1

Introductionto Martensite
andMartensitic Transformation

C o m p a r e d with that obtained by slow cooling, i r o n - c a r b o n steel quenched

from a high temperature has a very fine and sharp microstructure a n d is
much harder. The mechanical properties a n d structure of quenched steels
have long been studied because of their technological importance. The struc­
ture of quenched steel is called martensite in h o n o r of Professor A. Martens,
the famous pioneer G e r m a n metallographer who greatly extended Sorby's
initial work. Initially, the term was ambiguously adopted to denote the
microstructure of hardened but untempered steels. As the essential proper­
ties of quenched steel have become better known, the meaning of the word
has been gradually clarified as well as extended to nonferrous alloys in
which similar characteristics occur. Although the term martensite has oc­
casionally been used somewhat ambiguously, there exists a critical restric­
tion on the use of the word. A substance's structure must have certain
definite properties in order to be called martensitic structure; similarly, a
phase transformation must have certain properties in order to be called a
martensitic transformation. It is the object of this chapter to define marten­
site and martensitic transformations.
We shall take up first the basic properties of martensite in steels, par­
ticularly in carbon steels, and then discuss what martensite is in a wider
sense.

1
2 1 Introduction

(a) (b)
FIG. 1.1 (a) Body-centered cubic lattice (a iron), (b) Face-centered cubic lattice(γ iron).

1.1 Martensite in carbon steels

1.1.1 Allotropic transformations in iron

In order to discuss martensitic transformations in steel, we must consider

first the allotropic transformation of elemental iron. Iron changes phase in
the sequence a - > / J - > y - » < 5 o n heating. Alpha iron, which is the stable phase
at r o o m temperature, has the atomic arrangement shown in Fig. 1.1a, which
depicts a unit cell of the body-centered cubic (b.c.c.) lattice, in which the
atoms lie at the corners a n d body center of a cube. O n heating to 790°C
iron changes to the β phase, which has the same b.c.c. structure as α iron.
The sole distinction is that α iron is ferromagnetic whereas β iron is para­
magnetic. Since the magnetic change is not a change in crystal structure, we
now use the term α iron to include β iron. The next transformation, which
gives γ iron, takes place at 910°C (the A3 point). G a m m a iron has the face-
centered cubic (f.c.c.) atomic arrangement, in which the unit cell contains
atoms at the corners a n d face-centers of a cube, as shown in Fig. 1.1b. T h e
last solid-state transformation on heating, y -><5, takes place at 1400°C;
δ iron has the same b.c.c. structure as α iron. The y -> α transformation on
cooling is closely related to the martensitic transformation which we will
discuss later.

1.1.2 Phase diagram of carbon steels and the martensite start temperature,M s

The outline of the phase diagram for a binary F e - C alloy is given in

Fig. 1.2. The ferrite α solid solution in this diagram has the b.c.c. arrange­
ment of iron atoms, like pure α iron, the carbon atoms occupying randomly
1.1 Martensite in carbon steels 3

α + cementite
FIG. 1.2 Phase diagram of Fe-C system.

5 400h \

300 -

200-

100
o"0l I I I I1
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
I

C (%)

a small fraction of the sites m a r k e d χ , Δ , • in Fig. 1.3a. Since these sites

are interstitial sites lying between the iron atoms, the α phase is an inter­
stitial solid solution of iron and carbon. The austenite, orγ phase is also
an interstitial solid solution of iron a n d carbon, in which the iron a t o m s are
arranged in an f.c.c. lattice like that of pureγ iron, the carbon atoms occupying
randomly a fraction of the interstitial sites m a r k e d χ in Fig. 1.3b. In addi­
tion to the difference in structure, the α phase a n dγ phase have different

