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Article history: The tool steel X220CrVMo 13-4 (DIN 1.2380) containing (mass%) 2.2C, 13Cr, 4V, 1Mo and the binary
Received 23 April 2010 alloy Fe2.03 mass% C were studied using transmission electron microscopy, Mssbauer spectroscopy,
Received in revised form 12 July 2010 X-ray diffraction and internal friction with the aim of shedding light on processes occurring during deep
Accepted 19 July 2010
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,
Keywords:
the strain-induced partial dissolution of the carbide phase, and the abnormally low tetragonality of the
Martensitic transformation
Tool steels
virgin martensite are found and interpreted in terms of plastic deformation that occurs during martensitic
Deep cryogenic treatment transformation at low temperatures where the virgin martensite is sufciently ductile.
TEM 2010 Elsevier B.V. All rights reserved.
Mssbauer spectroscopy
Internal friction
X-ray diffraction
0921-5093/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2010.07.056
7028 A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039
For instance, -carbide is found in [10,11] to be precipitated ter, which resulted in 32% martensite. Thereafter, the spectra were
in the freshly formed martensite during its subsequent tempering measured in the transmission mode at the temperature of 65 K after
between 200 and 540 C. In contrast, as stated in [15], this pre- successive heating cycles within the temperature range between 65
cipitation already takes place during deep cooling of tool steels. and 293 K with holding for 10 min at each temperature.
According to [16], additional ne carbides are precipitated as tem- Tetragonality of virgin and aged martensites was measured
perature descends to 140 C. Recently, Das et al. [17] presented in CoK radiation using an X-ray diffractometer with the HUBER
data of scanning electron microscopy about two types of secondary goniometer 2, having the resolution of 0.005 . The tting of
carbides existing in the quenched CrMoV tool steel, small and large, diffraction patterns was carried out using the program ProFit.
both of each increase their fraction with holding time at 77 K. The samples were also analysed by mechanical spectroscopy
The role of the transformation in the improved wear to study the interaction between carbon atoms and dislocations.
resistance is also a controversial issue. According to [18], the bene- Internal friction spectra were measured in the temperature- and
cial effect of DCT is not related to the martensitic transformation amplitude-dependent damping modes within the temperatures
because the improvement in the properties is observed if the hold- between 196 C and RT using an inverted pendulum at frequen-
ing (soaking) of steel is carried out at temperatures at which the cies of about 15 Hz. Setting up of specimens and cooling to 196 C
martensitic transformation is already completed, and the lower the in the pendulum took less than 15 min.
holding temperature the more signicant the DCT effect is. There-
fore, the relaxation of stresses in martensite is considered to be the 3. Results
main process occurring during DCT (e.g. [19]). Somewhat contra-
dictory to this statement is the observation in [20] that the holding 3.1. Transmission electron microscopy of steel X220CrVMo 13-4
time is more important than the decrease in temperature (163 K for
24 h is more effective than 93 K for 6 h). The back scattering electron image of martensite as-quenched
It is relevant to note that martensitic transformation never goes at room temperature was obtained at a low magnication in order
to completion, and the retained austenite always exists in the struc- to get a view of the not-dissolved carbide particles (Fig. 1a). Three
ture of high-carbon martensites. This paper aims to present some types of particles different in their size can be distinguished, which
new results concerning processes taking place during the low- is generally consistent with the statement made in [17] about three
temperature martensitic transformation in high-carbon steels and types of carbides, namely the primary ones and large and small
thus shed light on some disputed points of deep cryogenic treat- secondary ones. A more detailed view was obtained using the sec-
ment.
2. Experimental
Fig. 2. (a) Carbide Me7 C3 in steel X220CrVMo 13-4 after holding in liquid nitro-
gen 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]
Fig. 3. (a) Carbide MeC in steel X220CrVMo 13-4 after holding in liquid nitrogen for
ondary electron image (Fig. 1b). The local chemical analysis of these 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]
particles revealed a different content of Cr, V and Mo (see Table 1).
