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of

ISSN (1897-3310)
Volume 9
Issue 4/2009

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

233 236

42/4

Investigations of high-temperature corrosion

of Cr-Ni cast steel
a

R. Zapaa *, B. Kalandyk
Department of Cast Alloys and Composites Engineering, Faculty of Foundry Engineering, University of Science and
Technology, Reymonta St. 23, 30-059 Cracow, Poland
*Corresponding author. E-mail address: renatazapala@poczta.onet.pl
Received 25.06.2009; accepted in revised form 07.07.2009

Abstract
Austenitic cast steels of Cr25-Ni32-Nb grade have found wide application in chemical and petrochemical industries. This study discusses
the problem of the kinetics of oxidation of these materials in the atmosphere of laboratory air at temperatures of 930 and 1000 C.
Considering the operating conditions of castings (centrifugally cast reformer tubes), the results of the oxidation test of specimens taken
from the zone of columnar crystals and equiaxial grains were presented.
Keywords: Fe-Cr-Ni alloys; Oxidation; High temperature corrosion; Oxidation kinetic; Scale

1. Introduction
Alloys assigned for high-temperature performance should
offer not only the required mechanical properties at high
temperatures (creep resistance) but also, and mainly, the
resistance to chemical degradation (heat and corrosion resistance).
Moreover, they should be materials relatively cheap and easy in
fabrication. To manufacture alloys that would satisfy all these
requirements is the task very difficult. In many cases, the addition
of an element while improving some of the properties deteriorates
other (to mention molybdenum as an example). The materials that
combine the above mentioned properties are, among others, ironbased alloys [14]. Yet, though iron is characterized by relatively
high melting point, its oxides formed in the oxidizing
environment cannot provide the required protection at
temperatures above 550 C [5]. Therefore, certain elements, like
chromium, aluminium, silicon, etc. are added to the alloys to
enhance the protective power of the scale. In the case of oxides,
the scale composed of Cr2O3 is one of those that offer the best
protective properties (besides -Al2O3) [3, 6].
The family of iron-based alloys also includes the heat-resistant
Cr25-Ni32-Nb cast steels that find application in construction of

the chemical and petrochemical installations, e.g. installations

used for methane steam catalytic conversion. The above
mentioned cast steel grades are successfully used for tubes
operating in primary steam reforming furnaces, where a mixture
of hydrocarbons and steam is transformed in synthesis gas, used
next in production of methanol or ammonia [7, 8]. Tubes are
exposed to long-term (10-12 years even) effect of high
temperatures (about 1050 C) and aggressive environments (air,
steam, carbon and sulphur compounds) [911].
In this study an attempt has been made to evaluate the resistance
to high-temperature corrosion of austenitic chromium-nickel cast
steels with addition of niobium, used for tubes operating in
installations for methane steam catalytic conversion.

2. Methods of investigation
The test material were laboratory tubes centrifugally cast from
austenitic chromium-nickel steel with addition of niobium. The
specimens of a disc-like shape and dimensions of
= 6 mm and h = 1 mm were cut out from the rods turned in
direction normal to the tube axis. To reveal various

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macrostructures present on the tube cross-section (typical of the

cast elements), the side surfaces of the rods were etched. Next, the
specimens were cut out from the zone of columnar crystals and
equiaxial grains. The specimens were mechanically polished to a
mirror shine and degreased in ultrasonic washer in the bath of
water with detergent. Chemical composition of the examined
materials is stated in Table 1.
Oxidizing was carried out for 24 h in the atmosphere of
laboratory air at atmospheric pressure and temperatures of 930
and 1000 C. The oxidizing rate was examined on LABSYS
apparatus made by SETARAM.
Table 1.
The chemical composition of cast steel examined
Material Chemical composition [wt% ]
C
Si
Mn
Cr
Ni
P1_r
0,29 1,99 1,06 24,99 30,82
P1_s
r equiaxed grains, s columnar grains

Nb

Mo

1,16

0,17

The scale formed on the alloy was examined under an optical

NEOPHOT 32 microscope. Additional examinations were made
under a JOEL 5500LV scanning electron microscope equipped
with EDS system made by IXRF, assigned for X-ray
microanalysis.

3. Results and discussion

Figure 1 ab shows the oxidizing process of austenitic
chromium-nickel cast steel with addition of niobium. The studies
of the process kinetics have proved that the run of the oxidation
curves plotted for the examined specimens can be, in
approximation, described by parabolic law.

