Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Received: 21 November 2013 / Revised: 9 January 2014 / Published online: 15 July 2014
The Chinese Society for Metals and Springer-Verlag Berlin Heidelberg 2014
Abstract A Cr-modified aluminide coating is prepared on a Ni-based superalloy using arc ion plating and subsequent
pack cementation aluminizing. Hot corrosion behavior of the Cr-modified aluminide coating exposed to molten Na2SO4/
K2SO4 (3:1) or Na2SO4/NaCl (3:1) salts at 900 C in static air are evaluated as well as the aluminide coating. The results
indicate that compared with the aluminide coating, the anti-corrosion properties of the Cr-modified aluminide coating in
the both salts are improved, which should be attributed to the beneficial effect of the Cr in the coating. The corrosion
mechanism of the Cr-modified aluminide coating, especially the role of Cr in the mixture salt corrosion, is discussed.
KEY WORDS:
Arc ion plating; Pack cementation aluminizing; Superalloy; Cr-modified aluminide coating;
Hot corrosion
1 Introduction
Currently, Ni-based superalloys are widely applied to turbine blades or other components of gas turbines for their
excellent high-temperature mechanical properties. These
components must exhibit a high level of resistance to the
oxidation and corrosion conditions generated by the combustion environment and be resistant to any associated
erosion/corrosion conditions produced as a result of particulate ingestion or solids formed by incomplete combustion [1]. The alloying requirements for these high
volume fraction gamma prime materials result in a reduction in corrosion resistance and therefore, surface coatings
are widely used. The general design philosophy is to select
123
628
2 Experimental
A Ni-based superalloy DSM11 with nominal composition
(wt%) of Al 2.9, Ti 4.9, Cr 13.5, Co 9.5, W 3.7, Mo 1.5, Ta
2.8, C 0.1 and balanced of Ni was used as the substrate.
Specimens with dimensions of 15 mm in diameter and
2 mm in thickness were ground with 800-mesh SiC paper,
peened in a wet atmosphere (200-mesh glass ball), and then
ultrasonically cleaned with acetone, ethanol, and deionised
water successively. The Cr-modified aluminide (for short
as AlCr) coating was prepared by depositing the Cr layer
firstly and then aluminizing by pack cementation. Before
deposition, bombardment cleaning was carried out after
base pressure of the chamber was pumped below
6 9 10-3 Pa. The working pressure was maintained at
0.2 Pa by flowing argon into the chamber. Detailed deposition parameters are given in Table 1. Pack powder mixture for aluminizing consisted of 96 wt% FeAl powders as
source of aluminum and 4 wt% NH4Cl as activator. The
specimens were buried in the powder mixture. The furnace
chamber was pumped to at least 1 9 102 Pa, then heated to
900 C. The soaking time was 5 h. The aluminized coating
was also prepared by pack cementation. The contents of the
two coatings are listed in Table 2.
Hot corrosion behaviors of the DSM11 alloy, the aluminized coating, and the AlCr coating specimens were
performed in a muffle furnace in static air. Before hot
corrosion test, specimens were placed on a hot plate and
then brushed with Na2SO4/K2SO4 (3:1) or Na2SO4/NaCl
Al
Ti
Cr
Co
Ni
AlCr coating
31.9
0.4
13.2
6.4
Bal.
aluminized coating
25.6
0.5
5.3
6.8
Bal.
Temperature(C)
Bombardment cleaning
2030
6070
-800
30
50100
Chromium target
2030
6070
-200
30
100150
123
629
Fig. 1 XRD patterns of the aluminized coating and the AlCr coating
Fig. 2 Cross-sectional BSE images of the two coatings: a AlCr coating; b aluminized coating
Fig. 3 Line scanning images on the cross-sections of the aluminized coating a, the AlCr coating b
123
630
(a)
(b)
Fig. 4 Corrosion kinetic curves of DSM11 substrate, aluminized coating, and AlCr coating in the mixed salts of Na2SO4/K2SO4 a, Na2SO4/
NaCl b at 900 C
123
surface of the oxide film will react with O2 again to generate Cl2. The newly generated Cl2 can diffuse into the
oxide film, and again react with the elements such as Cr
and Al. With the continuous reaction, the whole process of
hot corrosion accelerated. As a result, the mass loss
quantity increased. The corrosion kinetic curve shows a
significant increase of mass gain at initial stage up to 20 h,
and follows an obvious drop after 20 h. The severe mass
losses are caused by significant scale spallation and O2
fluxing, confirming it is necessary to apply protective
coatings on the alloy. For the aluminized coating, a rapid
increase of mass gain occurs in the first 20 h, with a
maximum mass gain of 1.75 mg/cm2 and then starts to fall.
The protective Al2O3 scale starts to crack, and spallation
also occurs. However, for the AlCr coating, the mass gain
maintains sustained increasing throughout the corrosion
process. The mass gain owing to the formation of the scales
is much bigger than the mass loss caused by scale spallation and dissolution. Obviously, the AlCr coating provides
much better protection to the alloy than the aluminized
coating in this kind of mixed salt.
3.3 Corrosion Scales
Figure 5a shows the XRD patterns of the surfaces of the
DSM11 alloys with the aluminized coating and the AlCr
coating after hot corrosion at 900 C in the mixture salt of
Na2SO4/K2SO4 (3:1). Besides the Cr2O3 scale, a large
amount of un-protective corrosion products, identified as
Cr3S4 and TiO2 are formed on the surfaces of the samples.