Their nature was claried using transmission mode with the corre-
sponding chemical analysis (see Figs. 24 and Table 1). The primary and Me2 C carbides, as compared to that of Me7 C3 carbide, can be
carbide, as particles of 510 m in size, was identied as Me7 C3 car- due to their stronger chemical stability, which results in a higher
bide with the hcp crystal lattice (Fig. 2). The small secondary carbide thickness of particles and, correspondingly, a weaker penetrability
particles of 0.11 m in size belong to the cubic carbide MeC (Fig. 3), for electrons and stronger diffuse electron scattering.
whereas the large secondary carbide precipitated as globules with Fig. 5 demonstrates a difference in the structure of martensites
size of 13 m is the hexagonal carbide Me2 C (Fig. 4). It is relevant obtained at room and low temperatures. A high density of twins
to note that weaker reections in the diffraction patterns of MeC along with dislocations and the rather large size of martensitic
7030 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).
domains are typical for the martensite quenched at RT (Fig. 5a). structure parameters in such multicomponent nuclear gamma
Finer twinning and a smaller size of the martensitic domains resonance spectra. It is thus not surprising that the available inter-
are distinguishing features of martensite transformed at 150 C pretations differ signicantly with respect to attributing spectral
(Fig. 5b). components to possible atomic congurations of iron and carbon
The analysis of electron diffraction has disclosed a number atoms.
of ne cementite particles in the martensite obtained by water Gielen and Kaplow [21] studied only aged FeC martensite and
quenching (see Fig. 6). Such cementite particles could also be interpreted the spectrum as consisting of two sextets correspond-
observed after deep cryogenic treatment. Again, the intensity of ing to pure iron atoms Fe0 and iron atoms having two carbon atoms
cementite reections is rather poor (Fig. 6b), which is not surpris- as nearest neighbors, Fe2 (see schemas in Fig. 9).
ing taking into account the small cementite fraction. Nevertheless, Moriya et al. [22], as well as Lesoille and Gielen [23] applied
it is sufcient for obtaining the dark eld image (Fig. 6c), which is the hypothesis given in [6] to the carbon distribution in the virgin
the rst observation of cementite in the as-quenched not tempered martensite and attributed component B to iron atoms with carbon
martensite of tool steels. 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 vir-
3.2. Carbon in the virgin Fe2.03%C martensite gin martensite. Furthermore, the location of some carbon atoms in
the tetrahedral sites would cause two additional sextets in the spec-
A binary FeC solid solution was used in order to shed light tra of the virgin martensite that should disappear during ageing,
on the mobility of carbon atoms in the virgin martensite, which which was not observed.
can be important for the interpretation of phenomena occurring Choo and Kaplow [25] and de Cristopharo and Kaplow [26] sug-
during DCT and for discussion of mechanisms responsible for the gested a repulsive distribution of carbon in the virgin martensite
abnormally low tetragonality of virgin FeC martensite. and interpreted components A, B, C as correspondingly belonging
Fig. 7 shows transmission Mssbauer spectra of the binary to the iron atoms as third, second, and rst neighbors of a carbon
Fe2.03 mass% C alloy after quenching from 1150 C in water atom in the octahedral site. Ino et al. [27] also attributed the compo-
followed by cooling to liquid helium and successive heating to nents C and B to the iron atoms as rst and second neighbors of iron
different temperatures with a holding time of 10 min at each atoms. One of the arguments in this interpretation was that the C
temperature. All measurements were carried out at 208 C. The component cannot belong to iron atoms in carbon clusters because
hyperne structure parameters are given in Table 2 for the virgin they do not exist in the virgin martensite. According to [2527],
and aged martensites. carbon clustering occurs only at room temperature resulting in the
Fig. 8 shows the outer line of the Mssbauer spectrum (nuclear formation of an Fe4 Cx structure. However, as shown in [28], where
transition 1/2 3/2) after holding at above mentioned temper- the Monte Carlo simulation of the FeC solid solution for obtaining
atures. As seen in Figs. 7 and 8, the spectrum of virgin martensite the CC interaction energies in the rst and second co-ordination
consists of six sextets with different values of the hyperne eld, spheres, which could be consistent with Mssbauer data, were per-
isomer shift and quadrupole interaction (see Table 2). Sextets 1, 2 formed, the pairs of carbon atoms in neighboring interstitial sites
and 3, 4, and 5, 6 can be combined into groups A, B, C, respectively, exist in the FeC austenite. Therefore, such pairs should be inherited
as carried out in many recent studies of FeC martensites. The sev- by the virgin martensite as a result of the diffusionless transforma-
enth component with Hi = 34.6 T, which is close to that in pure iron tion.