Fig.1. Oxidation of the Cr25-Ni32-Nb in an air at atmospheric

pressure and 930, 1000 C - equiaxed grains (a) and columnar
grains (b)
The values of parabola exponents for specimens taken from
the zone of columnar crystals and equiaxial grains subjected to the
oxidation process are given in Table 2.
Table 2.
Exponents in the kinetic equation for the specimens with equiaxed
grains and columnar grains
Oxidation

Material
P1_r
P1_s

930C
1,98
1,87

1000C
1,96
1,68

Table 3 compares the parabolic constant velocities kp obtained

for the examined material during oxidation process. Very small
(one order of magnitude) differences in the values of the constant
oxidation rates were observed in specimens oxidized at different
temperatures. At the examined temperatures, similar oxidation
rates were observed in specimens cut out from the zone of
columnar crystals and equiaxial grains. In the case of materials
oxidized at 1000 C, because of disturbances observed in the
plotted curves of oxidation kinetics, two constant oxidation rates
were adopted. However, no significant differences in the values of
the above mentioned constants were observed. Most probably, the
disturbances were due to the occurrence of cracks and/or pores
[12, 13], since the exposure of metallic core speeds up the
oxidation process, which in the diagram of the oxidation kinetics
assumes the form of characteristic steps. As soon as a new layer
is formed, the changes in the specimen weight get stabilized.
Because of these variations, the newly formed scale will not be
homogeneous and uniform enough, which will provoke its
premature detachment from the metallic core (Fig. 3).
Table 3.
Values of kp for the investigated alloy
Material
P1_r
P1_s

234

Values of k [ g 2 /(cm4 s1) ]

p
1000C
930C
A
B
2,8110-12
1,0410-11
1,1110-11
4,4710-12
1,2310-11
1,4110-11

ARCHIVES of FOUNDRY ENGINEERING Volume 9, Issue 4/2009, 233-236

Figure 2 shows the results of examinations of the surface of

specimens subjected to the effect of air at a temperature of 930
C. Figure 3 shows the same results for a temperature of 1000 C.
The surface of the scale formed at a temperature of 930 C during
the oxidation in air was coated with scattered crystalline forms of
different shapes (from flat to spherical) Fig. 2b. The performed
EDS analysis indicated that, irrespective of morphology, the
composition was rich in Cr, Mn and O. The enrichment in the
above mentioned elements was also characteristic of the areas of
the scale lying between the crystalline forms. This phase could be
spinel MnCr2O4 [14]. According to Jian et al., the said spinel may
be formed even at very low content of manganese in alloy.
Special attention deserves the fact that it is characterized by
definitely higher thermodynamic stability than Cr2O3 and MnO
[15, 16].

In the case of the examined specimens, two characteristic areas

can be distinguished on their surface:
with the scale residue (Fig. 3 a) enriched in Cr, Mn and O2
and with small quantities of Fe,
without the scale residue (Fig. 3 b) enriched in matrix
elements Ni, Si, Cr, Fe and Nb.

Chemical composition [wt% ]

Cr
Mn
Fe
35,86
35,89
1,48
38,04
31,17
1,39
52,30
15,87
1,22
Chemical composition [wt% ]
O
Si
Cr
Mn
Fe
Ni
Nb
1 15,67 1,54 12,52
0
37,73 32,71
b
2
2,82 2,06 12,40
0
44,69 38,01
3 17,69 1,51 10,24
0
34,76 28,95 6,84
Fig.3. Surface of specimen oxidized at 1000 C for 24h in air
a), b) magn. 1000x (SEM image with EDS analysis)

Samples
notation
1
a
2
3

Samples
Chemical composition [wt% ]
notation
O
Cr
Mn
1
34,92
43,99
21,08
2
41,89
49,22
8,88
3
36,08
55,17
8,75
4
42,08
36,34
21,39
Fig. 2. Surface of specimen oxidized at 930 C for 24h in air
a) magn. 50x, b) magn. 1000x (SEM image with EDS analysis)
The increasing temperature of oxidation is the factor
contributing to an even more serious degradation of the formed
scale. On the surface of the specimens oxidized at a temperature
of 1000 C, besides very scarce areas in which the scale adheres
strongly to the substrate, there are regions totally deprived of the
products of the reaction of oxidation.

O
26,77
29,39
30,60

4. Conclusions

The rate of high-temperature corrosion process in specimens

oxidized in the atmosphere of laboratory air at temperatures
of 930 and 1000 C does not depend on alloy macrostructure.
The run of oxidation curves is for both processes nearly
parabolic. In the case of the specimens taken from the zone
of equiaxial crystals, the course of the oxidation in air

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resembles more an ideal run (the values of parabola

exponents n 2).
The structure of the scale depends on the temperature at
which it has been formed. The scale formed during oxidation
in air at a temperature of 930 C revealed strong adherence
to the cast steel surface and was free from the cracks and
discontinuities. On the other hand, the scale formed at a
temperature of 1000 C suffered almost total degradation.

References
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