Scanning Auger electron spectroscopy study of the oxide lm formed on dendritic and interdendritic regions of C containing Fe3Al intermetallic

V. Shankar Rao a, M. Norell b, V.S. Raja

a b

a,*

Corrosion Science and Engineering, Indian Institute of Technology, Bombay, Powai, Mumbai 400 076, India Department of Materials Science and Engineering, Chalmers University of Technology, SE-412 96 G oteborg, Sweden

Abstract The oxide lms formed during early stage of oxidation at 800 C on dendritic and interdendritic regions of the cast Fe16Al1C (wt.%) alloy were studied using scanning Auger electron spectroscopy. Microhardness measurement and elemental depth proles by Auger spectroscopy reveal that the carbide, Fe3 AlC0:69 , is the major constituent of the interdendritic region, while dendrites are predominantly Fe3 Al phase. Between the two, the interdendritic region is found to be more prone to oxidation than the dendritic region, which was attributed to presence of carbides with low-Al content. In spite of the dierence in oxide lm thickness exhibited by both the phases, they consist of an inner aluminium oxide layer and an outer iron oxide layer.

Keywords: Intermetallics-iron aluminide; AES; XRD; Interfaces; Oxidation

1. Introduction In recent years, there has been increasing number of studies on the development of carbon containing iron aluminides, for high temperature applications [15]. This is

2718

because of two-fold benets carbon is reported to oer for iron aluminides. By enabling carbide formation, it oers strength to this material on one hand and reduces the environment embrittlement on the other [1,5,6]. Most of the studies on carbon containing aluminides are directed towards alloy development [1,2] and examination of their constituent phases [5,7], microstructures [3,4] and mechanical properties [5,8]. Since these materials are primarily developed for high temperature structural applications, they are expected to possess high temperature oxidation resistance. Oxidation behaviour of Fe3 Al and FeAl phases has been well documented by several investigators [912], but little was known on the oxidation behaviour of carbon containing iron aluminides until the oxidation studies of these alloys initiated in our laboratory. In the recent communications, we have reported the eect of carbon on long-term oxidation behaviour of Fe3 Al [13] and the eect of Al on the oxidation behaviour of FeAlC alloys [14,15]. In the rst study we have shown that the addition of carbon (0.141%) has only moderate eect in the temperature range 700900 C on the oxidation behaviour of these alloys, but it is responsible for raising the spallation tendency of the alloys at 1000 C [13]. In the second and third communications, we found that the carbide phase is more prone to oxidation in high-Al content alloys, whereas in low-Al content alloys it is the matrix phase [14,15]. Previous papers [1315] are concerned with long-term oxidation behaviour of these dual phase iron aluminides, with variation of C and Al content from one alloy to another. However, for a better understanding of the subject it is equally important to know the oxidation behaviour of each phase within an alloy. The present work examines the nature of oxides formed on dendritic and interdendritic regions of carbon containing Fe3 Al during the early stage of oxidation. This has been accomplished using scanning Auger electron spectroscopy. The dierent interfacial chemistry between oxide-dendrite and oxide-interdendrite region in the present alloy is believed to dierentiate the role of carbon at these two phases.

2. Experimental The alloy used in this study had a nominal composition of Fe16Al1C (wt.%). It was prepared by air induction melting followed by electroslag rening technique. Details on production and mechanical properties of this alloy can be found elsewhere in the literature [2,3]. Specimens for microscopy studies were obtained by polishing them through successive grades of silicon carbide emery papers starting with 220 down to 1000, followed by 1 l diamond paste and lastly etching. The etchant consisted of 33%CH3 COOH + 33%HNO3 + 1%HF + 33%H2 O by volume. Phases present in the alloy were identied by X-ray diraction (XRD) technique with CuKa radiation. Samples for oxidation studies were prepared in the same manner as was done for microscopy studies, except that they were not etched. Scanning Auger electron spectroscopy (AES) was employed to examine the nature of oxides formed during early stages of oxidation. Oxidation was carried out at 800 C under 200 mbar O2 for 10 min in a furnace, it was then transferred to the Auger chamber. A scanning Auger microscope of model PHI 660 operated with an electron beam of

