J. Cent. South Univ. Technol.

(2008) 15: 454−458

DOI: 10.1007/s11771−008−0085−9

Effects of cryogenic treatment on mechanical properties and

microstructure of Fe-Cr-Mo-Ni-C-Co alloy

ZHU Yuan-zhi(朱远志)1, 2, YIN Zhi-min(尹志民)2, ZHOU Yong(周 勇)3,

LEI Quan-feng(雷全锋)3, FANG Wen-sheng(方文胜)3

(1. Key Laboratory for Ferrous Metallurgy and Resources Utilization of Ministry of Education,
Wuhan University of Science and Technology, Wuhan 430081, China;
2. School of Materials Science and Engineering, Central South University, Changsha 410083, China;
3. Danjiang Aluminum Ltd. Co., Danjiangkou 442700, China)

Abstract: Fe-Cr-Mo-Ni-C-Co alloy was quenched in liquid nitrogen and held for 24 h. Hardness tester, OM, XRD, SEM were used
to investigate the mechanical properties and microstructures of the alloy. The results show that the hardness increases by 1−2 (HRC)
and the compressive strength decreases slightly after cryogenic treatment. The increase in hardness is attributed to the transformation
from austenite to martensite and the precipitation of the very tiny carbide η-Fe2C. The decrease in compressive strength is caused by
residual stress. The great amount of carbides, such as Cr7C3 and Fe2MoC, in the alloy and the obvious difference in thermal
expansion coefficient between these carbides and the matrix at the cryogenic temperatures lead to this residual stress. The
microscopy of cryogenic martensite is different from that of the non-cryogenic martensite. The cryogenic martensite is long and fine;
while the non-cryogenic martensite is short and coarse. There is obvious surface relief of the cryogenic martensite transformation. It
is not orientational of this kind surface relief and the boundary of this surface relief is smooth and in a shape of butterfly. The surface
relief in the non-cryogenic martensite is wide and arranged in parallel, and the boundary of surface relief is not smooth. These
characteristics may imply different growth ways of the two kinds of martensite.

Key words: Fe-Cr-Mo-Ni-C-Co alloy; powder metallurgy; microstructure; mechanical properties; cryogenic martensite

microstructure and mechanical properties of quenched

1 Introduction
Valve and valve seat are key parts installed in the
cylinder head of an engine to ensure the seal of the
engine chamber. Valve and valve seat are composed of a
tribopair. To lower the wear of this tribopair, a new type
of PM Fe-Cr-Mo-Ni-C-Co alloy was designed for valve
seat. The mechanical properties and microstructure of the
alloy at room temperature were reported in other
papers[1−7]. In installation, valve seat was assembled in
interference fit with the cylinder head. Concretely, the
valve seat was treated in liquid nitrogen and then quickly
inserted into the cylinder head. Thus, the valve seat was
fixed into the cylinder head firmly when its temperature
returns to room temperature[1−2]. Microstructures and
mechanical properties of the alloy will be affected by
cryogenic treatment. Therefore, it is necessary to
investigate whether a hardness of 39−45(HRC) and a
compressive strength of 650 MPa required by the users
can be ensured or not after cryogenic treatment. The
influences of cryogenic treatment on microstructures and
properties of quenched alloyed steel have been
reported[3−7]. However, few studies focus on
and tempered PM Fe-based alloy. Here, microstructure
and mechanical properties of PM Fe-Cr-Mo-Ni-C-Co
alloy in cryogenic treatment were studied.
2 Experimental procedure
The as-received alloy samples were quenched at
1 000 ℃ and tempered at 650 ℃ for 2 h according to
Ref.[8]. The alloy was dipped into liquid nitrogen
directly and held for 24 h, then fetched out. Density,
hardness and compressive strength were measured in a
way as illustrated in Ref.[9].
OM, SEM and TEM were also conducted to
investigate the microstructure evolution of the cryogenic
treated alloy.
3 Results
3.1 Mechanical properties
Mechanica1 properties and density of the alloy are
listed in Table 1. The results show that there is no change
in density after cryogenic treatment. Hardness has an
increase of 2.5(HRC) and there is a slight decrease in