(b)Ύ
FIG. 1.3 Atomic arrangements in (a) ferrite (a) and (b) austenite(γ): Ο , Fe atom; χ , Δ , • ,
positions available for C atom.
4 1 Introduction

carbon solubilities. As is shown in the phase diagram, the solubility of

carbon in the α phase is small and is at most 0.03% at the eutectoid tem­
perature, 720°C, whereas the m a x i m u m solubility of carbon in they phase
a m o u n t s to 1.7%,* corresponding to 8 at. %.
M s temperature. Quenching of steel generally means that the steel is
rapidly cooled to a low temperature from a temperature above the A3
temperature or the eutectoid temperature (Ax). Any α phase or cementite
that may be present in the heated condition is little changed on quenching.
W h a t is important is they phase. As the phase diagram shows, on slow
cooling they phase is decomposed into α phase and cementite. This is not
the case on quenching, for then the martensitic transformation, a main
subject of this book, takes place. This can be detected by observed rapid
changes of the physical properties, such as dilatation. The martensitic trans­
formation starts at a temperature designated as the M s temperature. Here
Μ signifies martensite and the subscript s designates start. The M s tem­
perature depends upon the carbon content, as is indicated by the dotted line
in Fig. 1.2. N o t e that this curve has a slope similar to that for the A3 tem­
perature but lies far below the A3 temperature line. The M s temperature of
pure iron is only about 700°C, which is much lower than the A3 point,
910°C. The reason for this difference will be presented later.

1.1.3 Crystal structure of martensite ( a ) in carbon steels

The crystal structure of martensite obtained by quenching they phase in

carbon steels has a body-centered tetragonal (b.c.t.) lattice which may be
regarded as an α lattice with one of the cubic axes elongated, as illustrated
in Fig. 1.4b, where the vertical axis is elongated. This is the structure of
martensite observed metallographically and the symbol α' is often used to
denote it, since the martensite structure may be thought to be derived from
the structure of the α phase. The prime is sometimes used as an indication
of the tetragonality due to carbon atoms in ordered solid solution, but in
this book a' will indicate the structure having characteristics of martensite,
even including the b.c.c. phase without carbon atoms when this phase is
produced by a martensitic transformation. The symbol (') will be used
generally to signify a martensite phase.
The lattice parameters of a' in steels vary with carbon content in a nearly
linear fashion (see Figs. 2.1, 2.2). The tetragonality c/a and the volume of
the unit cell increase with the carbon content. F r o m this fact alone it can
be deduced that a' is a solid solution of iron and carbon. The position for
carbon atoms in the lattice as determined by various measurements is that
marked χ in Fig. 1.4b. Therefore, a' is also an interstitial solid solution, but
f
Recently 2.0% was reported.
1.1 M a r t e n s i t e in c a r b o n s t e e l s 5

it differs from the ferrite shown in Fig. 1.3a: if the carbon a t o m s in a' occupy
the sites marked χ , they cannot enter into the sites m a r k e d Δ a n d • .
The solubility of carbon in a' is also small but not so small as in a, the
m a x i m u m carbon content of a' being at most 8 at. %; hence only a small
fraction of the sites m a r k e d χ are occupied. In this case the portion of
the lattice near the carbon a t o m is similar to that for the case of a carbon
a t o m in the b.c.c. lattice, as shown in Fig. 3.13, but is such that the car­
b o n a t o m pushes the nearest-neighbor iron a t o m m a r k e d 3 d o w n w a r d a n d
the a t o m marked 4 upward, producing local lattice distortion. The latter is
one of the main reasons why a' is hard.*
All the axes of lattice distortion due to the carbon atoms in the a' lattice
are arranged in the same direction, for example, along the vertical c axis in
Fig. 1.4b. These combine to m a k e the lattice tetragonal along the c axis.
This is not the situation in the α phase containing c a r b o n ; where the sites
of the three sets m a r k e d χ , Δ , • are occupied at r a n d o m , as shown in
Fig. 1.3a, the lattice is not tetragonal but cubic, with the three principal
axes merely extended equally.
The α' lattice is similar to a, as already described, but it may be regarded
as similar toy from a different standpoint. Figure 1.4a shows two unit cells
of they lattice. If in the heavy-lined portion of the figure we regard the axes
rotated 45° a r o u n d the vertical axis as the principal axes, they lattice can
also be considered as a b.c.t. lattice with axial ratio y / 2 , which is greater
than that of α'. Therefore, if we regard a' as a distorted lattice of y , a' may
also be regarded as a transition phase betweeny a n d a. A good correspon­
dence is also obtained between the carbon sites iny and a. The lattice cor­
respondence between (a) and (b) in Fig. 1.4 is called the Bain correspondence
f
Though such lattice distortion also exists in ferrite containing carbon atoms, it affects the
hardness little because the carbon content is very small. Moreover, other sources of hardening
in martensite (to be described later) are absent in ferrite and thus ferrite is not very hard.
6 1 introduction