2719

0.2 lA at 10 kV took the spectra. For depth proling, the specimen was bombarded by Ar ions and the sputtering rates were calibrated using Ta2 O5 lm of known thickness. The dierentiated Auger peaks were found to dierentiate the O signals related to the Al and Fe oxides; similarly Fe and Al signals were dier in the oxide and bulk. In the evaluation of the depth proles, these were used for a numerical separation 1 of the signals from the dierent states of these elements in the various layers. The details about the technique is discussed elsewhere [16]. 3. Results and discussion A typical room temperature XRD pattern of Fe16Al1C alloy is shown in Fig. 1. The d -values obtained from the patterns and the calculated lattice parameters are summarised in Table 1. For comparison the lattice parameter of the phases reported in JCPDS les are also shown. As brought out by Fig. 1, the XRD pattern reveals the presence of Fe3 Al and Fe3 AlC0:69 carbide phases. Fe3 Al has a b.c.c structure, whereas Fe3 AlC0:69 exhibits an f.c.c perovskitc-type structure. Notably, the peak intensity of various planes does not match with the reported intensity of the corresponding planes by JCPDS les (Table 1). These variations could occur due to possible preferential orientation of phases in the as-cast alloy. Appearance of an  is due to reection of the superlattice plane (2 0 0) extra peak at the d -value of 3.89 A of Fe3 Al. This indicates that it is an ordered structure. Furthermore, the lattice parameter of Fe3 Al in the present alloy is higher than that reported in JCPDS les, implying that carbon is soluble in Fe3 Al phase even at room temperature. In contrast to Fe3 Al, the Fe3 AlC0:69 phase of the alloy exhibits almost the same lattice parameter value as that reported in JCPDS les and hence is expected to have the same stoichiometry. The microstructure of the alloy was examined in a scanning electron microscope (SEM). A typical microstructure of the alloy as seen in SEM is brought out in Fig. 2. Two distinct regions are seen in the micrograph. The alloy clearly shows dendritic and interdendritic regions as expected in a cast alloy. Though a few authors have reviewed the FeAlC phase diagram [17,18], phase boundaries of various phases at dierent temperatures still remain uncertain. Examination of a vertical section of the FeAlC phase diagram corresponding to 15 wt.%Al, close to the present alloy, shows that with 1 wt.%C (corresponding to 3.89 at.%) Fe3 AlC solidies as a last liquid from the alloy [18]. Therefore, the interdendritic region must contain this phase. This aspect was further examined using microhardness and microanalytical techniques. Microhardness test in the interdendritic and dendritic regions, respectively, yielded average values of 475 (10) and 390 (10) kg/mm2 Vickers hardness for a 50 g applied load. The higher hardness exhibited by the interdendritic region indicates that it consists of Fe3 AlC phase. A secondary electron image of the oxidised alloy is shown in Fig. 3. Resemblance between this image and the one obtained from the as-cast sample (Fig. 2) is obvious.
1

Software called MultiPak from Physical Electronics was used.

2720

Fig. 1. Typical XRD pattern of the alloy identies Fe3 Al and Fe3 AlC0:69 phases.

Table 1 Results of XRD patterns of Fe16Al1C alloy d -Values ] [A 2.89 2.04 1.44 2.15 1.32 Plane (h k l) 200 220 400 111 220 I /Io Obs. 10.5 2.1 100 3.0 0.5 Ref. 4 100 80 100 80 ] Cell parameter [A Calculated a 5:82 Ref. a 5:793 Fe3 Al Phase (s) JCPDS card no. 06-0695

a 3:771

a 3:771

Fe3 AlC0:69

03-0965

Fig. 2. Scanning electron micrograph of Fe16Al1C alloy reveals the dendritic (white contrast area) and interdendritic (grey contrast area) regions.

2721

Fig. 3. Secondary electron image of the alloy, showing oxides morphology after oxidation at 800 C for 10 min. Auger analysis carried out at dendritic and interdendritic regions.

