Corrosion Science 49 (2007) 1869–1877

www.elsevier.com/locate/corsci

Hot corrosion behaviour of Ni3Al in

sulphate–chloride mixtures in the atmosphere
Aneta Magdziarz *, Zofia Kalicka
Faculty of Metals Engineering & Computer Science for Industry, AGH University of Science and
Technology, Al. Mickiewicza 30, 30-059 Krakow, Poland

Received 9 January 2006; accepted 17 October 2006

Available online 8 December 2006

Abstract

Hot corrosion of Ni3Al intermetallic compound in the presence of sulphate–chloride mixtures was
studied. A comminuted Ni3Al mixed with NaCl–Na2SO4, NaCl–Li2SO4, LiCl–Na2SO4, LiCl–Li2SO4
additions was oxidized in the air up to 1000 °C with linearly increasing temperature and isothermally
within the temperature range of 500–700 °C. The corrosion process was observed by thermogravi-
metric method using Mettler thermoanalyzer.
The experiments indicated that LiCl (10 wt.%)–Li2SO4 mixture was the most corrosive agent. It
was also found that by addition of MgO the corrosion of Ni3Al was reduced. Phase composition of
the corrosion products was established by X-ray diffraction analysis; there were detected Al2O3,
Al2S3, NaAlO2 (or LiAlO2) as intermediate products, nickel sulphides, NiO and NiAl2O4. NiAl2O4
spinel was formed only at the highest temperatures, while at lower temperatures alumina was present
instead of spinel.
Hot corrosion behaviour of Ni3Al in sulphate–chloride mixtures in air atmosphere.
Ó 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Intermetallics; A. Molten salts; C. High temperature oxidation; C. Hot corrosion; C. Oxidation

1. Introduction

Intermetallic compounds are a group of materials with a wide variety of useful proper-
ties for applications as resistors, magnets and superconductors, heating elements, structural
*
Corresponding author. Tel.: +48 12 617 25 60; fax: +48 12 633 36 73.
E-mail address: kalicka@metal.agh.edu.pl (A. Magdziarz).

0010-938X/$ - see front matter Ó 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2006.10.010
1870 A. Magdziarz, Z. Kalicka / Corrosion Science 49 (2007) 1869–1877

alloys and corrosion resistant coatings [1,2]. Among them aluminides are particularly
attractive due to their potential of forming of protective alumina layers at high tempera-
tures. They have low specific densities, relatively high melting temperatures and good heat
resistances [3]. Two intermetallic phases, NiAl and Ni3Al, are of interest for high temper-
ature applications. For instance Ni3Al-base alloys have been found to be promising struc-
tural materials for such high-temperature applications like gas turbine engines [1–3].
The oxidation mechanism of a pure Ni3Al has been already described extensively [4–6].
When Ni3Al is exposed to high-temperature oxidation at the air atmosphere, the main
products of the process are NiO and Al2O3. The products of high-temperature oxidation
are different depending on time and temperature. It was observed, that for an isothermal
oxidation at 1000 °C for 60 h, the oxide scales were composed of NiO (inner layer),
NiAl2O4 (intermediate), Al2O3 (outer layer) from the surface, while at 1200 °C the surface
was completely covered with Al2O3 [6].
Ni3Al is the material, which is currently used in the industry, when combustion gases
are produced. When fuels containing sulphur, sodium and vanadium are burned, sodium
sulphate (Na2SO4) and sodium vanadate (NaVO3) appear in combustion ashes [7,8].
Fused salts deposited on Ni3Al materials involve the loss of corrosive resistance of the lat-
ter at high temperatures. The corrosion behaviour has been thoroughly studied for nickel
[9] and then for Ni3Al [10]. The results have shown that the corrosion rate of Ni3Al is
significantly accelerated by the presence of the salt deposits of Na2SO4–NaCl with the
dominant part at Na2SO4. That type of the sulphate-induced hot corrosion of nickel
has been the subject of considerable research as nickel and nickel base alloys are particu-
larly prone to this type of corrosion [9]. All previous studies of the sulphate induced hot
corrosion have been made at the temperatures above the melting point of a pure Na2SO4
(m.p. 884 °C). The corrosion of Ni3Al at 900 °C produces scales containing NiO (outer
layer), Al2O3 (inner layer) and the spinel NiAl2O4 (intermediate layer) [10]. The corrosion
of Ni3Al in atmospheres containing SO2 is much faster then in oxygen gas and leads to
formation of scales containing mixtures of oxides and sulphides.
Effect of the other than sodium alkali metal sulphates on Ni3Al hot corrosion has not
been studied yet.
The present study is aimed at investigation of the effects of the mixtures of sodium and
lithium sulphates and their chlorides on Ni3Al corrosion.

