Materials Science and Engineering A 527 (2010) 70277039

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Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

Low-temperature martensitic transformation and deep cryogenic treatment of

a tool steel
A.I. Tyshchenko a , W. Theisen b , A. Oppenkowski b , S. Siebert b , O.N. Razumov a , A.P. Skoblik a ,
V.A. Sirosh a , Yu.N. Petrov a , V.G. Gavriljuk a,
a
b

G.V. Kurdyumov Institute for Metal Physics, 03142 Kiev, Ukraine

Ruhr University Bochum, Chair of Materials Technology, 44780 Bochum, Germany

a r t i c l e

i n f o

Article history:
Received 23 April 2010
Received in revised form 12 July 2010
Accepted 19 July 2010

Keywords:
Martensitic transformation
Tool steels
Deep cryogenic treatment
TEM
Mssbauer spectroscopy
Internal friction
X-ray diffraction

a b s t r a c t
The tool steel X220CrVMo 13-4 (DIN 1.2380) containing (mass%) 2.2C, 13Cr, 4V, 1Mo and the binary
alloy Fe2.03 mass% C were studied using transmission electron microscopy, Mssbauer spectroscopy,
X-ray diffraction and internal friction with the aim of shedding light on processes occurring during deep
cryogenic treatment. It is shown that the carbon atoms are essentially immobile at temperatures below
50 C, whereas carbon clustering in the virgin martensite occurs during heating above this temperature.
An increase in the density of dislocations, the capture of immobile carbon atoms by moving dislocations,
the strain-induced partial dissolution of the carbide phase, and the abnormally low tetragonality of the
virgin martensite are found and interpreted in terms of plastic deformation that occurs during martensitic
transformation at low temperatures where the virgin martensite is sufciently ductile.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Martensitic transformation in carbon steels at low temperatures has some special features. Kurdyumov and Maximova [1,2]
were the rst to show that, in contrast to the athermal and burst
character of martensitic formation at ambient and elevated temperatures, its kinetics at temperatures below RT are isothermal.
Moreover, as shown by studies of steel that has the martensitic
point Ms below room temperature [2], rapid cooling in liquid nitrogen retains a fully austenitic structure, whereas the isothermal
martensitic transformation starts during subsequent heating with
holding at temperatures above 77 K.
As rstly obtained in [3], the carbon martensite formed at low
temperatures is characterized by an abnormally low c/a ratio,
except for steels with high nickel (e.g. [4]) and aluminum (e.g. [5])
contents.
The low tetragonality was interpreted by means of two main
hypotheses based on ideas about the partial location of carbon
atoms in the tetrahedral interstitial sites as a result of the 

Corresponding author at: Department of Physical Principles for design of Steels

and Alloys, G.V. Kurdyumov Institute for Metal Physics, Vernadky Blvd. 36, UA03680, 142 Kiev, Ukraine. Tel.: +380 44 4243310; fax: +380 44 4243310.
E-mail address: gavr@imp.kiev.ua (V.G. Gavriljuk).
0921-5093/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2010.07.056

transformation through the intermediate phase [6] and that of

twinning on the {0 1 1} planes, which shifts some of the carbon
atoms in the octahedral sites on the a and/or b axes of the martensitic lattice without changing the location of the metal atoms [7].
The third feature of martensite formed at low temperatures is
the precipitation of orthorhombic -carbide, and not hexagonal
-carbide, during subsequent tempering (e.g. [811]). This precipitation is thought to result from the migration of carbon atoms
towards the dislocations during long holding at low temperatures.
The carbon clouds around the dislocations serve as nuclei for the
-carbide, which is consistent with previous studies by Hirotsu and
Nagakura [12] who rst observed rod precipitates of -carbide in
the vicinity of dislocations in the tempered high-carbon martensite.
The -carbide was also found at early stages of decomposition in
the ironcarbon martensite using the synchrotron radiation [13]. It
is relevant to note that precipitation of orthorhombic carbide in the
high-carbon martensite was theoretically predicted by Bagaryatsky
[14].
The nely dispersed and evenly distributed -carbide particles
are considered to be the main reason for the signicantly (more
than twice) improved abrasive wear resistance of high-carbon tool
steels as a result of deep cryogenic treatment (DCT).
At present, little is understood about the physical background of
DCT, and a number of published papers contain contradictory and
even mutually exclusive data and conclusions.

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A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

For instance, -carbide is found in [10,11] to be precipitated

in the freshly formed martensite during its subsequent tempering
between 200 and 540 C. In contrast, as stated in [15], this precipitation already takes place during deep cooling of tool steels.
According to [16], additional ne carbides are precipitated as temperature descends to 140 C. Recently, Das et al. [17] presented
data of scanning electron microscopy about two types of secondary
carbides existing in the quenched CrMoV tool steel, small and large,
both of each increase their fraction with holding time at 77 K.
The role of the  transformation in the improved wear
resistance is also a controversial issue. According to [18], the benecial effect of DCT is not related to the martensitic transformation
because the improvement in the properties is observed if the holding (soaking) of steel is carried out at temperatures at which the
martensitic transformation is already completed, and the lower the
holding temperature the more signicant the DCT effect is. Therefore, the relaxation of stresses in martensite is considered to be the
main process occurring during DCT (e.g. [19]). Somewhat contradictory to this statement is the observation in [20] that the holding
time is more important than the decrease in temperature (163 K for
24 h is more effective than 93 K for 6 h).
It is relevant to note that martensitic transformation never goes
to completion, and the retained austenite always exists in the structure of high-carbon martensites. This paper aims to present some
new results concerning processes taking place during the lowtemperature martensitic transformation in high-carbon steels and
thus shed light on some disputed points of deep cryogenic treatment.

