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Materials Engineering, Vol. 17, 2010, No. 1

STRUCTURAL CHANGES IN Cr-V LEDEBURITIC STEEL DURING

AUSTENITIZING AND QUENCHING
Peter Juri
Received 28th January 2010; accepted in revised form 16th February 2010

Abstract
The Vanadis 6 PM Cr-V ledeburitic steel was austenitized at temperatures from the range 1000 1200 oC
and nitrogen gas quenched. Structural changes were investigated by light microscopy and SEM. Obtained result
fixed that the M7C3-carbides underwent a complete dissolution in the austenite while MC-phase remained almost
completely unaffected. The saturation of the austenite by chromium and partly vanadium induced formation of
increased portion of non-martensitic structural components after quenching, due to decrease of MS and Mf
temperatures. Undissolved part of MC-carbides, located mainly on the grain boundaries, hinders effectively the
grains coarsening also at higher austenitizing temperatures.
Keywords: PM ledeburitic steel, microstructure, carbides, matrix saturation, martensite, bainite.

1. Introduction
The Cr-V ledeburitic steels for cold work
applications were developed firstly in the beginning
of 20th century. They early gained a high popularity
because of relatively simple alloying, good wear
resistance and excellent compressive strength. On the
other hand, they had a low resistance against the
initiation of brittle fracture, due to high portion of
large and non-uniformly distributed carbides, which
limited their operating reliability. This problem was
successfully solved only after introduction of the
rapid solidification effect into the standard
manufacturing of these materials. As a result, a wide
scale of Cr-V ledeburitic steels of an excellent
metallurgical quality is produced nowadays.
For the tool making it is necessary to obtain
the soft-annealed state of the material in order to
reduce its hardness to the minimum. On the other
hand, it is necessary to heat treat the tools made from
Cr-V ledeburitic steels before use since a proper heat
treatment gives the material the hardness, toughness,
wear resistance and other properties desired for a
sufficient functionality.
Standard heat treatment of Cr-V ledeburitic
steels consists of following steps: austenitizing,
holding at the temperature to dissolve a certain
amount of carbides and to homogenize the austenite,
quenching to a room (or sub-zero) temperature and
several times tempering, usually to the secondary

hardness peak. After these procedures, the hardness

reaches up to more than 60 HRC.
During the heating up to the austenitizing
temperature, the first carbides undergoing the
dissolution are the pearlite forming phases. However,
the concentration of carbon and alloying elements is
very low in the pearlite and its transformation into the
austenite does not lead to sufficient austenite
saturation. It is thus necessary to heat the material up
to higher temperature. As well known, a dominant
part of secondary carbides M7C3 undergoes
dissolution only at the temperatures from the range
950 1050 oC. The second carbide phase, e.g.
vanadium rich MC carbides, on the other hand,
remains almost completely undissolved. Its role in
heat treatment is predominantly passive fine
particles at the grain boundaries block the grain
coarsening and contribute to keep the material a good
toughness.
Quenching of the material must ensure desired
as-quench hardness, normally exceeding 62 HRC.
The Cr-V ledeburitic steels have an excellent
hardenability owing to high alloying level. After
quenching, the structure of the materials consists
mostly of martensite and retained austenite.
The portion of retained austenite increases with
increasing austenitizing temperature, because higher
austenitizing temperature leads to more saturated
austenite and decrease the temperatures Ms and Mf,

P. Juri, Doc. Dr. Ing. Department of Materials Engineering, Faculty of Mechanical Engineering, Czech
Technical University in Prague, Karlovo nm 13, 121 35 Prague, Czech Republic.
*
Corresponding author, e-mail address: p.jurci@seznam.cz

Materials Engineering, Vol. 17, 2010, No. 1

both below the zero [1]. As known from some CCTgraphs [2], also some portion of bainite can be formed
in the as-quenched structure, but with no risk of
substantial hardness decrease.

unaffected, but the martensite becomes blue and the

bainite red-violet [3].

The paper presents the results of investigations

what happens in the microstructure of the most widely
used PM ledeburitic Cr-V steel Vanadis 6, when it is
austenitized and quenched.

