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of
FOUNDRY ENGINEERING
Published quarterly as the organ of the Foundry Commission of the Polish Academy of Sciences

ISSN (1897-3310)
Volume 8
Issue 2/2008
115 120

25/2

Creep-resistant austenitic cast steel

B. Piekarski*, J. Kubicki
Szczecin University of Technology, Al. Piastw 17, 70-310 Szczecin
*Corresponding author. E-mail adress: bogdan.piekarski@ps.pl
Received 08.02.2008; accepted in revised form 17.03.2008

Abstract
The study reviews the reference literature and gives some results of own investigations concerning changes of phase composition that
take place in creep-resistant austenitic cast steel of two generations due to an ageing treatment. The cast steel of the first generation
contains in its chemical composition only the alloying additives like nickel, chromium and silicon. Compared with the first group, the
chemical composition of the second generation cast steel has been enriched with additions of niobium and/or titanium.
Keywords: Austenitic cast steel; Phase composition; Precipitation process.

1. Introduction
Among different types of austenitic cast steel, for operation at
high temperatures the cast steel containing nickel from 18 to 38%,
chromium from 15 to 26%, silicon up to 2.5% and carbon from
0,15 to 0,6% (% max.) is used most frequently. This chemical
composition guarantees obtaining a stable austenitic structure at
both high and ambient temperatures. Increasing the content of
iron in Fe-Ni-Cr alloys definitely deteriorates their heat- and
creep-resistance, though on the other hand it is the main costeffective factor in this group of materials.
The oldest standard on the chemical composition of creepresistant steel castings is the standard developed by ACI
(American Casting Institute). The cast steel designation system
introduced by this standard is still used in worldwide technology,
while the proposed alloy grades serve as a reference and example
in the development of various national standards. In Poland, since
2004, the European Standard PN-EN 10295 Creep-resistant
steel castings has been used. Compared with the former Polish
Standard PN-90/H-83159 Heat- and creep-resistant cast steel, it
covers a wider range of alloys and chemical compositions, fully
satisfying the current demand of different industry sectors.
At present, three generations of the creep-resistant austenitic
cast steels are used [1]:

1st generation. Common type cast steel. Its main alloying

elements are nickel, chromium and silicon. It started to be
used worldwide in 50-ties and 60-ties of the past century.
2nd generation. Common type cast steel, additionally
enriched with niobium and titanium. Introduced to industry
in 70-ties of the past century.
3rd generation. The cast steel stabilised with niobium and/or
titanium and, additionally, inoculated with rare earth metals.
Used in industry since 80-ties of the past century.
All other modifications introduced successively to the
chemical composition of creep-resistant austenitic cast steels
aimed at a simultaneous improvement of the following three
parameters: creep resistance, operating temperature and resistance
to the effect of aggressive gas environments [15]. To achieve
this purpose, numerous elements, like Nb, Ti, Zr, V, W, Co, Mo
were introduced to the Cr-Ni and Ni-Cr cast steels, as single
additions or in combination, and in amounts from tenth to several
percent. Due to this, it was possible to obtain a combined effect of
the solution hardening of matrix (austenite) and precipitation
hardening of both matrix and grain boundaries [1, 2].
Conferring long life to the elements of machines and
equipment operating at high temperatures is a complex design
task requiring careful examination of numerous factors that
determine the life of parts during performance. These factors fall
into the three basic categories [6]:
-

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115

Material-related factors determined by the behaviour of

material and the process of its manufacture. When the
material is put in service, it undergoes some changes caused
by its attempt to obtain a state closer to the state of thermodynamic equilibrium than the state possessed initially,
considered optimum for the utilisation properties. These,
very undesirable, changes can be counteracted mainly
through proper choice of the chemical and phase
constituents of the material.
2. Environmental factors resulting from the operating
conditions. They include mechanical loads, corrosive effect
of the environment, thermal shocks, friction, etc. These
processes may co-act with each other and with the abovementioned spontaneous transformations, speeding up or
slowing down their course.
3. Design and engineering factors related with casting design
and operation, including correct layout and manufacture of
casting, strict observance of recommendations regarding
proper performance conditions as well as diagnosis of
failures, correct maintainance and repair procedures, modifications introduced to the cast material and casting design as
a result of experience acquired during its performance.
The effect of the above mentioned factors, usually acting
jointly, is responsible for the following types of material
degradation: creep, thermal fatigue or thermal-mechanical
fatigue, corrosion and erosion [16].
In this study, using data given in the reference literature and
the results of own investigations, the effect of material-related
factors on the structural stability of cast steels of the first and
second generation was analysed and examined.

J(412)M7C3 / J(440)M23C6

1.