2. Experimental

The studies were made on mechanically comminuted Ni3Al. The oxidation behaviour of
Ni3Al samples mixed with the sulphate–chloride solid corrodents was investigated in the
air. The following mixtures were used: NaCl–Na2SO4, NaCl–Li2SO4, LiCl–Na2SO4,
LiCl–Li2SO4. The samples of Ni3Al mixed with above salts (always 30 wt. % added salts)
placed in platinum crucibles were studied by thermal analysis.
Recording of thermogravimetry (TG) curves for the samples heated in the air was per-
formed using a METTLER termoanalyzer. The obtained thermoanalytical diagrams
referred to the samples of 65 mg mass. The weight of Ni3Al compound in every sample
was the same (45.5 mg). At first experiments a 10 °C/min heating rate was applied within
the temperature range from 20 °C to 1000 °C, with the air-flow of 5 dm3/h. Then the tests
on isothermal oxidation at 500 °C, 600 °C, 650 °C and 700 °C for 5 h, with the same flow
of air, were performed. The oxidized samples were examined by means of X-ray diffraction
 A. Magdziarz, Z. Kalicka / Corrosion Science 49 (2007) 1869–1877 1871

analysis (XRD) and scanning electron microscopy (SEM) to establish their phase
composition.
The performed oxidation by the linear growth of temperature was aimed at investiga-
tion of the effects of NaCl content in the mixture with Na2SO4 and of the effect of substi-
tution of lithium for sodium in the sulphate–chloride mixture on corrosion behaviour of
Ni3Al, while for isothermal oxidation at establishing of the temperature dependence of
the oxidation rate of Ni3Al with NaCl–Li2SO4, LiCl–Na2SO4 and LiCl–Li2SO4 corro-
dents, and also of the effect of MgO additions.

3. Results

3.1. Influence of NaCl–Na2SO4 composition on Ni3Al corrosion

The preliminary tests on a pure Ni3Al and the Ni3Al mixed with NaCl, Na2SO4 and
NaCl–Na2SO4, in succession, were carried out. No oxidation was observed up to
1000 °C for pure Ni3Al and Ni3Al coated with nothing but pure NaCl only. However
the corrosive attack occurred in the presence of Na2SO4 either when pure or mixed with
NaCl. The detrimental effect of Na2SO4 on Ni3Al was observed at above 700–800 °C,
depending on NaCl content of the salts’ mixtures.
Fig. 1 shows TG curves of oxidation of Ni3Al under salts’ deposits. The oxidation pro-
cess with a pure Na2SO4 started at the highest temperature. The deposits of NaCl–Na2SO4
mixture containing 25 wt.% of NaCl induced oxidation at lower temperature. The lowest

70 wt.% Ni3Al- 30 wt. % salts

85

Na2SO4
80 NaCl-Na2SO4 proportion 1:3
NaCl-Na2SO4 proportion 1:9
Sample mass (mg)

75

70

65

60
0 200 400 600 800 1000
Temperature (oC)
Fig. 1. TG curves for linear heating of Ni3Al with addition (30 wt.%) of sodium sulphate and sodium sulphate–
chloride mixtures.
1872 A. Magdziarz, Z. Kalicka / Corrosion Science 49 (2007) 1869–1877