Received date: 2008−01−09; Accepted date: 2008−04−09

Corresponding author: ZHU Yuan-zhi, PhD, Associate Professor; E-mail: tozyzl@163.com
J. Cent. South Univ. Technol. (2008) 15: 454−458
compressive strength. Both hardness and compressive
strength can still satisfy the need of user.
3.2 Microstructure
Fig.1 shows the optical micrographs of the alloy. It
can be seen that the matrix of the as-received alloy is the
tempered sorbite, and the retained austenite (gray phase
within a grain) and the coarsened carbides distribute on
grain boundary. Usually, the matrix of quenched and
tempered ferrite alloy should be sorbite. But in this alloy,
the retained austenite in the matrix may be attributed to a
great deal of tiny carbides and solid solution of
chromium and carbon. After cryogenic treatment, part of
the retained austenite was transferred into martensite.
The original retained austenite was separated into small
pieces by the needle-like martensite.
To make an investigation of the microstructural
evolution, SEM analysis was performed, and the results
are shown in Fig.2. The microstructure of cryogenic
martensite is different from that of the non-cryogenic
martensite. In the cryogenic treated alloy, the cryogenic
martensite is long and thin. There is surface relief of the
cryogenic martensite transformation. There is no obvious
orientation in this kind of surface relief and the boundary
of this surface relief is smooth and in a shape of butterfly.
However, the non-cryogenic martensite is coarse and
short (Fig.2(a)). The surface relief in the non-cryogenic
martensite is wide and arranged in parallel. The
boundary of surface relief is not smooth. These
characteristics may imply different growth ways of the
two kinds of martensite.
Table 1 Comparison of mechanical properties of studied alloys after different heat treatments
Hardness(HRC)
Sample Density/(g·cm−3)
Measured
As-received 7.39 41.0
After cryogenic treatment 7.39 43.5
Fig.1 SEM images of studied alloys: (a) As-received alloy; (b) Cryogenic treated alloy
455
XRD analysis was also performed to investigate the
phase transformation in cryogenic treatment. The
diffraction patterns are shown in Fig.3.
From XRD pattern, compared with the as-received
alloy, two aspects of changes of the alloy by cryogenic
treatment are obvious. Firstly, the intensity of the
diffraction peak of retained austenite in the alloy after
cryogenic treatment becomes lower, which means that
the retained austenite has been transferred into martensite
in cryogenic treatment. Secondly, there is a diffraction
peak on the left of the main diffraction peak of retained
austenite. It is the diffraction peak of plane (020) of
η-Fe2C. It can be concluded that η-Fe2C precipitates in
the cryogenic treatment. Because the size of this carbide
is too small to be found in the SEM image.
TEM micrographs are shown in Fig.4. It can be seen
that there are carbides with a size of about 10 nm
precipitated on martensite plane. It is confirmed to be
η-Fe2C by the selected area diffraction.
4 Discussion
4.1 Hardness and strength of cryogenic treated alloy
Hardness of the alloy is increased after cryogenic
treatment, which is mainly attributed to the
transformation of the retained austenite into martensite.
Because martensite is a supersaturated solid solution.
The formation of martensite leads to lattice distortion.
The stress and strain field forms in the interface between
martensite and its adjacent austenite. The resistance of
Compressive strength/MPa
User requirement Measured User requirement
39−45 713 650
39−45 672 680
456
Fig.2 SEM images of alloy: (a) As received alloy; (b) Cryogenic
treated alloy
Fig.3 XRD patterns of alloys: (a) Cryogenic treatment; (b) As-
received
dislocation movement increases. Hence, the hardness and
the strength of the alloy increase. On the other hand, the
martensite separates the retained austenite into pieces,
which means that the retained austenite is refined.
According to Hell-Petch equation:
σs=σ0+Kyd−1/2 (1)
where σs is the yield strength; σ0 is the original strength;
d is the diameter of the grain and Ky is the constant. The
size of the austenite is less than 1/5 of the original one.
J. Cent. South Univ. Technol. (2008) 15: 454−458
Fig.4 TEM image (a), selected area diffraction pattern (b) and
index calibration of diffraction pattern (c) of cryogenic treated
alloy
However, the amount of austenite is just a small fraction
in the total and Ky is also small. Therefore, the increment
of strength and hardness is also minor.
Another change of the alloy in cryogenic treatment
is the precipitation of η-Fe2C from martensite. These
carbides are very fine and lead to an additional increase
in strength of the martensite. But because the fraction of
the martensite is small, the increase in strength is minor.
The fractograph is shown in Fig.5. It can be seen
that there are some fine and long (needle-like) phases in
the cryogenic treated alloy and these phases are not
J. Cent. South Univ. Technol. (2008) 15: 454−458
Fig.5 Fractographs of alloys: (a) As-received; (b) Treated at
cryogenic temperature
broken in the fracture of the alloy, which means that the
