Materials Science Forum Online: 2016-03-20

ISSN: 1662-9752, Vol. 849, pp 503-507

doi:10.4028/www.scientific.net/MSF.849.503
© 2016 Trans Tech Publications, Switzerland

Effects of Alloying Elements on the Properties of Ni-Mo-Cr Superalloys

with Low Thermal Expansion
Min Yua, Kaihong Caib and Zhenrui Lic
Beijing Beiye Functional Materials Corporation, Beijing, 100192,China
a
yumin_0819@163.com, bcaikaihong@hotmial.com, clizhenrui@bygcg.com

Keywords: High temperature low thermal alloy, Alloying elements.

Abstract. The effects of alloying elements including tungsten, molybdenum and cobalt on the
thermal expansion and mechanical properties of Ni-Mo-Cr superalloys were investigated. It was
founded that cobalt had no influence on the thermal expansion properties of the alloys. The addition
of proper amount of tungsten reduced the coefficient of thermal expansion and increased the
mechanical properties of alloy both at room temperature and at high temperature. Reducing the
amount of molybdenum and increasing the amount of tungsten were helpful to reduce the
coefficient of thermal expansion of the alloys at high temperature and improved the performance
consistency of the coefficient of thermal expansion from low to high temperature.

Introduction
Low thermal expansion superalloy is a kind of superalloys with low expansion coefficient. The
typical low expansion alloy is Fe-Ni alloy containing 36% nickel, that is, Invar alloy[1]. Addition of
cobalt may cause the minimum expansion coefficient emerged temperature moving to high
temperature, and thus further developed Fe-Ni-Co Kovar alloys. Although the expansion coefficient
of Invar alloys and Kovar alloys is low, the strength is too low, especially at high temperature,
which cannot be used as structural material. A series of Incoloy alloys [2] have been developed, by
adding some elements, such as niobium, titanium, aluminum or the like, to the matrix of Kovar
alloys. These alloys not only have low expansion coefficient which is being only a half of the
expansion coefficient of the ordinary superalloys, but also have largely increased strength at high
temperature which are up to the same level as Inconel718 alloy. Furthermore, these alloys are used as
high temperature structure materials, since they have good thermal fatigue performance, high
thermo-plastic and almost constant elastic modulus. Accordingly low thermal expansion superalloys
are suitable for producing various of aircraft engine rings and castings which work at the
temperature below 650℃ or 750℃[3].
At present, almost all low thermal expansion superalloys are Fe-Ni-Co alloys, which have
different properties developed by adding some different elements, such as niobium, titanium,
aluminum or the like. But a exception of low thermal expansion superalloys, that is, Ni-Mo-Cr alloy.
This alloy is different from the ordinary superalloys, which is non-ferromagnetic and not offset the
expansion of alloys by magnetostriction. This age-hardenable alloy, utilizes a long-range-ordering
reaction to form uniformly sized and distributed, extremely small (on the order of 10nm), ordered
particles [4]. Thus this alloy has excellent strength and ductility at elevated temperatures, low
thermal expansion characteristics and good oxidation resistance. Now many studies are designed to
characterize its properties, what is lacking is an attempt to understand the fundamentals of the
deformation and strengthening mechanisms in this alloy.
Now only a few corporations can mass-produce these alloys. From the references which have
been mentioned, the researches on Ni-Mo-Cr alloys are seldom discussed.
The main aim of this investigation is to study the effects of alloying elements on expansion and
mechanical properties of Ni-Mo-Cr superalloys.

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504 Special and High Performance Structural Materials

Experiment Procedures
Alloys with six different chemical composition has been researched, the specific composition as
illustrated in Table 1. Comparing 2# alloy and 3# alloy with 1# alloy, cobalt content gradually
increased. Comparing 5# alloy with 4# alloy, tungsten was added. Comparing 5# alloy with 6# alloy,
tungsten was added and molybdenum content was reduced.
Table 1 The chemical composition of the examined specimens（wt.%）
Alloy Cr Co Mo W Fe Ni
1# 7.48 1.46 25.0 / 2.07 balance
2# 7.52 5.09 25.0 / 2.58 balance
3# 7.48 7.13 25.0 / 2.39 balance
4# 7.86 1.99 22.1 / 0.95 balance
5# 7.91 1.99 22.3 6.79 <0.10 balance
6# 7.88 1.93 24.8 / <0.10 balance
All alloys were solution treated at high annealing temperature, and water quenched, insuring that
all secondary phase precipitates were fully dissolved. Then aged at low annealing temperature for
24h and cooled in air.
Cylindrical thermal expansion samples of Φ4×25mm were cut from bars of the six alloys, then
measured with the DIL 402 dilatometer produced by NETZSCH company. The calculation formula
of the coefficient of thermal expansion is

α=（LT-LR）/(T-TR) (1)