20

10
5
0

200

400

600

800

1000

Fig. 1. Effect of 36Ni-18Cr cast steel ageing time on the relative

volume content of carbides [8]
Compared to the first generation cast steel with the same
carbon content, the content of carbide eutectic increases as well as
the massiveness of carbides present in this eutectic [14]. Joint
additions of niobium and titanium introduced to cast steel give
rise to the formation of straight and complex simple carbides. In
each of these cases, the simple carbides are characterised by
different morphologies [15, 16].
The process of annealing changes in a significant way the
phase composition and morphology of the precipitates. In the first
generation cast steel, the secondary chromium carbides of the
M23C6 type start precipitating (Fig. 1). Their content in structure is
function of the annealing time and temperature and of the alloy
chemical composition carbon and chromium content mainly. An
increase in the content of carbide phase is accompanied by a
respective change in the chemical composition of the matrix, i.e. a
high-rate chromium impoverishment Fig. 2. An example of the
steel structure as-cast and after annealing is shown in Figure 3.

2. The structural stability of cast steel

116

Time, hrs

90

C, wt-%
- 0.21
- 0.31
- 0.39

Content of Cr, wt-%

85
80

carbids
75
20

matrix

15
10

Carbides fraction, wt-%

In as-cast state, the matrix of austenitic cast steels is

composed of a supersaturated solid solution of austenite. The
structure of these alloys usually comprises also a carbide-austenite
eutectic, distributed mainly on the ternary grain boundaries, and
in the case of alloys containing below 0.2%C single carbides
present in the grain boundaries [7, 8]. The number and size of the
carbide particles depend, first of all, on the cooling rate and
carbon content in alloy [810].
In the first generation cast steel, the precipitating primary
carbides are chromium carbides of the M7C3 and M23C6 type
(symbol M in the stoichiometric formula of carbides corresponds
to chromium atoms mainly, but also to the atoms of iron, nickel,
manganese, etc. [7, 10]). The content of chromium carbides of the
M7C3 type in the as-cast structure of steel increases (compared
with the M23C6 carbide content) along with an increasing carbon
content (Fig. 1) [8, 10]. In the second generation cast steel
containing carbide-forming elements (mainly Nb and/or Ti), the
structure of alloy undergoes some important changes in respect of
the structure described above. In as-cast state, the eutectic is
formed of M7C3 and/or M23C6 carbides (depending on the Cr/C
ratio) and (depending on the type of the stabilisers used) of simple
carbides of the TiC and/or NbC type [1, 7, 13].

C, wt-%
- 0.21
- 0.31
- 0.39

15

8
6
4
2
0
0

200

400

600

800

1000

Time, hrs

Fig. 2. Effect of 36Ni-18Cr cast steel annealing time on:

a) chromium content in carbides and matrix,
b) the content of carbide phase [8]
The shape and size of the precipitating secondary carbides
definitely affect the alloy creep behaviour and plastic properties.
In this respect, more beneficial are fine globular particles instead
of large precipitates [6]. The structure still contains chromium

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1000

coagulation M6C

950

Temperature, oC

carbides of the M7C3 and M23C6 type; the content of the former
ones drops to zero after a longer time of annealing (Fig. 1, 4),
mainly due to the M7C3 + M M23C6 transformation [7, 13].

900

M6C

850
800
750

7C
3

700

M23C6 + M

+M

M6C

650

6C

600

10

Time, hrs

100

1000

Fig. 5. Time and temperature effect on the formation of M6C

carbides in 0.4C-55Ni-25Cr cast steel [7]
b

The precipitates rich in nickel and silicon, present in the

microstructure of first generation steel casting withdrawn from
use, are shown in Figure 6, while the results of local microanalysis of the chemical composition are compiled in Table 1.

10 m

Fig. 3. Microstructure of 0.4C-17Cr-34Ni steel as-cast (a) and

after annealing at 900oC/ 100 h (b) [8]

Temperature, oC

1000

2
10 m

M23C6

900

7C +
3 M

800
700
600
1

Fig. 6. Microstructure of casting made from 36Ni-17C steel

operating for about 5000 hours in a heat treatment furnace [8]

23 C
6

M7C3

10

100

1000

Time, hrs

Fig. 4. Effect of time and temperature on the transformation of

M7C3 carbides into M23C6 carbides in 0.4C-25Cr-20Ni
cast steel [7]
The M7C3 M23C6 transformation is proceeding between the
M7C3 carbides and austenite, and it is possible to have both
transformations in-situ together with an independent nucleation of
M23C6 carbides and simultaneous dissolution of M7C3 carbides in
matrix. In low-carbon cast steel, the procesess of precipitation are
proceeding mainly along the grain boundaries, while in mediumand high-carbon cast steels they also take place inside the
austenite grains [810, 17]. The structure of the aged cast steel
may also comprise chromium nitrocarbides of the M2(C,N) type
[7]. Long-term annealing at temperatures below 950oC [7] makes
carbides of both M23C6 and M7C3 type undergo further
transformation into M6C carbides (Fig. 5). The M6C carbides may
contain even up to 40% nickel and 10% silicon [7]. Contrary to
M7C3 M23C6 transformation, the M7C3 (M23C6) M6C
transformation originates not on the carbide/ matrix interface but
most probably in the crystal lattice of chromium carbides [7, 18].