ter, which resulted in 32% martensite. Thereafter, the spectra were

measured in the transmission mode at the temperature of 65 K after
successive heating cycles within the temperature range between 65
and 293 K with holding for 10 min at each temperature.
Tetragonality of virgin and aged martensites was measured
in CoK radiation using an X-ray diffractometer with the HUBER
goniometer 2, having the resolution of 0.005 . The tting of
diffraction patterns was carried out using the program ProFit.
The samples were also analysed by mechanical spectroscopy
to study the interaction between carbon atoms and dislocations.
Internal friction spectra were measured in the temperature- and
amplitude-dependent damping modes within the temperatures
between 196 C and RT using an inverted pendulum at frequencies of about 15 Hz. Setting up of specimens and cooling to 196 C
in the pendulum took less than 15 min.
3. Results
3.1. Transmission electron microscopy of steel X220CrVMo 13-4
The back scattering electron image of martensite as-quenched
at room temperature was obtained at a low magnication in order
to get a view of the not-dissolved carbide particles (Fig. 1a). Three
types of particles different in their size can be distinguished, which
is generally consistent with the statement made in [17] about three
types of carbides, namely the primary ones and large and small
secondary ones. A more detailed view was obtained using the sec-

2. Experimental
A tool steel X220CrVMo 13-4 (DIN 1.2380) containing (mass%)
2.2C, 13Cr, 4V, 1Mo was used for the studies. The specimens used for TEM and X-ray diffraction had the size of
10 mm 10 mm 0.1 mm, those for Mssbauer spectroscopy and
internal friction measurements were 10 mm 10 mm 0.03 mm
and 0.8 mm 0.8 mm 60 mm, respectively. These specimens
were solution-treated at 1080 C for 20 min under protective pure
argon atmosphere and cooled using the ow of the cold argon.
Immediately after cooling, some of the specimens were cooled to
196 or 150 C with holding at these temperatures for 24, 36 or
48 h.
A JEM-2000 FXII transmission electron microscope, operating at
a voltage of 200 kV, was used for structural studies in the transmission mode, as well as for obtaining the back-scattered electron or
secondary electron images. A computer program LINK EDP served
for the analysis of diffraction patterns. The energy dispersive X-ray
spectrometer (EDS) and the quantitative program LINK RTS 2/FLS
with a virtual standard package were used for the local chemical
analysis. The maximum error did not exceed 5%.
Mssbauer spectra were recorded in the transmission mode. A
WISSEL Mssbauer spectrometer and a source of quanta 57 Co
in the Cr matrix with an activity of 100 mCi were used for measurements. The equipment was characterized by the line-width of
0.22 mm/s for the quanta source. The distribution of hyperne
elds was obtained using the programme DISTRI developed by Prof.
Rusakov, Moscow State University, Russia.
In order to exclude the effect of alloying elements and carbide
particles, which make Mssbauer spectra rather complicated, we
studied the state of the carbon atoms in the virgin martensite using
a binary FeC solid solution. A pure iron foil of 20 m in thickness was carburized at 1150 C under owing methane followed by
quenching in water, which allowed us to obtain the fully austenitic
state at RT. According to X-ray diffraction data, the carbon content in the obtained austenite was 2.03 mass%. The specimen was
then cooled to 4.5 K in the cryostat of the Mssbauer spectrome-

Fig. 1. (a) Back scattering electron image of steel X220CrVMo 13-4 after solution
treatment at 1080 C for 20 min and quenching in water; (b) the same: secondary
electron image.

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

7029

Fig. 2. (a) Carbide Me7 C3 in steel X220CrVMo 13-4 after holding in liquid nitrogen for 48 h. Points of local chemical analysis are marked by 13; (b) the electron
hcp .
diffraction from carbide particle, the zone axis [1 0 2]

ondary electron image (Fig. 1b). The local chemical analysis of these
particles revealed a different content of Cr, V and Mo (see Table 1).
Their nature was claried using transmission mode with the corresponding chemical analysis (see Figs. 24 and Table 1). The primary
carbide, as particles of 510 m in size, was identied as Me7 C3 carbide with the hcp crystal lattice (Fig. 2). The small secondary carbide
particles of 0.11 m in size belong to the cubic carbide MeC (Fig. 3),
whereas the large secondary carbide precipitated as globules with
size of 13 m is the hexagonal carbide Me2 C (Fig. 4). It is relevant
to note that weaker reections in the diffraction patterns of MeC

Fig. 3. (a) Carbide MeC in steel X220CrVMo 13-4 after holding in liquid nitrogen for
48 h. Points of local chemical analysis are marked by 13; (b) the electron diffraction
fcc .
from carbide particle, the zone axis [1 0 1]

and Me2 C carbides, as compared to that of Me7 C3 carbide, can be

due to their stronger chemical stability, which results in a higher
thickness of particles and, correspondingly, a weaker penetrability
for electrons and stronger diffuse electron scattering.
Fig. 5 demonstrates a difference in the structure of martensites
obtained at room and low temperatures. A high density of twins
along with dislocations and the rather large size of martensitic

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A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

Table 1
Identication of carbides and the content (at.%) of Cr, V, Mo in the carbides and in the matrix (see points 13 in Figs. 24).
Figure

Carbide type, size

Crystal lattice

Point of analysis

Cr

Mo

Fe

Fig. 2

Me7 C3
510 m

hcp

Fig. 3

MeC
0.11 m

fcc

Fig. 4

Me2 C
13 m

hcp

1
2
3
1
2
3
1
2
3

46.6
8.7
8.8
19.6
8.3
8.9
11.3
7.3
7.9

12.3
0.8
0.8
63.2
0.6
0.7
84.1
0.3
0.3

1.1
0.5
0.6
2.3
0.6
0.6
2.5
0.6
0.7

40.0
90.0
89.8
14.9
90.5
90.7
2.2
91.8
91.1

domains are typical for the martensite quenched at RT (Fig. 5a).