Hardness of the material in the as-received as

well as heat processed conditions was measured by
the Vickers hardness tester at a load of 98.1 N (HV
10) and loading for 10 s. Each specimen was
measured 10 times. The mean value and standard
deviation from the measurements of each specimen
was then calculated.

2. Experimental
For the investigations, the Cr-V ledeburitic
cold work tool steel Vanadis 6 made by powder
metallurgy of rapidly solidified particles was used.
The chemical composition of the material is given in
Table 1.
Tab. 1
Chemical composition of investigated material
Material
Vanadis 6

Mn

Si

Cr

Mo

2.1

0.8

5.8

1.5

Specimens made from the examined material

were vacuum austenitized at the temperatures from
the range 1000 1200 oC, holding time at each
temperature of 30 min., and nitrogen gas quenched,
without any further heat processing (sub-zero
processing, tempering).
Microstructural analysis has been carried out
using the light microscope NEOPHOT 32 and field
emission scanning electron microscope JEOL JSM
7600 with the EDS microanalysis. The point EDS
microanalysis of the matrix has been carried out in 40
different places on the metallographical specimen.
The mean value and standard deviation of measured
data was then calculated. The EDS mapping was done
in order to verify the composition of the carbides on
the grain boundary and inside the grains, after
quenching from different austenitizing temperatures.
For the light microscopical evaluation, two
etching agents were used. To make visible the
primary austenitic grain boundaries, the 3 % Nital
reagent was used. For the identification of
transformation constituents, the Beraha Martensite
agent was employed. In this case, the carbides remain

3. Results and discussion

Figure 1 shows the as-quenched microstructures of the material. If lower austenitizing
temperature was used then the microstructure consists
of the matrix with a relatively large portion of
undissolved (eutectic and a part of secondary)
carbides, Fig. 1a, b. With increasing austenitizing
temperature, the boundaries of primary austenitic
grains become visible, micrographs in Fig. 1c, d, e.
The portion of undissolved carbides slightly decreases
at the same time. As evident, the carbides are located
as on the grain boundaries so inside grains.
Measurement of austenitic grain size according to the
ASTM-method revealed that after the quenching from
lower temperature, it was 11.5 and it increased
slightly to 10 after the quenching from the
temperature of 1200 oC. These results are in good
agreement with the date published elsewhere [5],
where the grain coarsening of austenite is reported to
be slower for the PM ledeburitic steels due to high
content of fine carbides.
Figure 2 shows the micrographs of the material
quenched from identical austenitizing temperatures as
in Fig. 1, but etched using the Beraha Martensite
reagent. It is clearly visible that the structural portion
of carbides decreases with increased austenitizing
temperature. This also indicates that the matrix
becomes more saturated by carbon and alloying
elements, which was confirmed by EDS-analysis,
Table 2. The portion of the martensite (blue) slightly
decreases and bainite (red-violet) increases with
increased austenitizing temperature. In addition, it
seems that also the amount of retained austenite
increases. The increase of retained austenite amount
is, however, not dramatic. It is natural to expect an
Tab. 2

Amount of alloying elements dissolved in the matrix

Austenitizing temperature

1000

1050

1100

1150

1200

Cr

5.66 +-0.56

5.96+-0.22

6.85 +-0.33

6.96 +- 0.15

7.12 +-0.09

1.72 +- 0.32

1.76+-0.48

2.24 +-0.53

2.18 +- 0.43

2.66 +-0.37

Materials Engineering, Vol. 17, 2010, No. 1

1000 oC

15 m

1050 oC

15 m

1100 oC

15 m

1150 oC

15 m

Fig. 1. Microstructure of the Vanadis 6

ledeburitic steel after quenching from
different austenitizing temperatures

1200 oC

15 m

increased portion of retained austenite after quenching

from higher temperature. If higher austenitizing
temperature is used then more carbides is dissolved
and the austenite becomes more saturated by carbon
and alloying elements. This fact tends to decrease of
Ms and Mf temperatures, respectively. From the same
reason, also increased portion of bainite is natural to

be expected. When quenched by media of a room

temperature, the material is cooled down and
afterwards kept at a temperature between Ms and Mf.
Martensite is then formed only during cooling down
and the transformation is stopped when the material
achieves the quenchant temperature. Remaining part
of the austenite is then transformed mostly to bainite.