measured at 208 C, appears after aging at RT. A detailed interpretation was given by Genin et al. [29,30], who
tted the spectra of the virgin and aged FeC martensites using a
3.2.1. Interpretation of Mssbauer spectra combination of E, A, Ba , Bc , C, D, F components. According to [29,30],
The virgin and aged FeC martensites were measured in a num- the component E with the highest hyperne eld of 37.6 T repre-
ber of Mssbauer studies (see e.g. [2130]). So far, it is hardly sents an extended FeC multiplet in which an iron atom has two
possible to carry out ab initio calculations to obtain hyperne 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) Isomer shift,a 0.005 (mm/s) Quadrupol interaction 4 (mm/s)
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 . 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.
eral iron atoms at enlarged distances of 2.86 and 2.66 A. Genin et al.
suppose that this dilatation of the iron lattice is sufcient to coun- and 33.4 T are attributed to the iron atoms with an isolated carbon
terbalance the effect of two carbon neighbors which, in the absence atom (like Fe1 and Fe1 in Fig. 9a). In other words, the authors [29,30]
of dilatation, should decrease the hyperne eld at the iron nucleus suggest that the overlapping of wave electron functions is the same
at least by 6 T (see a corresponding relation in [31]). in the atomic pairs Fe1 C and Fe1 C, in spite of the fact that carbon
The component A with Hi = 36.2 T is interpreted by Genin et al. atoms located in the octahedral sites push Fe1 atoms much more
as belonging to pure iron atoms located sufciently far from the strongly than Fe1 atoms, thereby creating tetragonality in the iron
carbon atoms. The components Ba and Bc with Hi equal to 33.1 lattice.
7032 A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039
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]
of the orthorhombic lattices (c) dark
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 a weak component F with Hi = 16.5 T, which is ascribed to the iron
are attributed to isolated multiplets, i.e. to iron atoms having two atoms with three carbon nearest neighbors.
carbon atoms in the nearest neighborhood (Fe2 in Fig. 9c or d). The One can conclude from the above-performed analysis that, so
difference between C and D congurations is thought to come from far, in relation to Mssbauer spectra of virgin and aged FeC
the effect of next carbon neighbors in the D case. There also exists 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.
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 magnetization axis H. The angle should be equal to zero for the
= e2 qQ(3 cos2 1)/8, where e and Q are the electron charge and iron atoms on the c axis (see Fig. 9a) and 90 for those on the a or
the iron nuclear quadrupole moment, respectively, and is the b axes (see Fig. 9b). An additional argument was given by Ino et
angle between the electric eld gradient q and the direction of easy 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 3.3. Change in the phases of steel X220CrVMo 13-4 due to
higher than the anisotropic energy by which the direction of a spin cryogenic treatment
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. Mssbauer spectra of steel X220CrVMo 13-4 (DIN 1.2380) were
Sextets 5 and 6 belong to the iron atoms having two carbon measured after solution treatment at 1080 C followed by quench-
atoms as nearest neighbors with the angle equal to zero (Fig. 9c ing at RT and subsequent holding in liquid nitrogen or at 150 C.
for sextet 5) and 90 (Fig. 9d for sextet 6, see also the values of in As example, some data are presented in Figs. 1013. The spectra
Table 2). This is similar to the interpretation of C and D components consist of a single line, which belongs to the retained austenite,
in [29,30] with the only difference that sextets 5 and 6 have the a doublet with a quadrupole splitting of about 0.6 mm/s, which
same hyperne eld but different values of quadrupole interaction is attributed to the carbide phase, and four sextets of martensite.
because of different values. The tting of the martensitic component by four sextets was made
based on the distribution of hyperne elds (see Fig. 10b13b).