and the concept that the a' lattice could be generated from theγ lattice by
such a distortion as by decreasing the tetragonality fromyfl was adopted
in some earlier theories of the martensitic transformation mechanism in steels.

1.2 Characteristics of martensite in steel

The crystal structure of a' described in the preceding subsection is itself

one of the characteristics of martensite. O t h e r characteristics are as follows.

1.2.1 Diffusionless nature of the transformation

They phase retained after quenching has, of course, the same crystal
structure as they phase stable at higher temperatures, the lattice parameters
being unchanged except from contractions due to the decrease of tempera­
ture. It has the same carbon content as that of they phase at high tem­
perature. The lattice of a' is expanded in relation to that of a, the a m o u n t
depending on the carbon content. Moreover, there are no phases other than
a' and retainedy in the specimen. The structure as observed under the
microscope shows only these two phases. Therefore it may be considered
that no chemical decomposition takes place during the martensitic trans­
formation and a part or most parts ofγ transform diifusionlessly to α', the
compositions being unchanged. This is an extremely important factor in the
martensitic transformation.
A necessary condition for the occurrence of they -> a' transformation is
that the free energy of a' be lower than that of y . Moreover, since additional
energy, such as that due to surface energy and transformation strain energy,
is necessary for the transformation to take place, the difference between the
free energies ofy and a' must exceed the required additional energy. In
other words, a driving force or excess free energy is necessary for the trans­
formation to take place. Therefore, theγ to α' reaction cannot take place
until the specimen is cooled to a particular temperature below T 0 , the tem­
perature at which the free energy difference between austenite and martensite
of the same composition is zero (Fig. 1.5). The degree of supercooling is the
greater the larger the difference between the two crystal structures, because
it is more difficult for the change to occur when greatly differing structures
are involved. In the case of steel the difference between the two structures
is rather large and the difference between T 0 and M s may be as large as
200°C. This great difference in structure is the reason why the M s tempera­
tures are markedly below the extended A3 line in Fig. 1.2. (The A3 tem­
perature is higher than the T0 temperature.*)
f
A 3 represents the temperature at which y is in equilibrium with α -I- Fe 3C, whereasT 0
represents the temperature at whichγ and a' of the same carbon content are in metastable
equilibrium.
1.2 C h a r a c t e r i s t i c so f m a r t e n s i t ei n s t e e l 7

1.2.2Habi tplan e

When th e temperatur e fro m whic h steel s ar e quenche di s hig h enough , th e

product structur e become s coars e an d th e individua l crystal s o f a ' ca n b e
distinguished i n th e optica l microscop e (Fig .1.6) . I n th e ultralo w carbo n
steel th e crystal s appea r lath-shape d i n cros s section ; however , th e actua l
shapei s tha t o fa plat e o r needle , wher e ofte n th e forme r i s paralle l t o{11 1 } y
and th e latte r t o < 1 1 0 > rI n th e mediu m a n d hig h carbo n steel s th e crystal s
take th e for m o f b a m b o o leave s o r lenticula r plate s wit ha core , calle d th e
midrib, withi n them . Thi s cor ei s nearl y paralle l t o { 2 2 5 } yo r { 2 5 9 } y, th e
latter bein g m o r e frequen t i n hig h carbo n steels . Thu s martensit e crystal s
1
have m o r e o r les s definit e habi t p l a n e s wit h respec t t o th e crysta l lattic e o f
the paren t phas e y.