Table 1.
Microanalysis (wt.%.) of the precipitates shown in Figure 6
The place of analysis
Si
Fe
Cr
Ni
1 0.2
17.5
75.6
6.5
2 8.8
4.6
48.1
37.4
matrix 1.6
46.2
13.8
38.4
In cast steels of the first and second generation, annealing can
give rise to a combined precipitation of M23C6 carbides and phase
. However, the probability of the precipitation of this phase is
rather small, because in cast alloys carbon content is usually much
higher than it is in alloys assigned for plastic working. Carbon
binds chromium into carbides, and as an immediate result of this
effect a drop in the content of this element in matrix below a level
indispensable for the precipitation of phase is observed [20].
The cast steel containing above 0.05% carbon is after solutioning
characterised by an austenitic structure with M23C6 carbides.
During annealing at temperatures below 1000oC, from the
austenite after solutioning are precipitating carbides of the M23C6
type, while phase is nucleating only when carbon content in the
austenite drops to a critical level (for 25Cr-20Ni steel this level is
0.006%) [20]. So, obtaining a low carbon level in the matrix of
creep-resistant high-carbon cast steel is practically impossible,
especially when the cast steel matrix is expected to have at the
same time a high chromium concentration. Under given
conditions of annealing and above the predetermined critical

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117

carbon content, when the state of equilibrium between carbides

and austenite has been reached, austenite continues behaving like
a carbon-saturated solid solution [20]. Besides carbon content, the
precipitation of phase also depends on the chemical composition
of alloy [2] and its occurrence is usually preceded by a long-term
annealing (Fig. 7). A typical arrangement of the needle-like
precipitates of phase in the cast steel matrix is shown in Figure
8.

carbides than it is possible to obtain with the sole addition of

niobium [25].
a

Temperature, oC

1000
900

800

700
600
100

1000

10000

100000

Time, hrs

Fig. 8. Precipitates of phase in the structure of pipe

centrifugally cast from 24Cr-24Ni Nb steel
after 95000 hours of operation [19]
The strong carbide-forming elements, like niobium and/or
titanium are usually addded to cast steel to form carbides much
more stable than the chromium carbides and to obtain due to this
an improvement of numerous physical and mechanical properties.
For low-carbon steels, the knowledge in this field has a wellgrounded fundamentals [6, 11, 21, 22].
The phase composition of the second generation cast steel is
more complex than that of the cast steel of the first generation,
mainly because its structure contains the co-existing complex and
simple carbides of both primary and secondary origin (Fig. 9).
In the structure of low-carbon cast steel during performance
are nucleating only carbides of the M23C6 and MC type. Carbides
of the MC type may contain chromium, the amount of which
usually decreases with the elapsing time of ageing [24, 25]. After
a long- term annealing, even two strong, carbide-forming
elements added jointly to steel are not capable of either stabilising
or improving the resistance to the growth of MC precipitates
this effect, by the way, is also obtained when only one of the two
elements is present. In cast steel containing niobium and titanium,
both these elements are found in the precipitates of MC carbides
[23, 24]. An addition of niobium and titanium to 25Cr-20Ni cast
steel produces structure with more uniform distribution of the
secondary precipitates and less continuous network of eutectic

118

10 m

Fig. 9. Microstructure of 30Ni-18Cr cast steel after the process of

annealing at 900oC/ 300h [23]: a) 0.03Nb and 0.03Ti, b) 0.08Ti
and 1.75Nb
Investigations of the effect of titanium and niobium on the
structure of 0.4C-25Cr-20Ni cast steel indicate that niobium does
promote the precipitates refinement at a temperature of 950oC but
with temperature this role is taken over by titanium (Fig. 10). The
morphology and distribution of the secondary carbides in matrix
depend on a total titanium/ niobium-carbon ratio (Fig. 11). The
content of the secondary simple carbides in the structure of cast
steel at a given temperature and time can be used for calculation
of the true operating temperature of the individual parts of
casting. An example of the practical application of quantitative
metallography is given in [15].
0,45
0,40

Size of carbids, m

Fig. 7. Time and temperature effect on the precipitation of phase

in 0.4C-25Cr-20Ni cast steel [7]

0,35

without of Nb or Ti
1,79%Nb
0,76%Ti
0,15%Ti+0,6%Nb

0,30
0,25

900

950

1000

1050

1100

Temperature, C

Fig. 10. Effect of stabilisers and temperature on the size

of secondary carbides in 0.4C-25Cr-20Ni cast steel after 1000
hour annealing [13]
In stabilised cast steels also the primary simple carbides are
not stable. Their decomposition is said to follow the reaction of
MC + M M6C [7]. The formation of M6C carbides is usually
accompanied by a drop in the content of other carbides present in
the cast steel structure with simultaneous increase in the total
content of carbide phases (Fig. 12).

