Rapid quenching of austenite to room temperature often results in the formation of
martensite, a very hard structure in which the carbon, formerly in solid solution in
the austenite, remains in solution in the new phase. Unlike ferrite or pearlite,
martensite forms by a sudden shear process in the austenite lattice which is not
normally accompanied by atomic diffusion.
Ideally, the martensite reaction is a diffusionless shear transformation, highly
crystallographic in character, which leads to a characteristic lath or lenticular
microstructure. The martensite reaction in steels is the best known of a large group
of transformations in alloys in which the transformation occurs by shear without
change in chemical composition. The generic name of martensitic transformation
describes all such reactions.
It should however be mentioned that there is a large number of transformations which
possess the geometric and crystallographic features of martensitic transformations,
but which also involve diffusion. Consequently, the broader term of shear
transformation is perhaps best used to describe the whole range of possible
transformations.
The martensite reaction in steels normally occurs athermally, i.e. during cooling
in a temperature range which can be precisely defined for a particular steel. The
reaction begins at a martensitic start temperature Ms
which can vary over a wide temperature range from as high as 500°C to well below
room temperature, depending on the concentration of γ-stabilizing alloying
elements in the steel.
Once the Ms is reached, further transformation takes
place during cooling until the reaction ceases at the Mf
temperature. At this temperature all the austenite should have transformed to
martensite but frequently, in practice, a small proportion of the austenite does not
transform. Larger volume fractions of austenite are retained in some highly alloyed
steels, where the Mf temperature is well below room
temperature.
To obtain the martensitic reaction it is usually necessary for the steel to be
rapidly cooled, so that the metastable austenite reaches Ms.
The rate of cooling must be sufficient to suppress the higher temperature
diffusion-controlled ferrite and pearlite reactions, as well as other intermediate
reactions such as the formation of bainite. The critical rate of cooling required
is very sensitive to the alloying elements present in the steel and, in general,
will be lower the higher total alloy concentration.
Each grain of austenite transforms by the sudden formation of thin plates or laths
of martensite of striking crystallographic character. The laths have a well-defined
habit plane and they normally occur on several variants of this plane within each
grain. The habit plane is not constant, but changes as the carbon content is
increased.
Martensite is a supersaturated solid solution of carbon in iron which has a
body-centred tetragonal structure, a distorted form of bcc iron. It is interesting
to note that carbon in interstitial solid solution expands the fcc iron lattice
uniformly, but with bcc iron the expansion is nonsymmetrical giving rise to
tetragonal distortion.
Analysis of the distortion produced by carbon atoms in the several types of site
available in the fcc and bcc lattices, has shown that in the fcc structure the
distortion is completely symmetrical, whereas in the bcc one, interstitial atoms
in z positions will give rise to much greater expansion of iron-iron atom distances
than in the x and y positions.
Assuming that the fcc-bcc tetragonal transformation occurs in a diffusionless way,
there will be no opportunity for carbon atoms to move, so those interstitial sites
already occupied by carbon will be favored. Since only the z sites are common to
both the fcc and bcc lattices, on transformation there are more carbon atoms at
these sites causing the z-axis to expand, and the non-regular the martensite,
as well as the shape deformation for a number of martensitic transformations
including ferrous martensites. It is, however, necessary to have accurate data,
so that the habit planes of individual martensite plates can be directly associated
with a specific orientation relationship of the plate with the adjacent matrix.
Martensitic planes in steel are frequently not parallel-sided; instead they are
often perpendicular as a result of constraints in the matrix, which oppose the shape
change resulting from the transformation. This is one of the reasons why it is
difficult to identify precisely habit planes in ferrous martensite. However, it
is not responsible for the irrational planes, but rather the scatter obtained in
experiments.
Another feature of higher carbon martensites is the burst phenomenon, in which one
martensite plate nucleates a sequence of plates presumably as a result of stress
concentrations set up when the first plate reaches an obstruction such as a grain
boundary or another martensite plate.
Perhaps the most striking advances in the structure of ferrous martensites occurred
when thin foil electron microscopy was first used on this problem. The two modes
of plastic deformation are needed for the in-homogeneous deformation part of the
transformation, i.e. slip and twinning. All ferrous martensites show very high
dislocation densities of the order of 1011 to 1012cm2,
which are similar to those of very heavily cold-worked alloys. Thus it is usually
impossible to analyze systematically the planes on which the dislocations occur or
determine their Burgers vectors.