Materials Engineering, Vol. 17, 2010, No. 1

1000 oC

15 m

1050 oC

15 m

1100 oC

15 m

1150 oC

15 m

Fig. 1. Microstructure of the Vanadis 6

ledeburitic steel after quenching from different
austenitizing temperatures

1200 oC

15 m

One can expect a rapid increase of retained

austenite amount after quenching, especially from
very high temperatures. Such a phenomenon was
reported by various authors for Cr-ledeburitic steels
when overheated during the austenitizing [1,4,6].
However, no dramatic retained austenite amount
increase was found in the case of the Vanadis 6 steel.

One reason of that can be the composition of the

material. The steel contains lower amount of the
M7C3-phase than the 12%Cr-ledeburitic steels. On the
other hand, the second main carbidic phase is the MCphase. These carbides dissolve only hardly in the
austenite. The total alloying elements content
dissolved in the austenite is then lower than that

Materials Engineering, Vol. 17, 2010, No. 1

1000 oC

1050 oC

1100 oC

1150 oC

Fig. 2. Microstructure of the Vanadis 6

ledeburitic steel after quenching from different
austenitizing temperatures, colour etching
using the Beraha-martensite agent

1200 oC
measured for 12 % Cr-ledeburitic steels [1]. The MCcarbides do neither contribute to the increase of
carbon- and alloying elements content nor to the
decrease of Ms and Mf temperatures. The second
reason, connected with the first one, is the presence of
bainite.
Compared
to
purely
martenistic
transformation, lower amount of retained austenite
can be expected when bainite is formed.
In the case of 12 % Cr-ledeburitic steels, the
overheating is connected with sharp hardness
decrease. This is due to high amount of retained

austenite. The hardness of the Vanadis 6 steel is in

Table 3. It is clearly shown that the hardness is
constant after the quenching from the temperatures
from the range 1000 1200 oC. Small differences can
be considered to be within the range of measurement
uncertainty. These results indicate that the Vanadis 6,
as a representative material of Cr-V ledeburitic steels,
is not as sensitive to softening due to high portion of
retained austenite as the Cr-ledeburitic steels.
Figure 3a shows SEM micrographs from the
sample quenched from the austenitizing temperature

Materials Engineering, Vol. 17, 2010, No. 1

Fe

Cr

3 m

Fig. 4. EDS maps from the microstructure of the material, austenitized at 1000 oC, Fig. 3b
of 1000 oC. The structure consists of matrix, which
contains mainly the martensite, and carbides. These
carbides are located as at the primary grain boundaries
so inside the grains. Detail micrograph made at high
magnification, Fig. 3b, shows that a lot of carbides
inside the grains have a very small dimension, mostly
in nano-scale. On the other hand, the carbides at the
grain boundaries are greater and their diameter ranges
between 1 and 2 m. One can assume that the nanoscaled carbides could be the rests of the M7C3,
after their partial dissolution of M7C3 phase in
the austenite. This explanation seems to be
relatively correct since the dissolution temperature for
this phase is around 1000 oC and, in addition, these
particles were not detected in the micrographs made
from the samples austenitized at temperatures higher
than 1100 oC. But also some coarse particles are the
M7C3-phase, as fixed by EDS mapping, Fig. 4.
This is rather surprising on the first sight because one
can expect rather the dissolution of the M7C3carbides. On the other hand it is known that in many
Tab. 3
Hardness of the Vanadis 6 ledeburitic steel
after quenching
Austenitizing
temperature
Hardness
HV 10