micro-strength of the phases is high. But in the
as-received alloy, the needle-like phases are not detected
(Fig.5(b)). It is sure that these phases are martensite.
Additionally, secondary cracks can also be seen in the
fractograph of the cryogenic treated alloy. The cracks
originate from carbides distributed on grain boundaries.
Some cracks separate the carbides into two parts. It is
obvious that the micro-parts in the alloy shrink in the
cooling process. But the expansion coefficient of
carbides is much lower than those of ferrite and austenite.
There is tensile stress on the carbides. During the rising
of temperature after cryogenic treatment, there is
compressive stress on the carbides. The stress on
carbides during the cryogenic treatment is schematically
illustrated in Fig.6.
It can be seen that the compressive stress on the
carbides during the rising of temperature after cryogenic
treatment would balance the tensile stress in the cooling
process. Therefore, there are no obvious changes in the
mechanical properties of the alloy.
4.2 Microstructures
4.2.1 Formation of martensite
When the austenite is quenched to room
temperature, it transfers into supersaturated solid
457
solution—martensite. The formation of martensite leads
to residual compressive stress on the adjacent austenite,
which makes the transformation of austenite into
martensite more difficult. Even if the temperature of the
alloy is cooled to room temperature, some austenite still
cannot be transferred into martensite. Moreover,
multi-alloy elements in the alloy stabilize the austenite at
elevated temperature[10−14]. Even if the alloy has been
tempered at 600 ℃, the austenite cannot be decomposed
completely (see Fig.7). The retained austenite is
transferred into martensite at a much higher driving force
during the cryogenic treatment.
Fig.6 Stress on carbides in alloy during heat treatment process
at cryogenic temperature: (a) Cooling to cryogenic temperature;
(b) Heating to room temperature
Fig.7 Retained austenite in alloy quenched at 1 000 ℃ and
tempered at 600℃
There is great difference in the micrograph of
cryogenic martensite and non-cryogenic martensite.
There is obvious surface relief in the cryogenic
martensite transformation. It is not orientational of this
kind of surface relief and the boundary of this surface
relief is smooth and in the shape of butterfly. The surface
relief in the non-cryogenic martensite is wide and
arranged in parallel. The boundary of surface relief is not
smooth. The probable reason is that the matrix is
relatively soft when martensite forms in the quenching
process at relatively high temperatures. It is easy for
martensite to nucleate and grow. However, for cryogenic
treatment, the temperature is much lower. And
additionally, the carbon content in the alloy is very high
and a lot of fine dispersed carbides are distributed in
matrix, which enhances the resistance of martensite
transformation and martensite growth. These
458
characteristics may imply different growth ways of the
two kinds of martensite. The martensite can just grow
along so-called “soft” location.
4.2.2 Dynamics of carbide precipitation
At a very low temperature during cryogenic
treatment, the diffusion of atoms is very slow. In the
cooling process, the great bulk shrinkage of the alloy
makes the FCC austenite transfer into BCC martensite.
This phase transformation leads to the increase in density
of dislocations and vacancies. The supersaturated
dislocations and vacancies enhance the diffusion
coefficient of carbon. Carbon atoms are driven to
segregate dislocations by the interaction of stress field
around dislocations with interstitial carbon atoms. This
microstructural evolution induces the precipitation of
very tiny carbides during the cryogenic treatment. At a
liquid nitrogen temperature, the diffusion of carbon is
extraordinarily slow. However, in the heating process
after the cooling process, carbides precipitate. The
precipitation temperature of carbides is over 100 K[15].
5 Conclusions
1) The hardness of the Fe-based alloy increases 1−2
(HRC) and compressive strength decreases slightly after
cryogenic treatment.
2) The increase in hardness is attributed to the
transformation from austenite to martensite and the
precipitation of the very tiny carbide η-Fe2C. The
decrease in compressive strength is caused by residual
stress. The great amount of carbides such as Cr7C3 and
Fe2MoC in the alloy and the big difference between these
carbides and the matrix in thermal expansion coefficient
at the cryogenic temperatures lead to this residual stress.
3) There is surface relief in the cryogenic martensite
transformation. There is no obvious orientation in this
kind surface relief and the boundary of this surface relief
is smooth and in the shape of butterfly. The surface relief
in the non-cryogenic martensite is wide and arranged in
parallel and the boundary of surface relief is not smooth.
These characteristics may imply different growth ways
of the two kinds of martensite.
J. Cent. South Univ. Technol. (2008) 15: 454−458
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