The lower carbon (<0.5% C) martensites on the whole exhibit only
dislocations. At higher carbon levels very fine twins (5-10 nm wide) commonly occur.
In favorable circumstances the twins can be observed in the optical microscope, but
the electron microscope allows the precise identification of twins by the use of
the selected area electron diffraction technique. Thus the twin shears can be
analyzed precisely and have provided good evidence for the correctness of the
crystallographic theories discussed above. However, twinning is not always fully
developed and even within one plate some areas are often untwined. The phenomenon
is sensitive to composition.
The evidence suggests that deformation by dislocations and by twinning are
alternative methods by which the lattice invariant deformation occurs. From general
knowledge of the two deformation processes, the critical resolved shear stress for
twinning is always much higher than that for slip on the usual slip plane. This
applies to numerous alloys of different crystal structure.
Thus it might be expected that those factors, which raise the yield stress of the
austenite, and martensite, will increase the likelihood of twinning. The important
variables are:
- carbon concentration;
- alloying element concentration;
- temperature of transformation;
- strain rate.
The yield stress of both austenite and martensite increases with carbon content,
so it would normally be expected that twinning would, therefore, be encouraged.
Likewise, an increase in the substitutional solute concentration raises the strength
and should also increase the incidence of twinning, even in the absence of carbon,
which would account for the twins observed in martensite in high concentration
binary alloys such as Fe-32%Ni.
A decrease in transformation temperature, i.e. reduction in Ms,
should also help the formation of twins, and one would particularly expect this in
alloys transformed, for example, well below room temperature.
It should also be noted that carbon concentration and alloying element concentration
should assist by lowering Ms. As martensite forms over a
range of temperatures, it might be expected in some steels that the first formed
plates would be free of twins whereas the plates formed nearer to
Ms would more likely be twinned.
However, often plates have a mid-rib along which twinning occurs, the outer regions
of the plate being twin-free. This could possibly take place when the
Ms is below room temperature leading to twinned plates
which might then grow further on resting at room temperature.
Lath Martensite
This type of martensite is found in plain carbon and low alloy steels up to about
0.5 wt% carbon. The morphology is lath or plate-like, where the laths are very long.
These are grouped together in packets with low angle boundaries between each lath,
although a minority of laths is separated by high angle boundaries. In plain carbon
steels practically no twin-related laths have been detected.
Medium Carbon Martensite
It is perhaps unfortunate that the term acicular is applied to this type of
martensite because its characteristic morphology is that of perpendicular plates,
a fact easily demonstrated by examination of plates intersecting two surfaces at
right angles.
These plates first start to form in steels with about 0.5% carbon, and can be
concurrent with lath martensite in the range 0.5 %-l.0 % carbon. Unlike the laths,
the lenticular plates form in isolation rather than in packets, on planes
approximating to {225} and on several variants within one small region of a grain,
with the result that the structure is very complex.
The burst phenomenon probably plays an important part in propagating the
transformation, and the austenite is thus not as uniformly or as efficiently
eliminated as with lath martensites. This physical difference cannot be unconnected
with the fact that higher percentages of retained austenite occur as the carbon
level is increased, and the martensite is predominantly lenticular. The micro
twinning referred to earlier is found predominantly in this type of martensite,
which forms at lower Ms temperatures, as the carbon
content increases.
High Carbon Martensite
When the carbon content is >1.4wt%, the orientation relationship changes from
Kurdjumov-Sachs to Nishiyama, and the habit plane changes to around {259}. The
change is not detectable microscopically as the morphology is still lenticular
plates which form individually and are heavily twinned.
Detailed crystallographic analysis shows that this type of martensite obeys more
closely the theoretical predictions than the {225} martensite. The plates are
formed by the burst mechanism and often an audible click is obtained.
The {259} martensite only forms at very high carbon levels in plain carbon steels,
although the addition of metallic alloying elements causes it to occur at much lower
carbon contents, and in the extreme case in a carbon-free alloy such as Fe-Ni when
the nickel content exceeds about 29 wt%.
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