The existence of S in the corrosion products proves that
S2- can diffuse from the surface of the oxidation film into
the substrate through the rapid diffusion channel, which is
formed by the low-melting phase. As for the aluminized
coating and the AlCr coating, the corrosion scales formed
on both coatings are mainly composed of a-Al2O3. A large
amount of b-NiAl phase is also detected, which
(a)
631
(b)
Fig. 5 XRD patterns of the DSM11 substrate, the aluminized coating and the AlCr coating after corrosion at 900 C for 100 h in mixed salts of
Na2SO4/K2SO4 a, Na2SO4/NaCl b
Fig. 6 SEM images showing the surfaces of DSM11 substrate a, aluminized coating b, AlCr coating c after corrosion at 900 C for 100 h in the
salt of Na2SO4/K2SO4
123
632
Fig. 7 Cross-sectional BSE images of DSM11 substrate a, aluminized coating b, AlCr coating c after corrosion at 900 C for 100 h in the salt
of Na2SO4/K2SO4
Fig. 8 SEM images showing the surfaces of DSM11 substrate a, aluminized coating b, AlCr coating c after corrosion at 900 C for 100 h in the
salt of Na2SO4/NaCl
Fig. 9 Cross-sectional BSE images of DSM11 substrate a, aluminized coating b, AlCr coating c after corrosion at 900 C for 100 h in the salt
of Na2SO4/NaCl
123
633
1
3
SO3 S2 O2 :
2
2
123
634
4 Conclusions
(1)
(2)
(3)
123
References
[1] J.R. Nicholls, D.J. Stephenson, Met. Mater. 7, 156 (1991)
[2] J. Ma, S.M. Jiang, H.Q. Li, W.X. Wang, J. Gong, C. Sun,
Corros. Sci. 53, 1417 (2011)
[3] J. Smialek, Metall. Trans. A 18, 164 (1987)
[4] E. Godlewska, K. Godlewski, Oxid. Met. 22, 117 (1984)
[5] G.W. Goward, D.H. Boone, Oxid. Met. 3, 475 (1971)
[6] W.F. Gale, J.E. King, Metall. Trans. A 23, 2657 (1992)
[7] P. Hancock, Mater. Sci. Technol. 3, 536 (1987)
[8] N. Eliaz, G. Shemesh, R.M. Latanision, Eng. Fail. Anal. 9, 31
(2002)
[9] E.L. Simons, G.V. Browning, H.A. Liebhafsky, Corrosion 11,
505 (1955)
[10] D.W. McKee, D.A. Shore, K.L. Lurthra, J. Electrochem. Soc.
125, 411 (1978)
[11] I. Gurrappa, Oxid. Met. 51, 353 (1999)
[12] M.K. Hossain, S.R.J. Saunders, Oxid. Met. 12, 1 (1978)
[13] D. Deb, S.R. Iyer, V.M. Radhakrishnan, Mater. Lett. 29, 19
(1996)
[14] W.C. Hagel, Corrosion 21, 316 (1965)
[15] J.R. Nicholls, N.J. Simms, W.Y. Chan, H.E. Evans, Surf. Coat.
Technol. 149, 236 (2002)
[16] N. Birks, G.H. Meier, in Introduction to High Temperature
Oxidation of Metals, (Edward Arnold, London, 1983)
[17] P. Kofstad, in High Temperature Corrosion, (Elsevier Applied
Science Publishers Ltd., New York, 1988)
[18] C.S. Giggins, F.S. Pettit, France patent 11545 (1979)
[19] S.W. Yang, Oxid. Met. 15, 375 (1981)
[20] P.S. Liu, K.M. Liang, H.Y. Zhou, S.R. Gu, A.D. Lin, X.F. Sun,
H.R. Guan, T. Jin, K.N. Yang, Surf. Coat. Technol. 52, 497
(2001)
[21] R. Bianco, R.A. Rapp, J. Electrochem. Soc. 137, 211 (1990)
[22] R. Bianco, M.A. Harper, R.A. Rapp, J. Met. 43, 68 (1991)
[23] R. Sivakumar, Oxid. Met. 17, 27 (1982)
[24] K. Godlewski, E. Godlewska, Oxid. Met. 26, 125 (1986)
[25] N. Otsuka, R.A. Rapp, J. Electrochem. Soc. 137, 53 (1990)
[26] R.A. Rapp, Corrosion 42, 568 (1986)
[27] Z.B. Bao, Q.M. Wang, W.Z. Li, X. Liu, J. Gong, T.Y. Xiong, C.
Sun, Corros. Sci. 51, 860 (2009)
[28] R.A. Rapp, Corros. Sci. 44, 209 (2002)
[29] I. Gurrappa, Surf. Coat. Technol. 139, 272 (2001)
[30] S.M. Jiang, X. Peng, Z.B. Bao, S.C. Liu, Q.M. Wang, J. Gong,
C. Sun, Corros. Sci. 50, 3213 (2008)
[31] Q.M. Wang, Y.N. Wu, P.L. Ke, H.T. Cao, J. Gong, C. Sun, L.S.
Wen, Surf. Coat. Technol. 186, 389 (2004)