3.2.2. Carbon distribution in the virgin and aged martensites The areas under spectra components, as determined from Mss-
Based on the proposed interpretation of Mssbauer spectra, bauer spectra, are given in Table 3. The mean square amplitude
the following preliminary characteristics of carbon distribution in of atomic vibrations is not remarkably different in the austenitic
the virgin martensite and carbon behavior during ageing can be and martensitic phases, however it is signicantly decreased in the
assumed: 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
(i) The hypotheses attributing the abnormally low tetragonal-
doublet in Mssbauer spectrum is higher than the fraction of car-
ity of virgin martensite to the occurrence of carbon atoms in
bides in the studied steel. Thus, the change in the area under spectra
the tetrahedral sites [6] or their distribution on the a, b, or c
components due to cryogenic treatment allows to only obtain a
sublattices of octahedral sites [7] are not consistent with the
knowledge about the change of fractions of corresponding phases,
hyperne structure of Mssbauer spectra and their evolution
not their precise amount.
during the heating of virgin martensite.
In relation to the martensitic phase (see Figs. 10b13b), the dis-
(ii) It is clear from the spectra presented in Figs. 7 and 8 that,
tribution of hyperne elds reveals four intensive components in
at holding temperatures below 50 C, nothing changes in
the martensitic spectrum with a rather large half-width of lines
the virgin martensite, i.e. the carbon atoms remain immobile.
that are in fact attributed to several overlapped components, which
If account is taken of the fact that carbon migration expo-
is due to the effect of rst, second, and so on, neighboring solute
nentially decreases with decreasing temperature, it can be
atoms of different kinds on the hyperne eld at the nuclei of the
concluded that carbon atoms cannot move towards the dislo-
iron atoms. Each single carbon atom as the nearest neighbor of an
cations during deep cryogenic treatment of tool steels, as has
iron atom in the martensite lattice decreases the hyperne eld at
been suggested in a number of DCT studies (see Section 1).
(iii) The decrease in intensity of sextets 3 and 4 and the growth
Table 3
of sextets 5 and 6 starting from holding at 50 C is evidence
Relative areas (%) under components of martensite, retained austenite and casrbide
of carbon clustering, which is consistent with the available and under the lines Fe0 and Fe1 in the martensitic component of Mssbauer spectra
observations of the modulated structure in the aged high- in steel X220CrVMo 13-4. Data for Fe0 and Fe1 are normalized to 100% of martensite.
carbon martensites (e.g. [32,33]). Sextet 7, with the hyperne
Cooling after solution treatment Martensite RA Carbide Fe0 Fe1
eld approaching that of pure iron, appears due to carbon
Quenching at RT 81.7 7.7 10.6 27.2 34.0
clustering. Sextet 1 with the increased hyperne eld in com-
RT 196 C (24 h) 86.6 4.1 9.3 24.3 37.3
parison with the pure -iron remains after ageing, which can RT 196 C (36 h) 87.0 3.9 9.1 22.8 38.8
be attributed to dilatation at the coherent boundaries between RT 196 C (48 h) 87.3 3.7 9.0 19.9 43.3
the carbon-rich and carbon-depleted areas in the modulated RT 150 C (24 h) 89.1 3.5 7.4 15.2 46.3
aged martensite. RT(1 week) 196 C (24 h) 85.6 5.8 8.6 21.2 36.5
7036 A.I. Tyshchenko et al. / Materials Science and Engineering A 527 (2010) 70277039
X-ray diffraction patterns of steel X220CrVMo 13-4 after (i) What is the reason for the increase in the density of dislocations
quenching at RT and holding at 196 C for 24 h are shown in 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 tem-
pering, how the carbon atoms can reach the dislocations at low
temperatures?
(iii) What happens with carbide phases in the course of deep cryo-
genic treatment?
Based on the analysis of the available data and taking into [48,49]. Stability of vanadium carbides should be much higher in
account the results obtained in the present study, the following comparison with the vanadium-containing cementite.
model is proposed. The dispersed cementite particles can be obviously dissolved
The freshly formed virgin martensite is characterized by a due to deformation in the course of low-temperature martensitic
decreased strength and comparatively high ductility (see e.g. transformation. They are also observed after cryogenic treatment,
[4042]). The hardness, brittleness, and even microcracking [43] and the exact extent of cementite dissolution cannot be determined
are acquired due to subsequent ageing at RT. by means of transmission electron microscopy.