1000

1050

1100

1150

1200

841
+- 17

844
+- 25

850
+- 7

831
+- 14

857
+- 7

5 m

2 m

Fig. 3. Microstructure of the Vanadis 6 ledeburitic

steel after quenching from 1000 oC, a overview,
b detail, SEM

Materials Engineering, Vol. 17, 2010, No. 1

Fe

Cr

3 m

Fig. 4. EDS maps from the microstructure of the material, austenitized at 1000 oC, Fig. 3b

cases, the M7C3-phases undergo easily the coarsening

at high temperatures. Moreover, the M7C3 carbides
contain some amount of vanadium, up to 10%, that
increases their thermal stability. Similar particles were
identified also in the sample quenched from 1050 oC,
Figs. 5 and 6. But in next micrographs and EDSmaps, made from the samples austenitized at a
temperature 1100 oC and higher, these particles are no
more visible, Figs. 7 10 (the tracks with elevated
Cr-content on the Cr-field in the EDS maps
correspond only to the chromium content in MCphase). This indicates that after the coarsening, their
dissolution in the austenite followed. In Table 2, an
increased Cr-content in the matrix after austenitizing
at 1100 oC is clearly shown. This is connected with
complete dissolution of the M7C3 phase.
The carbides at the grain boundaries are mostly
of the MC-phase. As shown in Table 2, the
concentration of the alloying elements in the matrix
increases only very slightly above the temperature of
1100 oC, e.g. when the M7C3 carbides are already
completely dissolved. This indicates that the MC
phase underwent the dissolution only in a very limited
amount. The role of the MC-carbides in the heat
treatment process, however, is very important because
they hinder the coarsening of the austenite grains
effectively. This is the explanation why the grain size
remains affected by the austenitizing temperature in
a very limited manner.

5 m

2 m

Fig. 5. Microstructure of the Vanadis 6 ledeburitic

steel after quenching from 1050 oC, a overview,
b detail, SEM

Materials Engineering, Vol. 17, 2010, No. 1

Fe

Cr

2 m

Fig. 6. EDS maps from the microstructure of the material, austenitized at 1050 oC, Fig. 5b

5 m

5 m

1 m

2 m

Fig. 7. Microstructure of the Vanadis 6 ledeburitic

steel after quenching from 1100 oC, a - overview,
b - detail, SEM

Fig. 9. Microstructure of the Vanadis 6 ledeburitic

steel after quenching from 1200 oC, a overview,
b detail, SEM

Materials Engineering, Vol. 17, 2010, No. 1

Fe

Cr

2 m
o

Fig. 8. EDS maps from the microstructure of the material, austenitized at 1100 C, Fig. 7b

Fe

Cr

2 m

Fig. 10. EDS maps from the microstructure of the material, austenitized at 1200 oC, Fig. 9b

10

Materials Engineering, Vol. 17, 2010, No. 1

4. Conclusions

Therefore, the presence of the bainite and

small portion of retained austenite did not cause the
lowering of as-quenched hardness.

The paper was focused to investigation what

happens when the widely used cold work tool steel
Vanadis 6 is austenitized and quenched. The results
can be summarized as follows:
The M7C3 carbides were dissolved in the
austenite completely up to a temperature of 1100 oC.
Their dissolution is connected with saturation of the
austenite with carbon and alloying elements.
The MC carbides, on the other hand,
remained almost completely undissolved also stable
also after heating up to 1200 oC and contributed to the
austenite saturation in a very limited extent. They role
in the heat treatment is rather passive the particles
hindered the grain coarsening and the material kept
fine grains up to very high temperature.
Increasing saturation of the austenite led to
elevated non-martensitic structures content after
quenching. But the increase of the portion of bainite
and mainly that of the retained austenite is not as high
as reported for the 12%Cr-ledeburitic steels.

Acknowledgements
The author wishes to thank Mrs. Anna
Macchov from the University of ilina for
the excellent collaboration in colour metallography.

References
[1] Berns, H.: Hrterei - Tech. Mitt. 29 (1974), 236.
[2] The Vanadis 6 steel, prospect brochure, Uddeholm AB,
Hagfors, Sweden, 2001.
[3] Skoovsk, P.; Podrbsk, T.: Colour Metallography
of Ferrous Alloys, ilina University, ilina, 2001.
[4] Schwendemann, H. et al.: Hrterei-Tech. Mitt. 41
(1986), 66.
[5] Kulmburg, A. et al.: Hrterei-Tech. Mitt., 45, 1990, 4,
p. 200.
[6] Nykiel, T.; Hryniewicz, T.: In.: Proc. of the 11th Int.
Federation for Heat Treatment and Surf. Engineering,
Florence, Italy, Vol. 1. 87.