Wherein LT is the sample length at T temperature, LR is the sample length at room temperature, T
is test temperature, and TR is room temperature.
Room temperature tensile tests were conducted in accordance with GB/T228-2010 Specification
on WDW3100 Electronic tensile testing machine. High temperature tensile tests were conducted in
accordance with GB/T4338-2006 Specification on NT-56 universal testing machine and the test
temperature is 650℃.
Scanning electron microscope (SEM) was used to examine microstructure. Secondary electron
mode was used for analyzing carbide morphology. Backscattered imaging was used to
quantitatively identify the composition of carbides. Carbide morphologies of the samples were
examined in transverse planes.
Results and Discussion
Effects of cobalt on alloy performance. Fig.1 shows the thermal expansion behavior of 1#alloy,
2#alloy and 3# alloy. Comparing 2# alloy with 3# alloy, it can be seen that the coefficient of thermal
expansion of the alloys were almost constant with the increasing of cobalt content. Comparing 2#
alloy and 3# alloy with 1# alloy, cobalt content of 1# alloy was significantly decreased, and there
are not much difference between the coefficients and in particular, the coefficient of thermal
expansion of 2# alloy was higher than that of 1# alloy by 1.9%. According to a literature [5], the
content of the content of iron directly affected the expansion coefficient of the alloys, and the iron
content became larger, the coefficient of thermal expansion became higher. As described by the
literature, in this work, the mass fraction of iron in 1# alloy was 2.07%, which was likely to be the
cause of the decrease of coefficient of thermal expansion.
Effects of tungsten on alloy performance. Fig.2 shows the thermal expansion behavior of 4# alloy
and 5# alloy. It can be seen that addition of proper amount of tungsten can reduce the coefficient of
thermal expansion. This is because that Ni-25%Mo-8%Cr alloy derives its low thermal expansion
from small precipitates (in size on the order of 10nm) of an orthorhombic Ni2(Mo, Cr), which is
Long range ordered intermetallic phase forming during long time aging. And the addition of
tungsten, it is possible to increase the volume fraction of Ni2 (Mo, Cr) phase, or form new phases
which are beneficial to reduce the coefficient of thermal expansion.
 Materials Science Forum Vol. 849 505

The coefficient of thermal expansion (10-6/℃)

14.5
1#
2#
14.0 3#

13.5

13.0

12.5

12.0

400 500 600 700 800

Temperature (℃)
Fig. 1 Thermal expansion curves of 1# alloy, 2# alloy and 3# alloy
15.0
4#
The coefficient of thermal expansion (10 /℃)

14.5 5#
-6

14.0

13.5

13.0

12.5

12.0

11.5

11.0

10.5

10.0
400 500 600 700 800
Temperature(℃)
Fig. 2 Thermal expansion curves of 4#alloy and 5#alloy

Table 2 Tensile properties of 4 # alloy and 5 # alloy at room temperature

Properties 4# 5#
Tensile strength Rm (Mpa) 909 1437
Yield strength RP0.2 (Mpa) 416 919
Elongation A(%) 58 19
Reduction Z(%) 64 22
With the addition of tungsten, the tensile strength of 5# alloy reached 1437MPa, which was 1.6
times as much as 4# alloy. The yield strength of 5# alloy was 919Mpa, which was 2.2 times as
much as 4# alloy, as showed in Table 2. In the nickel based superalloys, the atomic radius of
tungsten is larger than that of the nickel, cobalt and iron. The tungsten atoms in the nickel based
superalloys cause significant expansion of the lattice, which will form large long range stress field.
The yield strength is significantly increased because of the formation preventing the dislocation to
move.
Table 3 Tensile properties of 4 # alloy and 5 # alloy at 650℃
Properties 4# 5#
Tensile strength Rm(Mpa) 580 860
Yield strength RP0.2(Mpa) 300 725
Elongation A(%) 18.5 6.0
Reduction Z(%) 23.8 8.0
506 Special and High Performance Structural Materials

The 650℃ tensile properties of the two alloys were basically consistent with that of the room
temperature tensile, as showed in Table 2 and Table 3. Tensile strength and yield strength of 5#
alloy at 650℃ were higher than that of 4# alloy, but the elongation and section expansion rate were
less. Because of that, the processing difficulty of 5# alloy is obviously higher than 4# alloy.
In order to improve the tensile strength and yield strength at different temperature, It can add
tungsten to alloys, as showed in Table 2 and Table 3.The microstructure of the 5#alloy was observed
by scanning electron microscope, it can be seen that a large amount of carbides appeared in the
grains and at grain boundaries after the solution and aging treatment as showed in Fig.3 and Table 4.
Because of these carbides, the aging effect of the alloy is increased and the mechanical properties of
the alloys are improved.

Fig. 3 SEM image of 5#alloy

Table 4 Chemical composition of precipitated phase in 5# alloy（at.%）
Position C Mn Mo Cr W Fe Co Ni
1 29.93 0.38 22.20 7.04 3.79 0.28 1.89 34.49
2 34.73 0.54 25.09 3.02 4.68 0.45 1.37 30.12
Effects of molybdenum on alloy performance. The thermal expansion curve of 5# alloy at high
temperature was relatively flat, as showed in Fig. 4. It can be seen that reducing the amount of
molybdenum and increasing the amount of tungsten are helpful to reduce the coefficient of thermal
expansion of the alloys at high temperature and improve the performance consistency of the
coefficient of thermal expansion from low to high temperature.
15.0
5#
The coefficient of thermal expansion (10 /℃)

14.5
6#
-6

14.0

13.5

13.0

12.5

12.0

11.5

11.0

10.5

10.0
400 500 600 700 800
Temperature (℃)
Fig. 4 Thermal expansion curves of 5# alloy and 6# alloy
 Materials Science Forum Vol. 849 507

Conclusion
1) It was founded that cobalt has no influence on the thermal expansion properties of the alloys.
2) Addition of proper amount of tungsten can reduce the coefficient of thermal expansion and
increase the mechanical properties of alloy both at room temperature and at high temperature.
3) Reducing the amount of molybdenum and increasing the amount of tungsten are helpful to
reduce the coefficient of thermal expansion of the alloys at high temperature and improve the
performance consistency of the coefficient of thermal expansion from low to high temperature.

Acknowledgements
High Technology Research and Development Program of China. (No.2012AA03A511)

References
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[2] Qi Huan, Review of Inconel718 alloy: Its history, properties, processing and developing
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[3] Zhang Shaowei, Application and development of Low-thermal expansion superalloy, Aviation
Engineering & Maintenance[J], 1994,(9) 5
[4] Srivastava s k. Low-thermal expansion, high Strength Ni-Cr-Mo alloy, for Gas Turbines. In
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