Therefore, the plastic deformation is expected to occur during The strain-induced dissolution of the primary Me7 C3 carbides is
the martensitic transformation at low temperatures due to the a controversial issue. Chromium in the pearlitic carbon steels assists
volume effect of the martensitic transformation. In addition, the the dissolution of cementite under cold work [48,49] because
dislocation creep can proceed due to stresses caused by differing it increases the enthalpy of binding between carbon atoms and
thermal coefcients of dilatation for austenite and martensite. dislocations [46], whereas its contribution to strengthening of
The plastic deformation of virgin martensite should lead to two interatomic bonds in the carbide lattice is not so large in compari-
important consequences: (i) an increase in the dislocation density son with vanadium.
and (ii) the capture and transport of immobile carbon atoms by The change in the intensities of the martensite components due
moving dislocations. to the low-temperature martensitic transformation, namely weak-
The transport of interstitial atoms by the gliding dislocations is ening of the component Fe0 (see Fig. 14 and also Figs. 10b12b),
usually discussed in relation to hydrogen in metals (see e.g. [44]). A gives the evidence that the concentration of alloying elements in
theoretical analysis for the dislocation transfer of interstitial atoms the martensite increases due to carbide dissolution.
in crystals was recently made in [45]. In accordance with the mechanism of strain-induced carbide
Thus, the carbon clouds around the dislocations are not formed dissolution, the carbon atoms of dissolved carbides are captured by
due to the migration of carbon atoms towards dislocations. They dislocations and cannot affect the intensities of martensitic lines in
result from the capture of carbon atoms by dislocations gener- Mssbauer spectra. Therefore, only substitutional atoms like Cr, V
ated and gliding during the plastic deformation. Because of high and Mo can be responsible for the decrease in the fraction of pure
enthalpy of binding between carbon atoms and dislocations in the iron due to cryogenic treatment. The content of these elements in
-iron (about 0.8 eV, see e.g. [46]), these carbon clouds do not take cementite cannot be different from their average content in steel,
part in the formation of the modulated structure during aging of if to take into account that the ne cementite particles are pre-
virgin martensite and become the sites for the nucleation of the cipitated during self-tempering below Ms temperature. Thus, the
-carbide particles at subsequent tempering, which is consistent increase in the concentration of substitutional alloying elements in
with TEM studies of nucleation during tempering of a high-carbon the solid solution occurs and it can be only due to dissolution of
martensite [12]. special carbides, most likely Me7 C3 .
The results of the amplitude-dependent internal friction mea- While discussing the obtained TEM images of carbide phases
surements in liquid nitrogen (Fig. 15) support the idea of carbon (Figs. 24), it is relevant to note that their partial dissolution due
segregation at the dislocations during the low-temperature gliding to plastic deformation cannot be clearly identied using TEM,
of dislocations. The increase in the holding time in liquid nitro- which is a reason why the phenomenon of strain-induced cemen-
gen decreases the mobility of dislocations, which, at such a low tite dissolution was rst discovered not using TEM, but Mssbauer
temperature, can only result from the capture of immobile carbon spectroscopy. Under cold work of pearlitic steels, the cementite is
atoms by moving dislocations. A reason for their movement is plas- dissolved due to dislocations pulling the carbon atoms from the
tic deformation during the isothermal martensitic transformation surface of cementite plates and, to a smaller extent, due to their
and dislocation creep. cutting accompanied by the carrying-out of carbon atoms by the
gliding dislocations. This is why the only effect observed by means
4.2. Carbide precipitates and their behavior in the course of of TEM is the blurred contrast at the ferrite-cementite interface (see
cryogenic treatment 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)
The studied tool steel contains particles of primary carbide particles.