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0,5

l,
0,4

0,3

and this may mean that they are a by-product of the MC G

transformation. The results of the chemical analyses in microregions [23] prove the presence of a nickel- and silicon-rich phase
on the MC carbide/matrix interface.

1100

1000

1
1,0

0,5

(Ti+Nb)/C

Fig. 11. Changes in microstructure of 0.4C-25Cr-20Ni cast steel

caused by joint addition of niobium and titanium after the process
of annealing at 1050oC/ 1000 hours [13]:
1 mean carbide dimensions, 2 mean carbide spacing

Temperature, oC

0,1

1.63%Si

1.84%Si

0,2

M23C6+G+NbC

900

2.62%Si
800

M23C6+NbC
700
1

10

20

50

100

Content of carbids, wt-%

Time, hrs
connecting
M23C6
NbC
M6C

Fig. 13. The curves of phase transformation in a time-temperature

system for 0.4C-35Ni- 20Cr-1.97Nb cast steel [29]

M23C6
Time, hrs

Fig. 12. Kinetics of M6C carbide precipitation in 25Cr-20Ni

(2.1Si-1.56Nb) cast steel
annealed at a temperature of 800oC [14]
However, the authors of some studies [2628] doubt it very
much that the precipitating nickel- and silicon-rich phases can be
the M6C type carbides. According to these authors it is much
more probable that the precipitating phases are phase G of a
symbol of M6Ni16Si7. An optimum temperature for the formation
of phase G in 25Cr-20Ni cast steel is 750800oC [26]. The
presence of this phase in the form of precipitates around the
particles of NbC carbides lying on the grain boundaries was
observed as early as after two hours of annealing (Fig. 13). The
process of the formation of phase G in austenitic cast steel
promotes an increase of the silicon content in alloy. In 35Ni-20Cr
cast steel, the beginning of the precipitation of phase G is shifting
together with the silicon content towards shorter times of
annealing and higher temperatures, with an upper value of
temperature exceeding 980oC (Fig. 13). Annealing at a
temperature equal to or higher than 980oC does not result even
after a very long time of annealing (up to 2400 hours) in MC G
transformation [15, 29]. The results of the studies described in
[2931] also point out to a significant role of silicon in the
process of phase G formation. No traces of phase G were
observed in the structure of samples made from the 25Cr-20Ni
cast steel stabilised with niobium and titanium and containing
0.7%Si, exposed to the effect of creep for 2647 hours at a
temperature of 8001000oC.
Within an area of the formation of phase G, the presence of
chromium carbide precipitates has also been observed (Fig. 14),

G
M23C6

10 m

Fig. 14. Examples of the presence of phase G in stabilised 30Ni18Cr cast steel; annealing at 900oC/ 300 hours [16]: a) 1 % Ti, b)
1.67% Nb, 0.05% Ti.
However, opinions of researchers vary as to the occurrence in
austenitic cast steel of M6C carbide or phase G.
Over the past decade, some remarks appeared in literature on
the presence in the structure of the niobium-stabilised and aged
36Ni-18Cr cast steel of phase rich in silicon and of a low carbon
content, called silicide and having the structure of M6C carbide
[32, 33]. From the results of studies presented in [34] it follows
that the structure of this phase extends over a wide range of
chemical compositions, e.g. A3B3C, A2B3SiC, where carbon can
be replaced with atoms of silicon, and A are atoms of V, Cr, Mn,
Fe, Co or Ni, while B are atoms of Nb, Ta, Mo or W.
B

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119

3. Conclusions
As follows from the above presented analysis of the reference
literature, an addition of niobium and/or titanium introduced to
the creep-resistant austenitic cast steel cannot guarantee obtaining
a fully stable structure in this alloy within the range of operating
temperatures, i.e. 600900oC.
It can be generally stated that in cast steels with an addition of
the stabilising elements it is possible to have the transformation of
MC-type carbides into phase G during casting operation at high
temperatures. The authors of this study did not find in the
available literature a single proof of an unfavorable effect of the
said phase on the utilisation properties of the creep-resistant
austenitic cast steel.

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