Finer twinning and a smaller size of the martensitic domains
are distinguishing features of martensite transformed at 150 C
(Fig. 5b).
The analysis of electron diffraction has disclosed a number
of ne cementite particles in the martensite obtained by water
quenching (see Fig. 6). Such cementite particles could also be
observed after deep cryogenic treatment. Again, the intensity of
cementite reections is rather poor (Fig. 6b), which is not surprising taking into account the small cementite fraction. Nevertheless,
it is sufcient for obtaining the dark eld image (Fig. 6c), which is
the rst observation of cementite in the as-quenched not tempered
martensite of tool steels.
3.2. Carbon in the virgin Fe2.03%C martensite
A binary FeC solid solution was used in order to shed light
on the mobility of carbon atoms in the virgin martensite, which
can be important for the interpretation of phenomena occurring
during DCT and for discussion of mechanisms responsible for the
abnormally low tetragonality of virgin FeC martensite.
Fig. 7 shows transmission Mssbauer spectra of the binary
Fe2.03 mass% C alloy after quenching from 1150 C in water
followed by cooling to liquid helium and successive heating to
different temperatures with a holding time of 10 min at each
temperature. All measurements were carried out at 208 C. The
hyperne structure parameters are given in Table 2 for the virgin
and aged martensites.
Fig. 8 shows the outer line of the Mssbauer spectrum (nuclear
transition 1/2 3/2) after holding at above mentioned temperatures. As seen in Figs. 7 and 8, the spectrum of virgin martensite
consists of six sextets with different values of the hyperne eld,
isomer shift and quadrupole interaction (see Table 2). Sextets 1, 2
and 3, 4, and 5, 6 can be combined into groups A, B, C, respectively,
as carried out in many recent studies of FeC martensites. The seventh component with Hi = 34.6 T, which is close to that in pure iron
measured at 208 C, appears after aging at RT.
3.2.1. Interpretation of Mssbauer spectra
The virgin and aged FeC martensites were measured in a number of Mssbauer studies (see e.g. [2130]). So far, it is hardly
possible to carry out ab initio calculations to obtain hyperne

structure parameters in such multicomponent nuclear gamma

resonance spectra. It is thus not surprising that the available interpretations differ signicantly with respect to attributing spectral
components to possible atomic congurations of iron and carbon
atoms.
Gielen and Kaplow [21] studied only aged FeC martensite and
interpreted the spectrum as consisting of two sextets corresponding to pure iron atoms Fe0 and iron atoms having two carbon atoms
as nearest neighbors, Fe2 (see schemas in Fig. 9).
Moriya et al. [22], as well as Lesoille and Gielen [23] applied
the hypothesis given in [6] to the carbon distribution in the virgin
martensite and attributed component B to iron atoms with carbon
in the tetrahedral sites. It is relevant to note that neutron diffraction
studies (e.g. [24]) do not reveal carbon in the tetrahedral sites of virgin martensite. Furthermore, the location of some carbon atoms in
the tetrahedral sites would cause two additional sextets in the spectra of the virgin martensite that should disappear during ageing,
which was not observed.
Choo and Kaplow [25] and de Cristopharo and Kaplow [26] suggested a repulsive distribution of carbon in the virgin martensite
and interpreted components A, B, C as correspondingly belonging
to the iron atoms as third, second, and rst neighbors of a carbon
atom in the octahedral site. Ino et al. [27] also attributed the components C and B to the iron atoms as rst and second neighbors of iron
atoms. One of the arguments in this interpretation was that the C
component cannot belong to iron atoms in carbon clusters because
they do not exist in the virgin martensite. According to [2527],
carbon clustering occurs only at room temperature resulting in the
formation of an Fe4 Cx structure. However, as shown in [28], where
the Monte Carlo simulation of the FeC solid solution for obtaining
the CC interaction energies in the rst and second co-ordination
spheres, which could be consistent with Mssbauer data, were performed, the pairs of carbon atoms in neighboring interstitial sites
exist in the FeC austenite. Therefore, such pairs should be inherited
by the virgin martensite as a result of the diffusionless transformation.
A detailed interpretation was given by Genin et al. [29,30], who
tted the spectra of the virgin and aged FeC martensites using a
combination of E, A, Ba , Bc , C, D, F components. According to [29,30],
the component E with the highest hyperne eld of 37.6 T represents an extended FeC multiplet in which an iron atom has two
carbon atoms at the shortest possible distances of 2.0 A and sev-

Table 2
Patrameters of hyperne structure in Mssbauer spectrum of Fe2.03 mass% C for the virgin martensite. Sextet 7 appears after ageing at 20 C. Measurements at 208 C.
Sextet

Hyperne eld (T)

1
2
3
4
5
6
7

37.4
35.7
33.5
31.6
28.0
27.8
34.6

In relation to -iron.

