorded whenever phase diagrams where first measured.
Statements like "the addition of x lowers A3" are now clear.
The circular insets give a schematic idea of what the structure would like at the
compositions and temperatures indicated.
The next thing to know is that the phase diagrams above is actually not the true iron-
carbon phase diagram. I lied to you. Some mixture of cementite and iron is not the
configuration that allows the system to achieve total nirvana. That would be a iron
- graphite mixture.
All the cementite forming is just a transient phase on the way to nirvana; it will
decay into pure carbon (graphite) and iron in due time. Due time, however,
means millennia and more at room temperature for plain carbon steel.
Cementite, in other words, is a very long-lived metastable phase under normal
conditions. It thus makes sense to use it for something that is not a true phase
diagram for purists, but that sane normal folks will call "phase diagram" anyway.
We are also justified in doing this because the "real" iron - graphite phase
diagram looks almost exactly like the iron - cementite "phase diagram". Here is
the proof:
 Iron - carbon phase diagram in comparison to
the iron cementite phase diagram

Does that mean that we don't have to worry about graphite being formed? Yes and
no. Like almost always, it depends:
For plain carbon steel with carbon concentrations below 2 %, you needn't worry,
indeed. Graphite is never formed and the usual phase diagram covers everything
nicely.
For cast-iron, with carbon concentrations up to a few percent you need to worry.
Graphite might form, depending on conditions.
For alloy steel, the usual thing nowadays, you need to worry, too. Some alloying
elements, in particular silicon (Si) but also nickel (Ni), promote graphite
formation.
 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.
• Firstly, there is the A1, temperature at which the eutectoid reaction occurs (P-S-K),
which is 723°C in the binary diagram.
• Secondly, there is the A3, temperature when α-iron transforms to γ-iron. For pure iron
this occurs at 910°C, but the transformation temperature is progressively lowered along
the line GS by the addition of carbon.
• The third point is A4 at which γ-iron transforms to δ-iron, 1390°C in pure iron, hut this is
raised as carbon is added. The A2, point is the Curie point when iron changes from the
ferro- to the paramagnetic condition. This temperature is 769°C for pure iron, but no
change in crystal structure is involved. The A1, A3 and A4 points are easily detected by
thermal analysis or dilatometry during cooling or heating cycles, and some hysteresis is
observed. Consequently, three values for each point can be obtained. Ac for heating, Ar
for cooling and Ae (equilibrium}, but it should be emphasized that the Ac and Ar values
will be sensitive to the rates of heating and cooling, as well as to the presence of
alloying elements.
The great difference in carbon solubility between γ- and α-iron leads normally to the
rejection of carbon as iron carbide at the boundaries of the γ phase field. The
transformation of γ to α - iron occurs via a eutectoid reaction, which plays a dominant
role in heat treatment.
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.

The austenite- ferrite transformation

Under equilibrium conditions, pro-eutectoid ferrite will form in iron-carbon alloys
containing up to 0.8 % carbon. The reaction occurs at 910°C in pure iron, but takes
place between 910°C and 723°C in iron-carbon alloys.
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.

The austenite-cementite transformation

The Dube classification applies equally well to the various morphologies of cementite
formed at progressively lower transformation temperatures. The initial development of
grain boundary allotriomorphs is very similar to that of ferrite, and the growth of side
plates or Widmanstaten cementite follows the same pattern. The cementite plates are
more rigorously crystallographic in form, despite the fact that the orientation relationship
with austenite is a more complex one.
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.
The austenite-pearlite reaction
Pearlite is probably the most familiar micro structural feature in the whole science of
metallography. It was discovered by Sorby over 100 years ago, who correctly assumed
it to be a lamellar mixture of iron and iron carbide.
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.