Me7 C3 , which is enriched in Cr, secondary carbides MeC and Me2 C, Thus, the observed change in Mssbauer spectra of martensite
enriched in V, and ne cementite precipitates. The cubic MeC car- due to cryogenic treatment can be interpreted in terms of partial
bide obviously plays the role of the intermediate phase in the dissolution of cementite and some special carbides.
course of Me2 C precipitation. The presence of cementite is rather
intriguing. It is reasonably to suppose that it precipitates within 4.3. Abnormally low tetragonality of virgin martensite
the temperature range between the martensitic point Ms and RT,
where the cooling rate is rather low. It follows from the analysis of Mssbauer spectra of the vir-
The partial dissolution of the carbide phase, as follows from gin binary Fe2.03%C martensite that carbon atoms do not occupy
the decrease in the intensity of paramagnetic doublet in Mss- tetrahedral sites or octahedral sites in their b or c sublattices, which
bauer spectra, can be related to the effect of plastic deformation in is at variance with the corresponding hypotheses of the low c/a
the course of the low-temperature martensitic transformation. The ratio. The results obtained in the present study are interpreted in
strain-induced dissolution of cementite during plastic deformation terms of plastic deformation of the virgin martensite leading to the
of plain carbon steels was observed in 1972 using Mssbauer spec- partial capture of carbon atoms by moving dislocations. This sug-
troscopy [47]. A review of the experimental data is given in [48,49]. gests that the segregation of carbon atoms at the dislocations is the
In the 1990s, this effect was studied using the 3d APFIM technique real reason for the decreased tetragonality of the virgin martensite.
(e.g. [50,51]]). It is worth noting that the subsequent increase in the c/a ratio
In relation to the partial strain-induced dissolution of special during ageing of the virgin martensite at room temperature, which
carbides, it seems to be hardly possible for MeC and Me2 C carbides was rst observed in [3] and repeated in other similar studies, is not
because they contain much vanadium. Even be dissolved in cemen- due to dilution of carbon clouds around the dislocations. The bind-
tite, vanadium decreases its strain-induced dissolution because ing enthalpy between carbon atoms and dislocations in the pure
of strong increase of the interatomic bonds in cementite lattice 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 7039
elements like Cr [46]. Thus, it is hardly possible that carbon atmo- [10] M. Pellizari, A. Molinari, in: J. Bergstrm, et al. (Eds.), Proceedings of the
spheres around the dislocations can be exhausted during ageing of 6th International Tooling Conference, Karlstad University, Karlstad, Sweden,
September 1013, 2002, pp. 547557.
martensite. [11] T. Yugandhar, P.K. Krishnan, C.V. Bhaskar Rao, R. Kalidas, in: J. Bergstrm, et
A more plausible explanation for this partial recovery of tetrag- al. (Eds.), Proceedings of the 6th International Tooling Conference, Karlstad
onality is based on the coherent stresses at the boundaries between University, Karlstad, Sweden, September 1013, 2002, pp. 559569.
[12] Y. Hirotsu, S. Nagakura, Acta Metall. 20 (1972) 645655.
the carbon-rich and carbon-depleted areas in the aged marten- [13] M.J. Van Cenderen, A. Bttger, R.J. Cernik, E.J. Mittemeijer, Metall. Trans. A 24
site, similar to tetragonality of NiTi martensite containing Ni3 Ti (1993) 19651973.
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[15] D. Jun, X. Hohgshen, Heat Treat. Met. 25 (1998) 5559.
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ing dislocations during the cryogenic treatment and corresponding (Eds.), Proceedings of 7th International Tooling Conference, Politechnico di
decrease of the carbon content in the martensite should result in the Torino, Torino, Italy, May 25, 2006, pp. 151158.
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[18] D.N. Collins, Heat Treat. Met. 2 (1996) 4042.
neighbors (the component Fe0 in Mssbauer spectra). The oppo- [19] R.G. Tated, S.R. Kajale, K. Iyer, in: M. Rosso, M. Actis Grande, D. Ugues (Eds.),
site effect of the decrease in the intensity of the component Fe0 , as Proceedings of 7th International Tooling Conference, Politechnico di Torino,
observed in this study, is due to the strain-induced dissolution of Torino, Italy, May 25, 2006, pp. 135145.
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