0.2
0.3
0.4
0.4
0.3
0.3
0.15

Isomer shift,a 0.005 (mm/s)

Quadrupol interaction 4 (mm/s)

0.207
0.157
0.124
0.229
0.197
0.185
0.096

0.027
0.012
0.076
0.210
0.512
0.273
0.009

0.005
0.005
0.01
0.01
0.01
0.01
0.01

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

Fig. 4. (a) Carbide Me2 C in steel X220CrVMo 13-4 after holding in liquid nitrogen for
48 h. Points of local chemical analysis are marked by 13; (b) the electron diffraction
from carbide particle, the zone axis [1 6 4]hcp .

Genin et al.
eral iron atoms at enlarged distances of 2.86 and 2.66 A.
suppose that this dilatation of the iron lattice is sufcient to counterbalance the effect of two carbon neighbors which, in the absence
of dilatation, should decrease the hyperne eld at the iron nucleus
at least by 6 T (see a corresponding relation in [31]).
The component A with Hi = 36.2 T is interpreted by Genin et al.
as belonging to pure iron atoms located sufciently far from the
carbon atoms. The components Ba and Bc with Hi equal to 33.1

7031

Fig. 5. (a) Structure of martensite in steel X220CrVMo 13-4 as-quenched at RT; (b)
the same after subsequent holding at 150 C for 24 h.

and 33.4 T are attributed to the iron atoms with an isolated carbon
atom (like Fe1 and Fe1 in Fig. 9a). In other words, the authors [29,30]
suggest that the overlapping of wave electron functions is the same
in the atomic pairs Fe1 C and Fe1 C, in spite of the fact that carbon
atoms located in the octahedral sites push Fe1 atoms much more
strongly than Fe1 atoms, thereby creating tetragonality in the iron
lattice.

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A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

of the orthorhombic lattices (c) dark

Fig. 6. (a) Structure of martensite as-quenched at RT; (b) diffraction pattern, the zone axis [1 1 1] of the body centered cubic and [3 6 1]
eld image in the light of cementite reection [2 1 0] .

Finally, the components C and D with Hi equal to 28.3 and 26.2 T

are attributed to isolated multiplets, i.e. to iron atoms having two
carbon atoms in the nearest neighborhood (Fe2 in Fig. 9c or d). The
difference between C and D congurations is thought to come from
the effect of next carbon neighbors in the D case. There also exists

a weak component F with Hi = 16.5 T, which is ascribed to the iron

atoms with three carbon nearest neighbors.
One can conclude from the above-performed analysis that, so
far, in relation to Mssbauer spectra of virgin and aged FeC
martensites, there is no interpretation that is fully satisfactory.

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

7033

Fig. 7. Mssbauer spectra of the alloy Fe2.03 mass%C after quenching in water,
cooling to 4.5 K (as-quenched), and subsequent holding for 10 min at 150, 0, and
20 C. All measurements were carried out at 65 K.

The change in the spectra caused by heating the virgin martensite from 208 C to RT provides some hints for their interpretation.
This change is seen after heating at 50 C and higher temperatures (see Figs. 7 and 8). The component B essentially disappears,
whereas the component C increases in its intensity. Due to ageing at RT, the outer lines are shifted to the gravity center of the
spectrum, which is obviously caused by a new component 7. As
a result, component 1, with the highest hyperne eld, becomes
more visible.
Based on the above presented data and taking into account the
change in the spectra due to the ageing of martensite, an interpretation of the Mssbauer spectra can be proposed which is similar
to that in [29,30], but with some essential distinctions.
Sextet 1 belongs to pure iron atoms that are located far away
from the carbon atoms as nearest neighbors. The increase in the
hyperne eld in comparison with the -iron is obviously caused
by lattice dilatation. This is component E in [29,30], that was
attributed to iron atoms having two carbon neighbors at the closest
distances. We do not believe that lattice dilatation can counterbalance the giant decrease, about 6 T, in the hyperne eld caused by
carbon atoms as nearest neighbors.
Sextets 24 come from the iron atoms as third, second, and rst
neighbors of a single carbon atom in the octahedral site on the c

axis (iron atoms Fe1 , Fe1 , Fe
in Fig. 9a). It is hardly possible that
1
sextets 2 and 3 (Ba and Bc in [29,30]) could have the same hyperne
elds because overlapping of the iron and carbon electron shells is
quite different for the Fe1 and Fe1 atoms.
It also follows from the spectra in Figs. 7 and 8 that partitioning of single carbon atoms on the c and a or b axes, as proposed
in [7] for interpretation of abnormally low tetragonality, has no
place. This would lead to an increase in the number of corre-

Fig. 8. The outer line (nuclear transition 1/2 3/2) of the Mssbauer spectra of
the alloy Fe2.03 mass%C after quenching in water, cooling to 4.5 K (as-quenched)
and subsequent holding for 10 min at 150, 100, 50, 0, 20 C. All measurements
were carried out at 65 K.

Fig. 9. Congurations of iron and carbon atoms as derived from the interpretation of
Mssbauer spectra. H is the axis of easy magnetization, q is the electric eld gradient.

7034

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

Fig. 10. (a) Mssbauer spectrum of steel X220CrVMo 13-4 after solution treatment at 1080 C and quenching at RT; (b) distribution of hyperne elds in the martensite.