Table 1
Oxidation products detected by X-ray diffraction for Ni3Al heated with 30 wt.% mixture of NaCl–Na2SO4
(proportion 1:9) to different temperatures
T (°C) Products
740 NiO Ni3S2 NiS NaAlO2 –
800 NiO Ni3S2 – Na17Al5O16 –
1000 NiO – – – NiAl2O4

temperature of the corrosion attack was observed for the saline mixture with about
10 wt.% NaCl and 90 wt.% Na2SO4 (eutectic point at 625 °C). The TG curves for all sam-
ples had similar shape.
X-ray diffraction analyses were made for the samples of Ni3Al with NaCl (10 wt.%)–
Na2SO4, heated up to 740 °C, 800 °C and 1000 °C, then cooled down. The results are pre-
sented in Table 1. The oxidation products were mainly composed of NiO, no pure Al2O3
was detected. Sodium aluminate NaAlO2 was observed at the first stage of the oxidation
process but at the higher temperatures it was transformed into NiAl2O4 spinel. Some
amounts of Ni3S2 were detected at 740 °C and 800 °C and NiS at 740 °C as well.

3.2. Effect of substitution of the lithium salts for the sodium salts

Starting from the above studied mixture of 10 wt.% NaCl–90 wt.% Na2SO4, the next
experiments were focused on the effect of substitution of lithium for sodium cation in

70 wt.% Ni3Al - 30 wt.%salts

80

NaCl-Na2SO4 (1:9)
76 NaCl-Li2SO4 (1:9)
LiCl-Na2SO4 (1:9)
Sample mass (mg)

LiCl-Li2SO4 (1:9)

72

68

64

60
0 200 400 600 800 1000
Temperature (oC)
Fig. 2. TG curves for linear heating of Ni3Al with addition (30 wt.%) of sodium and lithium sulphate–chloride
mixtures.
 A. Magdziarz, Z. Kalicka / Corrosion Science 49 (2007) 1869–1877 1873

Table 2
Oxidation products detected by X-ray diffraction for Ni3Al heated with 30 wt.% mixture of LiCl–Li2SO4
(proportion 1:9) to different temperatures
T (°C) Products
700 NiO Ni3S2 Ni3.1S2 Al2S3 – –
800 NiO – Ni3.1S2 Al2S3 LiAlO2 –
900 NiO Ni3S2 Ni3.1S2 – – NiAl2O4
1000 NiO Ni2.8S2 – – – NiAl2O4

the deposits. The comparison of TG plots for Ni3Al oxidation in NaCl–Na2SO4, LiCl–
Na2SO4, NaCl–Li2SO4 and LiCl–Li2SO4 deposits is presented in Fig. 2. The mixture of
lithium salts (10 wt.% LiCl–90 wt.% Li2SO4), with melting point at 495 °C, appeared to
be the most corrosive agent – the oxidation process of Ni3Al appeared on TG curve at
about 660 °C. However, lithium–sodium salts’ mixtures did not induce oxidation of Ni3Al
at lower temperature than sodium–sodium mixture.
The oxidation products formed in 10 wt.% LiCl–90 wt.% Li2SO4 surroundings were
analyzed by X-ray diffraction (Table 2). There were found Al2S3 and LiAlO2 as the inter-
mediate products existing within the temperature range of 700–800 °C. Contrary to NaCl–
Na2SO4 mixtures induced corrosion, nonstoichiometric nickel sulphides were found with
no stoichiometric NiS. As previously (Table 1), NiO was the main product at every
temperature and nickel aluminate NiAl2O4 was detected as the final product stable at high
temperatures (900 °C and 1000 °C).

3.3. Isothermal oxidation of Ni3Al in sulphate–chloride mixtures

Isothermal oxidation tests for Ni3Al with different salts mixtures were performed in the
air at 500 °C, 600 °C, 650 °C and 700 °C for 5 h (Figs. 3–5). In general, the courses of oxi-
dation were dependent on the temperature and the salts deposits composition. The higher
rate of oxidation at 700 °C was observed for 10 wt.% LiCl–90 wt.% Li2SO4 deposit (Fig. 3)
while a little smaller one for 10 wt.% NaCl–90 wt.% Li2SO4 (Fig. 4). For the case of
10 wt.% LiCl–90 wt.% Na2SO4 mixture, the mass gain plot at 700 °C showed an interme-
diate stage of reduced rate (Fig. 5). That mixture has been previously qualified (Fig. 1) as a
slightly less corrosive agent than the other ones. It is worth of notice that at such low tem-
perature as 500 °C, the oxidation of Ni3Al proceeded with a quite high rate for the all ana-
lysed mixtures.
The oxidation products formed at 700 °C and 650 °C in the mixture of Ni3Al with
10 wt.% LiCl–90 wt.% Li2SO4 are presented in Tables 3 and 4. By 5 h of heating, the for-
mation of NiAl2O4 spinel was not observed, either at 650 °C or 700 °C. Contrary to the
experiments performed at the higher temperatures (Tables 1 and 2) the alumina was found.
It was persisted the longer time at lower temperature. Aluminum sulphide Al2S3 existed
only during a short time interval of the isothermal heating (similarly as in Table 2).