1.2.3Lattic eorientatio nrelationship s

The crystallographi c axe so f a ' crystal s produce d i na γ crysta l als o hav e

a definit e relatio n t o thos e o f th e untransforme d par t o f th e y crystal . I n
carbon steel s th e orientatio n relationship s ar e

( l l l ) y| | ( 0 1 1 ) a, , [ Τ 0 1 ] 7 | | [ Ϊ Γ ΐ ] α,

These canno t b e obtaine d directl y fro m th e paralle l line s picture d i n Fig .1.4 ,
but ma y b e obtaine d b y makin g paralle l th e tw o shade d triangula r plane s
in(a ) an d(b) , a s wel l a s on e o f th e direction s lyin g o n eac ho f thos e triangula r
planes. Thes e relation s ar e calle d th e K u r d j u m o v - S a c h s ( K - S ) relations ,
after thei r discoverers . I n F e - 3 0 % N i alloy s th e orientatio n relationship s
are

( l l l ) y| | ( 0 1 1 ) a, , [ 1 1 2 ] y | | [ 0 T l ] a, ;

these ar e calle d th e Nishiyam a (N ) relations . Th e paralle l plane s ar e th e

same a s i n th e K - S relations , wherea s th e directiona l relationshi pi s deviate d
f
I ngeneral ,th eindice so fth ehabi tplan ear eirrational .
 1 Introduction

from the K - S relations by about 5°. In nickel steels (22% N i - 0 . 8 % C) the

orientation relationships are

(in),-(on).., poi], ~ piru

within approximately Γ and 2.5°, respectively. These can be considered as
intermediates between the two relations just described. These are called
1.2 Characteristics of martensite in steel 9

the G r e n i n g e r - T r o i a n o relations. T h u s one of the characteristics of the

martensite transformation is that in steel of a given composition there are
definite orientation relations.

1.2.4 Surface relief—shape change

An upheaval, or surface relief, is produced on a free surface when a mar­

tensite crystal forms. F o r example, in materials having M s temperatures
below r o o m temperature, such as high N i steels, surface upheaval may be
studied on surfaces prepolished by electrochemical etching in they phase
state at r o o m temperature after having been cooled from a high tempera­
ture. As the martensite is formed subsequently by cooling below the M s
temperature, an upheaval is produced at the free polished surface, as il­
lustrated in Fig. 1.7a. The surface relief is not irregular but the angle of
incline of the upheaval has a definite value which depends on the crystal
orientation. In the same way, a fiducial scratch line is bent at they -u!
interface, as illustrated in Fig. 1.7b. The angle by which such a scratch
has been bent is also definite in value, depending on the crystal orientation.
The surface relief or bending of a scratch line is a surface manifestation
of the definite shape change in the crystal that occurs during they -oc'
transformation.

1.2.5 Transformation by cooperative movement of atoms

As described earlier, the martensitic transformation is a diffusionless one

and therefore a volume ofγ changes to a' of a different structure without
atomic interchange. H o w the α' crystal is formed in this case is important.
It might be thought that the a' crystal could be formed from they crystal
by individual atomic movements but this cannot be so. The fact that the a'
crystal formed has a definite habit plane, definite orientation relations with
y , and definite surface relief leads us to the conclusion that these features
10 1 Introduction

FIG. 1.8 Shape change during martensitic transformation.

are the results of coordinated and ordered rearrangement of the atomic con­
figuration which takes place during transformation. It is considered that
the atomic movements, though accompanied to some extent by thermal
vibrations, are not free, as in a liquid or gas, but that as the transformation
interface moves, the motions of neighboring atoms are coordinated to p r o ­
duce the new crystal.