Fig. 11. (a) Mssbauer spectrum of steel X220CrVMo 13-4 after solution treatment at 1080 C, quenching at RT and subsequent holding at 196 C for 48 h; (b) distribution
of hyperne elds in the martensite.

sponding sextets due to the difference in quadrupole interactions

= e2 qQ(3 cos2  1)/8, where e and Q are the electron charge and
the iron nuclear quadrupole moment, respectively, and  is the
angle between the electric eld gradient q and the direction of easy

magnetization axis H. The angle  should be equal to zero for the

iron atoms on the c axis (see Fig. 9a) and 90 for those on the a or
b axes (see Fig. 9b). An additional argument was given by Ino et
al. [27], who have shown that the exchange energy for keeping the

Fig. 12. (a) Mssbauer spectrum of steel X220CrVMo 13-4 after solution treatment at 1080 C, quenching at RT and subsequent holding at 150 C for 24 h; (b) distribution
of hyperne elds in the martensite.

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

7035

Fig. 13. Mssbauer spectrum of steel X220CrVMo 13-4 after solution treatment at 1080 C, quenching at RT, ageing at RT for 1 week and subsequent holding at 196 C for
24 h.

spins parallel each other on the c axis is two orders of magnitude

higher than the anisotropic energy by which the direction of a spin
is turned toward a carbon atom located on the a or b axes. Thus, the
pairs of non-parallel spins in the martensite cannot be formed.
Sextets 5 and 6 belong to the iron atoms having two carbon
atoms as nearest neighbors with the angle  equal to zero (Fig. 9c
for sextet 5) and 90 (Fig. 9d for sextet 6, see also the values of in
Table 2). This is similar to the interpretation of C and D components
in [29,30] with the only difference that sextets 5 and 6 have the
same hyperne eld but different values of quadrupole interaction
because of different  values.
3.2.2. Carbon distribution in the virgin and aged martensites
Based on the proposed interpretation of Mssbauer spectra,
the following preliminary characteristics of carbon distribution in
the virgin martensite and carbon behavior during ageing can be
assumed:
(i) The hypotheses attributing the abnormally low tetragonality of virgin martensite to the occurrence of carbon atoms in
the tetrahedral sites [6] or their distribution on the a, b, or c
sublattices of octahedral sites [7] are not consistent with the
hyperne structure of Mssbauer spectra and their evolution
during the heating of virgin martensite.
(ii) It is clear from the spectra presented in Figs. 7 and 8 that,
at holding temperatures below 50 C, nothing changes in
the virgin martensite, i.e. the carbon atoms remain immobile.
If account is taken of the fact that carbon migration exponentially decreases with decreasing temperature, it can be
concluded that carbon atoms cannot move towards the dislocations during deep cryogenic treatment of tool steels, as has
been suggested in a number of DCT studies (see Section 1).
(iii) The decrease in intensity of sextets 3 and 4 and the growth
of sextets 5 and 6 starting from holding at 50 C is evidence
of carbon clustering, which is consistent with the available
observations of the modulated structure in the aged highcarbon martensites (e.g. [32,33]). Sextet 7, with the hyperne
eld approaching that of pure iron, appears due to carbon
clustering. Sextet 1 with the increased hyperne eld in comparison with the pure -iron remains after ageing, which can
be attributed to dilatation at the coherent boundaries between
the carbon-rich and carbon-depleted areas in the modulated
aged martensite.

3.3. Change in the phases of steel X220CrVMo 13-4 due to

cryogenic treatment
Mssbauer spectra of steel X220CrVMo 13-4 (DIN 1.2380) were
measured after solution treatment at 1080 C followed by quenching at RT and subsequent holding in liquid nitrogen or at 150 C.
As example, some data are presented in Figs. 1013. The spectra
consist of a single line, which belongs to the retained austenite,
a doublet with a quadrupole splitting of about 0.6 mm/s, which
is attributed to the carbide phase, and four sextets of martensite.
The tting of the martensitic component by four sextets was made
based on the distribution of hyperne elds (see Fig. 10b13b).
The areas under spectra components, as determined from Mssbauer spectra, are given in Table 3. The mean square amplitude
of atomic vibrations is not remarkably different in the austenitic
and martensitic phases, however it is signicantly decreased in the
carbide lattice because of prevailing covalent interatomic bonds.
Therefore, the probability of gamma quanta absorption is much
higher in the carbide phase, so that the relative area under carbide
doublet in Mssbauer spectrum is higher than the fraction of carbides in the studied steel. Thus, the change in the area under spectra
components due to cryogenic treatment allows to only obtain a
knowledge about the change of fractions of corresponding phases,
not their precise amount.
In relation to the martensitic phase (see Figs. 10b13b), the distribution of hyperne elds reveals four intensive components in
the martensitic spectrum with a rather large half-width of lines
that are in fact attributed to several overlapped components, which
is due to the effect of rst, second, and so on, neighboring solute
atoms of different kinds on the hyperne eld at the nuclei of the
iron atoms. Each single carbon atom as the nearest neighbor of an
iron atom in the martensite lattice decreases the hyperne eld at
Table 3
Relative areas (%) under components of martensite, retained austenite and casrbide
and under the lines Fe0 and Fe1 in the martensitic component of Mssbauer spectra
in steel X220CrVMo 13-4. Data for Fe0 and Fe1 are normalized to 100% of martensite.
Cooling after solution treatment

Martensite

RA

Carbide

Fe0

Fe1

Quenching at RT
RT 196 C (24 h)
RT 196 C (36 h)
RT 196 C (48 h)
RT 150 C (24 h)
RT(1 week) 196 C (24 h)