3.4. Protective effect of MgO addition

Sulphate–chloride mixtures appeared to be less corrosive when MgO was added. The
results of the oxidation of Ni3Al at 700 °C during 5 h of the heating in the presence of
1874 A. Magdziarz, Z. Kalicka / Corrosion Science 49 (2007) 1869–1877

10 wt.% LiCl - 90 wt.% Li2SO4

20
o
500 C
o
550 C
o
600 C
o
650 C
o
16 700 C
Mass gain (mg)

12

0
0 1 2 3 4 5
Time (h)
Fig. 3. Mass gain vs. time plots of Ni3Al with 10 wt.% LiCl–90 wt.% Li2SO4 mixture during isothermal oxidation
in the air for 5 h.

10 wt.% NaCl- 90 wt. % Li2SO4

20
500 o C
600 o C
650 o C
16
700 o C
Mass gain (mg)

12

0
0 1 2 3 4 5
Time (h)
Fig. 4. Mass gain vs. time plots of Ni3Al with 10 wt.% NaCl–90 wt.% Li2SO4 during isothermal oxidation in the
air for 5 h.
 A. Magdziarz, Z. Kalicka / Corrosion Science 49 (2007) 1869–1877 1875

10 wt.% LiCl - 90 wt.% Na2SO4

20

16
500 oC
600 oC
650 oC
Mass gain (mg)

12 700 oC

0
0 1 2 3 4 5
Time (h)
Fig. 5. Mass gain vs. time plots of Ni3Al with 10 wt.% LiCl–90 wt.% Na2SO4 during isothermal oxidation in the
air for 5 h.

Table 3
Oxidation products for Ni3Al with 30 wt.% mixture of LiCl–Li2SO4 (proportion 1:9) after isothermal heating at
700 °C during 5 h
Time (h) Products
0.16 NiO Ni3S2 Al2O3 Al2S3 – Li2Ni8O10
0.5 NiO Ni3S2 – Al2S3 – –
1 NiO Ni3S2 Al2O3 – – Li2NiO2.9
5 NiO Ni3S2 – – LiAlO2
Ni2.8S2
Ni3.1S2
Ni7S6

Table 4
Oxidation products for Ni3Al with 30 wt.% mixture of LiCl–Li2SO4 (proportion 1:9) after isothermal heating at
650 °C during 5 h
Time (h) Products
0.33 NiO Ni3S2 – Al2S3 – –
NiS1.03
0.5 NiO Ni3S2 Al2O3 – LiNiO2 LiAlO2
1 NiO Ni3S2 Al2O3 – – LiAlO2
NiS1.03
5 NiO Ni3S2 Al2O3 – – LiAlO2
Ni7S6
1876 A. Magdziarz, Z. Kalicka / Corrosion Science 49 (2007) 1869–1877

20

LiCl- Li2SO4 (1:9) with MgO (30 wt.%)

LiCl- Li2SO4 (1:9) without MgO
16
Mass gain (mg)

12

0
0 1 2 3 4 5
Time (h)
Fig. 6. Mass gain vs. time plots of Ni3Al with 10 wt.% LiCl–90 wt.% Li2SO4 during isothermal oxidation at
700 °C in the air for 5 h with and without addition of MgO.

10 wt.% LiCl–90 wt.% Li2SO4 with and without MgO addition are compared in Fig. 6.
The effect of reduction of the oxidation rate is evident, even at such a high temperature.