1.2.6 Generation of lattice imperfections

As illustrated in Fig. 1.8, during transformation the framed volume ofγ

in (a) is imagined to change into that in (b). This produces a vacant volume in

inside the crystal in precisely this way because opposing stresses exerted by
the surrounding matrix are applied to the transforming region to restrict
the shape change. Elastic strains are not sufficient to relax these stresses,
so the transforming region must undergo a considerable a m o u n t of plastic
deformation. This complementary deformation m a y be produced by the
movement of dislocations, as in the case of conventional plastic deforma­
tion. The motion of perfect dislocations givesslip and that of partial dis­
f
locations givesstacking faults orinternal twins (Fig. 1.9). Since a n u m b e r
of dislocations sufficient to m a k e u p for the lattice deformation is required,
the dislocation density produced must be markedly larger for theγ - • α'
transformation of steel than during ordinary plastic deformation. Lattice
imperfections giving evidence of the so-called second distortion* are actually
observed under the electron microscope within a' crystals. Figure 1.10 shows
an example in which the specimens are the same as those used in Fig. 1.6.
In low carbon steels (a), the a' crystals are lath-shaped and dislocations can
be seen throughout the crystals. In medium carbon steels (b), a n u m b e r of
f
For simplicity, the plane of the transformation shear and that of the slip or twinning shear
are considered to be parallel, but this is not generally so.
* The concept of a first deformation, consisting of a change in the shape of the unit cell, and
a second deformation to relax the transformations is for convenience of thinking; the two
deformations actually take place simultaneously.
1.3 General characteristics and definition 11

/ /
/ /
/ / (b)
/ /
/ /
/ /

Austenite Martensite
FIG. 1.9 Complementary shear—shear accompanying lattice deformation to relieve internal
stresses, (a) No lattice-invariant shear, (b) Slip shear (leaving dislocations and stacking faults),
(c) Twinning shear (leaving internal twins).

fine bands of internal twins can be seen, the spacing being a b o u t 100 A. In
high carbon steel (c), the portion that contains internal twins is increased.
O n e of the main characteristics of martensite is that it contains m a n y
lattice imperfections and this is an important feature that was overlooked
in earlier studies.

1.3 General characteristics and definition of martensite

So far the characteristics of martensite have been described mainly for

carbon steels. We will next consider which of these characteristics are essen­
tial to martensite in the b r o a d sense.
First we consider the presence of carbon atoms in the lattice. P u r e iron
cooled at an extremely high velocity has all the characteristics of ordinary
martensite except that n o carbon is contained in the lattice. In this case, it
is reasonable to call the quenched state of iron martensite: In such b r o a d
usage of the term martensite, the existence of carbon producing tetragonality
is not a requirement.
All the other characteristics described in the preceding section are neces­
sary for martensite. We can now give a general definition of martensite a n d
the martensitic transformation: A martensitic transformation is a phase
12 1 Introduction

FIG. 1.10 Electron micrographs of quenched carbon steels (same steels as in Fig. 1.6).
(After Inoue and Matsuda.1) (a) 0.2% C, lath-shaped martensite (α' crystals contain a large
number of dislocations); (b) 0.8% C, lens-shaped martensite (α' crystals contain dislocations and
internal twins); (c) 1.4% C, lens-shaped martensite (α' crystals contain many internal twins).
Reference 13

transformation that occurs by cooperative atomic movements. T h e product

of a martensitic transformation is martensite. T h a t a given structure is p r o ­
duced by a martensitic transformation can be confirmed by the existence
of the various characteristics that have been discussed, especially the dif-
fusionless character, the surface relief, a n d the presence of m a n y lattice
imperfections. Such characteristics are therefore criteria for the existence of
martensite.
A given martensite may have m a n y other characteristics which, though
suggesting martensite, are not necessarily proofs in themselves that a mar­
tensitic transformation has occurred. F o r example, high hardness was a
necessary property of martensite at the time when the word "martensite"
was first adopted but it is no longer regarded as a good criterion. Equally,
rapidity of transformation does not generally apply to martensite because,
though in most steels the time of formation of an a' crystal is of the order
7
of 1 0 " sec, the growth in some alloys is so slow that the process may be
followed under a microscope. Although the existence of a habit plane a n d
an orientation relation is a necessary consequence of a martensitic trans­
formation, it in turn is not a sufficient criterion, because some precipitates
that are definitely not classified as martensite also have such characteristics.
In the b r o a d sense of the term, a great many examples of martensite have
been confirmed in metals, as will be described in the following chapters.
F o r example, there is another type of martensite in iron alloys, a n d a n u m ­
ber of types of martensite have been observed in nonferrous alloys.

Reference

1. T. Inoue and S. Matsuda, Unpublished, Fundamental Research Labs., Nippon Steel Corp.