81.7
86.6
87.0
87.3
89.1
85.6

7.7
4.1
3.9
3.7
3.5
5.8

10.6
9.3
9.1
9.0
7.4
8.6

27.2
24.3
22.8
19.9
15.2
21.2

34.0
37.3
38.8
43.3
46.3
36.5

7036

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

its nucleus by nearly 3.0 T (e.g. [31,34]). For chromium in -iron,

this effect is equal to 2.7 T [35], and for vanadium it is 2.6 T [36].
A detailed interpretation of the hyperne eld distribution in
the FeCrVC martensite is not reliable owing to the high complexity of its chemical composition and problems concerned with the
occurrence of the carbide phase. As a rough approximation, in
accordance with their hyperne elds, four resolved sextets of the
spectrum are denoted as belonging, respectively, to iron atoms
having no carbon, chromium, and vanadium (Fe0 ) and one (Fe1 ),
two (Fe2 ) or three (Fe3 ) carbon or chromium or vanadium atoms
in the nearest neighborhood. This interpretation does not pretend to be any exact clarication of the atomic distribution in the
studied martensite; however, it allows us to derive some important features of processes occurring during the low-temperature
martensitic transformation.
As expected, the fraction of retained austenite decreases
after cooling below room temperature (compare Fig. 10a with
Figs. 11a and 12a). However, it is unusual that, in spite of the same
conditions of solution treatment, the cooling in liquid nitrogen was
accompanied by a decrease in the carbide fraction (see Table 3).
This result suggests that the carbide retained after the solution
treatment and quenching at RT is partly dissolved in the course
of the low-temperature martensitic transformation and the larger
the fraction of freshly formed martensite the more intense is the
low-temperature carbide dissolution.
The attempt was made to test whether the observed effect of
deep cryogenic treatment occurs if the retained austenite is stabilized due to ageing at RT before cooling to low temperatures.
Fig. 13 presents a Mssbauer spectrum obtained after ageing for
1 week at RT and subsequent holding at 196 C for 24 h. In comparison with the data for the same cryogenic treatment without
preliminary ageing at RT (see Table 3), one can see that the stabilization of the retained austenite decreased the amount of the
low-temperature martensite, which is natural. Unexpected is that,
in case of preliminary ageing at RT, the effect of carbide dissolution
increases.
The change in the relative intensities of martensitic components
Fe0 and Fe1 with increasing time of holding at 196 C and after
holding for 24 h at 150 C is shown in Figs. 10b12b and in Fig. 14
where the outer lines of the martensitic spectrum (nuclear transition +1/2 +3/2) are presented. The numerical data are given
in Table 3. It can be seen that, with increasing fraction of transformed virgin martensite, the intensity of component Fe0 decreases
and the component Fe1 becomes more intensive. In other words,
the content of alloying elements in the martensitic solid solution increases in the course of cryogenic treatment. This result is
obviously related to the partial dissolution of carbides during the
low-temperature martensitic transformation. It is also remarkable
(see Figs. 11, 12, 14b and 14c, and Table 3) that, in relation to the
concentration change in the martensitic solid solution and carbide
dissolution, the treatment at 150 C is more effective than that in
liquid nitrogen.
3.4. Interaction between carbon atoms and dislocations
The amplitude- and temperature-dependent internal friction in
steel X220CrVMo 13-4 was measured in order to study dislocation
pinning by carbon atoms. In the absence of relaxation or hysteretic
processes, the damping background is caused by the vibrations of
dislocation segments (e.g. [37,38]). It is proportional to the area
swept by dislocations for one cycle of vibrations, i.e. to dislocation
velocity. With increasing strain amplitude, this area is expected to
increase if the dislocations are free to move. Fig. 15 presents the
amplitude-dependent internal friction in the studied steel measured immediately after cooling to the liquid nitrogen temperature
and after subsequent holding at this temperature for 12 h. Holding

Fig. 14. Outer line Fe0 (nuclear transition +1/2 +3/2) in the martensitic component of Mssbauer spectra measured after quenching of steel X220CrVMo 13-4 at
RT (a) and holding at 196 C for 48 h (b) and at 150 C for 24 h (c).

in liquid nitrogen decreases the damping, particularly at increased

strain amplitudes. This result suggests that the mobility of the dislocations decreases as the low-temperature holding time increases.
The evolution of internal friction during heating after cooling
in liquid nitrogen is shown in Fig. 16 at two different vibration frequencies. There are two peaks, the positions of which do not depend
on the frequency. Thus, both of them are not associated with any
relaxation processes.
The rst one is obviously caused by the isothermal martensitic
transformation, i.e. it has a hysteretic nature. As a result of thermal

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

Fig. 15. Amplitude-dependent internal friction in steel X220CrVMo 13-4 after

quenching at RT followed by cooling in liquid nitrogen (lled circles) and subsequent
holding at this temperature for 12 h (open circles). Measurements were carried out
at 85 K.

activation, the martensitic transformation is retarded or proceeds

slowly at 196 C and is activated during subsequent heating. The
same behavior of magnetic saturation was observed in [2]) during
the holding of steel 100Mn6 at low temperatures.
The second peak is located close to the temperature range of
the relaxation (280 K) in the bcc iron, which is caused by the
paired kink formation at screw dislocations (see e.g. [39]). However,
such kinds of relaxation exist only in pure metals and disappear
in the interstitial solid solutions. This is why, in contrast to the
relaxation peak, the temperature of the second peak does not
depend on the frequency.
Taking into account that the mobility of dislocations increases
with increasing temperature and, as follows from Mssbauer spectra (see Figs. 7 and 8), the carbon atoms in the ironcarbon
martensite become sufciently mobile starting from 50 C, this
non-relaxation peak can thus be attributed to dislocations which
become sufciently mobile to move at temperatures above 100 C
increasing thereby the damping background. The ageing of virgin
martensite at temperatures above 50 C limits the amplitude of
their vibrations. This interpretation suggests that, in spite of carbide
dissolution in the course of cryogenic treatment, some part of dislocations produced by low-temperature martensitic transformation
remains sufciently free of carbon atoms.
3.5. Tetragonality of marensite after deep cryogenic treatment
X-ray diffraction patterns of steel X220CrVMo 13-4 after
quenching at RT and holding at 196 C for 24 h are shown in

Fig. 16. Change of internal friction with increasing temperature in steel X220CrVMo
13-4 with preliminary cooling in liquid nitrogen. Measurements were carried out at
two frequencies 0.8 and 4.9 Hz, the strain amplitude is 0.5 105 .