4. Conclusions

The experiments carried on the oxidation of a comminuted Ni3Al in the air atmosphere
indicate that Ni3Al is losing his corrosive resistance to oxidation at high temperatures
when a sulphate–chloride mixture of sodium or lithium is deposited on it. All experiments
were carried out with the samples containing 30 wt.% of added salts. Among the salts
studied, the LiCl (10 wt.%)–Li2SO4 appeared to be the most corrosive mixture, which is
indicated by the fact that the oxidation process starts at a lower temperature than for
the case of NaCl (10 wt.%)–Na2SO4. Melting points of NaCl–Na2SO4 (1:9) and LiCl–
Li2SO4 (1:9) are respectively, 625 °C and 495 °C, so the corrosion processes are accelerated
by electrochemical phenomena. However, every mixture of the salts used (not only LiCl–
Na2SO4) induced corrosion of Ni3Al at 500 °C with the rate, which was low but not to be
neglected. It was found that MgO addition to the salts deposit may, to some degree, pro-
tect Ni3Al material against hot corrosion.
According to the results of the phase composition analyses, the oxidation process of
Ni3Al in the air in the presence of sulphate–chloride mixtures of sodium or lithium may
be presented schematically as follows:
Ni3 Al ! Al2 S3 ! Al2 O3 ! NaAlO2 or LiAlO2 ! NiAl2 O4
and
Ni3 Al ! nickel sulphides and NiO ! NiAl2 O4
 A. Magdziarz, Z. Kalicka / Corrosion Science 49 (2007) 1869–1877 1877

NiO was the main product at every temperature and finally it was present together with
nickel aluminate NiAl2O4 at high temperatures (900–1000 °C). During 5 h of heating
at 700 °C a spinel NiAl2O4 was not detected. Alumina was detected only as an intermedi-
ate product, converting into the spinel NiAl2O4 at high temperatures. At the lower temper-
ature the alumina was persisted the longer time. Nickel formed sulphides, Ni3S2 or non
stoichiometric for every sample studied. NiS was detected only in one sample at 740 °C.
In the corrosion products analyzed at 650 °C and higher temperatures there were not
found any chlorine, because NaCl and LiCl salts are very volatile.

Acknowledgements

The work was supported by the Polish State Committee for Scientific Research (KBN)-
Grant No 4 T08B 049 25.
The samples of Ni3Al studied were prepared by Polish Academy of Science (Kraków)
by synthesis from high-purity metals in a vacuum induction furnace under argon and cast-
ing into graphite moulds.
The authors acknowledge gratefully the X-ray analysis made by Mr. S. Kotas (Polish
Academy of Science, Kraków).

References

[1] M. Schütze, Corrosion and Environmental Degradation, Wiley-VCH, Weinheim, 2000.

[2] J.H. Westbrook, R.L. Fleischer, Intermetallic Compounds, John Wiley & Sons, England, 2000.
[3] C.T. Liu, J. Stringer, J.N. Mundy, L.L. Horton, P. Angelini, Ordered intermetallic alloys: an assessment,
Intermetallics 5 (1997) 579–595.
[4] A. Velon, D.-Q. Yi, Influence of Cr on the oxidation of Fe3Al and Ni3Al at 500 °C, Oxid. Met. 57 (2002)
13–31.
[5] Z. Liu, W. Geo, Oxidation behaviour of cast Ni3Al alloys and microcrystalline Ni3Al + 5% Cr coatings with
and without Y doping, Oxid. Met. 55 (2001) 481–504.
[6] S.C. Choi, H.J. Cho, Y.J. Kim, D.B. Lee, High-temperature oxidation behaviour of pure Ni3Al, Oxid. Met.
46 (1996) 51–72.
[7] E. Otero, A. Pardo, J. Hernaez, F.J. Perez, The hot corrosion of IN-657 superalloy in Na2SO4–V2O5 melt
eutectic, Corros. Sci. 32 (1991) 676–683.
[8] P. Kofstad, High Temperature Corrosion, Elsevier Applied Science, London, 1988.
[9] P.L. Karl, P. Kofstad, Sulphate-induced hot corrosion of nickel, Oxid. Met. 21 (1984) 233–270.
[10] Y. Niu, F. Gesmundo, F. Viani, W. Wu, The corrosion of Ni3Al in a combustion gas with and without
Na2SO4–NaCl deposits at 600–800 °C, Oxid. Met. 42 (1994) 265–284.