7037

Fig. 17. Fragments of X-ray diffraction patterns of steel X220CrVMo 13-4 after
quenching at RT (open circles) and holding at 196 C for 24 h (lled circles).
Table 4
Tetragonality of martensites after quenching at RT and cryogenic treatment.
Treatment

c/a

Quenching at RT
RT 196 C (24 h)

1.022
1.012

Fig. 17. It is seen that the cryogenic treatment causes a decrease

in the tetragonality of martensite (see also Table 4). This result
is consistent with many studies of the martensite in steels having the martensitic start temperature Ms below 50 C (see e.g.
[3]). According to these observations, the martensite formed at low
temperatures acquires a decreased tetragonality which increases
during subsequent heating to RT, but does not reach the value
obtained for steels with the same carbon content if the martensite
is formed at RT.
4. Discussion
4.1. A model for processes occurring during the low-temperature
martensitic transformation
Questions regarding the physical nature of deep cryogenic treatment can be formulated as follows:
(i) What is the reason for the increase in the density of dislocations
due to holding at low temperatures, as it is manifested in a
number of studies of DCT?
(ii) If the clouds of carbon atoms at dislocations are the sites for
precipitation of nely dispersed -carbide at subsequent tempering, how the carbon atoms can reach the dislocations at low
temperatures?
(iii) What happens with carbide phases in the course of deep cryogenic treatment?
The obtained experimental data are at variance with the available interpretations of DCT which are described in the Introduction.
First, the martensitic transformation is not nished at temperatures of about 80 C that is the highest temperature for so-called
conventional treatment. Moreover, at all, the full austenite-tomartensite transformation does not occur in the studied steel, as
well as in any high-carbon steel. Second, the carbon atoms are
essentially immobile at temperatures below 50 C and, therefore,
they cannot migrate towards the dislocations for formation of carbon segregations which should be nuclei for subsequent -carbide
precipitation during tempering.

7038

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

Based on the analysis of the available data and taking into

account the results obtained in the present study, the following
model is proposed.
The freshly formed virgin martensite is characterized by a
decreased strength and comparatively high ductility (see e.g.
[4042]). The hardness, brittleness, and even microcracking [43]
are acquired due to subsequent ageing at RT.
Therefore, the plastic deformation is expected to occur during
the martensitic transformation at low temperatures due to the
volume effect of the martensitic transformation. In addition, the
dislocation creep can proceed due to stresses caused by differing
thermal coefcients of dilatation for austenite and martensite.
The plastic deformation of virgin martensite should lead to two
important consequences: (i) an increase in the dislocation density
and (ii) the capture and transport of immobile carbon atoms by
moving dislocations.
The transport of interstitial atoms by the gliding dislocations is
usually discussed in relation to hydrogen in metals (see e.g. [44]). A
theoretical analysis for the dislocation transfer of interstitial atoms
in crystals was recently made in [45].
Thus, the carbon clouds around the dislocations are not formed
due to the migration of carbon atoms towards dislocations. They
result from the capture of carbon atoms by dislocations generated and gliding during the plastic deformation. Because of high
enthalpy of binding between carbon atoms and dislocations in the
-iron (about 0.8 eV, see e.g. [46]), these carbon clouds do not take
part in the formation of the modulated structure during aging of
virgin martensite and become the sites for the nucleation of the
-carbide particles at subsequent tempering, which is consistent
with TEM studies of nucleation during tempering of a high-carbon
martensite [12].
The results of the amplitude-dependent internal friction measurements in liquid nitrogen (Fig. 15) support the idea of carbon
segregation at the dislocations during the low-temperature gliding
of dislocations. The increase in the holding time in liquid nitrogen decreases the mobility of dislocations, which, at such a low
temperature, can only result from the capture of immobile carbon
atoms by moving dislocations. A reason for their movement is plastic deformation during the isothermal martensitic transformation
and dislocation creep.
4.2. Carbide precipitates and their behavior in the course of
cryogenic treatment
The studied tool steel contains particles of primary carbide
Me7 C3 , which is enriched in Cr, secondary carbides MeC and Me2 C,
enriched in V, and ne cementite precipitates. The cubic MeC carbide obviously plays the role of the intermediate phase in the
course of Me2 C precipitation. The presence of cementite is rather
intriguing. It is reasonably to suppose that it precipitates within
the temperature range between the martensitic point Ms and RT,
where the cooling rate is rather low.
The partial dissolution of the carbide phase, as follows from
the decrease in the intensity of paramagnetic doublet in Mssbauer spectra, can be related to the effect of plastic deformation in
the course of the low-temperature martensitic transformation. The
strain-induced dissolution of cementite during plastic deformation
of plain carbon steels was observed in 1972 using Mssbauer spectroscopy [47]. A review of the experimental data is given in [48,49].
In the 1990s, this effect was studied using the 3d APFIM technique
(e.g. [50,51]]).
In relation to the partial strain-induced dissolution of special
carbides, it seems to be hardly possible for MeC and Me2 C carbides
because they contain much vanadium. Even be dissolved in cementite, vanadium decreases its strain-induced dissolution because
of strong increase of the interatomic bonds in cementite lattice

[48,49]. Stability of vanadium carbides should be much higher in

comparison with the vanadium-containing cementite.
The dispersed cementite particles can be obviously dissolved
due to deformation in the course of low-temperature martensitic
transformation. They are also observed after cryogenic treatment,
and the exact extent of cementite dissolution cannot be determined
by means of transmission electron microscopy.
The strain-induced dissolution of the primary Me7 C3 carbides is
a controversial issue. Chromium in the pearlitic carbon steels assists
the dissolution of cementite under cold work [48,49] because
it increases the enthalpy of binding between carbon atoms and
dislocations [46], whereas its contribution to strengthening of
interatomic bonds in the carbide lattice is not so large in comparison with vanadium.
The change in the intensities of the martensite components due
to the low-temperature martensitic transformation, namely weakening of the component Fe0 (see Fig. 14 and also Figs. 10b12b),
gives the evidence that the concentration of alloying elements in
the martensite increases due to carbide dissolution.
In accordance with the mechanism of strain-induced carbide
dissolution, the carbon atoms of dissolved carbides are captured by
dislocations and cannot affect the intensities of martensitic lines in
Mssbauer spectra. Therefore, only substitutional atoms like Cr, V
and Mo can be responsible for the decrease in the fraction of pure
iron due to cryogenic treatment. The content of these elements in
cementite cannot be different from their average content in steel,
if to take into account that the ne cementite particles are precipitated during self-tempering below Ms temperature. Thus, the
increase in the concentration of substitutional alloying elements in
the solid solution occurs and it can be only due to dissolution of
special carbides, most likely Me7 C3 .
While discussing the obtained TEM images of carbide phases
(Figs. 24), it is relevant to note that their partial dissolution due
to plastic deformation cannot be clearly identied using TEM,
which is a reason why the phenomenon of strain-induced cementite dissolution was rst discovered not using TEM, but Mssbauer
spectroscopy. Under cold work of pearlitic steels, the cementite is
dissolved due to dislocations pulling the carbon atoms from the
surface of cementite plates and, to a smaller extent, due to their
cutting accompanied by the carrying-out of carbon atoms by the
gliding dislocations. This is why the only effect observed by means
of TEM is the blurred contrast at the ferrite-cementite interface (see
e.g. [52]). The same blurred contrast can be observed at the surface
of Me7 C3 (see Fig. 2a) and even in MeC and Me2 C (Figs. 3a and 4a)
particles.
Thus, the observed change in Mssbauer spectra of martensite
due to cryogenic treatment can be interpreted in terms of partial
dissolution of cementite and some special carbides.
4.3. Abnormally low tetragonality of virgin martensite
It follows from the analysis of Mssbauer spectra of the virgin binary Fe2.03%C martensite that carbon atoms do not occupy
tetrahedral sites or octahedral sites in their b or c sublattices, which
is at variance with the corresponding hypotheses of the low c/a
ratio. The results obtained in the present study are interpreted in
terms of plastic deformation of the virgin martensite leading to the
partial capture of carbon atoms by moving dislocations. This suggests that the segregation of carbon atoms at the dislocations is the
real reason for the decreased tetragonality of the virgin martensite.
It is worth noting that the subsequent increase in the c/a ratio
during ageing of the virgin martensite at room temperature, which
was rst observed in [3] and repeated in other similar studies, is not
due to dilution of carbon clouds around the dislocations. The binding enthalpy between carbon atoms and dislocations in the pure
bcc iron is about 0.8 eV and it increases due to the alloying with

A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039

elements like Cr [46]. Thus, it is hardly possible that carbon atmospheres around the dislocations can be exhausted during ageing of
martensite.
A more plausible explanation for this partial recovery of tetragonality is based on the coherent stresses at the boundaries between
the carbon-rich and carbon-depleted areas in the aged martensite, similar to tetragonality of NiTi martensite containing Ni3 Ti
precipitates [53].
It is also worth noting that the capture of carbon atoms by gliding dislocations during the cryogenic treatment and corresponding
decrease of the carbon content in the martensite should result in the
increase of the fraction of iron atoms having no carbon as nearest
neighbors (the component Fe0 in Mssbauer spectra). The opposite effect of the decrease in the intensity of the component Fe0 , as
observed in this study, is due to the strain-induced dissolution of
the carbide phases and should be absent in studies of steels having
no carbides.
5. Conclusions
1. Martensitic transformation in high-carbon steels at low temperatures is accompanied by plastic deformation of virgin
martensite, which is a physical reason for benecial effect of
deep cryogenic treatment of tool steels.
2. An important consequence of plastic deformation is the capture
of immobile carbon atoms by moving dislocations and the formation of carbon clusters that can serve as sites for nucleation
of ne -carbide particles during subsequent tempering.
3. Plastic deformation occurring during the low-temperature
martensitic transformation causes partial dissolution of carbide
particles.
4. The abnormally low tetragonality of the virgin martensite transformed at low temperatures can be attributed to the capture of
carbon atoms by moving dislocations, thus decreasing the carbon
content in the martensitic solid solution.
5. The obtained results can be used to deepen our understanding
of the processes occurring during deep cryogenic cooling of tool
steels.
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