AES analysis of oxides was performed on the dendritic and interdendritic region in the above micrograph. AES depth proles of the elements of oxides formed on the dendritic as well as on the interdendritic regions are presented in Fig. 4. The oxides of Fe and Al seem to exist as two dierent layers, except for some mixing at their interface. Auger spectra taken on the dendritic and interdendritic regions after complete removal of oxide layer are shown in Fig. 5. No detectable carbon could be found from the dendritic region (Fig. 5a). The interdendritic region accounts for 14 at.% C (Fig. 4b) which corresponds to a carbide phase with formula of Fe3 AlC0:69 as detected by XRD pattern. Moreover, SEM could not reveal the presence of Fe3 Al in the interdendritic region even at higher magnication. Experimental data show that the interdendritic regions are predominantly carbides, although it is not possible to rule out the existence of Fe3 Al phase in the interdendritic region. Hence, the oxidation behaviour of this region is approximated to the oxidation behaviour of carbide phase. Normally cast alloys exhibit segregation of impurities at the interdendritic areas. As revealed by the comparison of Auger spectra of Fig. 5a and b, the interdendritic region does not show the detrimental impurities such as Mn, S, P, which adversely aect the oxidation behaviour of alloy. The absence of these impurities in the interdendritic region could be attributed to the ability of electroslag rening process to minimise them. The thickness of each oxide layer formed on the two phases obtained from Fig. 4 is given in Table 2. The sputtering rate of iron oxide is closer to that of Ta2 O5 , while for aluminium oxide it is about 30% slower than Ta2 O5 [19]. In making estimation we assume that any variations in the sputter rate will aect both the dendritic and interdendritic regions in the same way. The data show that the interdendritic region forms as much as four times thicker oxide than the dendritic region. On the other hand, oxides formed on both the regions appear similar in the following ways: (a) both show layers of well separated oxides, (b) both exhibit a transition layer where both cations are intermixed and (c) oxide thickness ratios (Al oxide/Fe oxide) are almost the same (Table 2). Existence of both the cations in the narrow zone between the two oxide layers of aluminium and

2722

80
O outer O inner Al inner Al bulk Fe outer Fe bulk

Atomic Concentration (%)

60

40

20

0 0 200 400 600 800

(a)
100

Sputter Depth (nm)

Atomic Concentration (%)

80

60

Carbide O surf O inner Al inner Al bulk Fe outer Fe bulk

40

20

0 0 500 1000 1500 2000 2500

(b)

Sputter Depth (nm)

Fig. 4. AES depth proles of oxide lm formed after 10 min at 800 C at (a) dendritic and (b) interdendritic region.

iron oxides could mean either the iron and aluminium oxides co-exist or an oxide containing both these cations form. The present study does not resolve this aspect, though it is likely that peak shapes would be dierent if a new phase having both Fe and Al co-exist. To some extent, the appearance of this intermediate layer is also due to the depth resolution of the ion sputtering. Notably, during sputtering the oxide layers of the carbide phase show no signals of carbon until they are removed completely. This corroborates that carbon does not interfere with oxide properties, either by ionic or electronic transport process. Whereas S is reported to be interfere with oxides in the form of FeS during oxidation of Fe3 Al alloy [20]. Velon and Olefjord reported the formation of a thin 15.9 nm bilayer oxide on iron aluminide, where cations of Fe and Al respectively exist on outer and inner layers, when Fe3 Al (28 at.% Al) was oxidised at 300 C for 50 h [16]. Unfortunately, these results cannot be compared with the present work, as their study was concerned with behaviour of the aluminide at 300 C, a temperature much lower than that was applied in the present study. This is because of the fact that below 500 C, unlike at higher temperatures, Al diusion towards the surface of the alloy becomes slow.

2723

N (E)/dE

Al

Fe Fe Fe
200 400 600 800 1000 1200 1400

(a)

Kinetic Energy (eV)

N (E)/dE

Al

Fe Fe Fe
200 400 600 800 1000 1200 1400

(b)

Kinetic Energy (eV)

Fig. 5. Typical Auger electron spectra of (a) dendritic and (b) interdendritic regions, after complete removal of the oxide lm by sputtering.

Table 2 Oxide lm thickness at dendritic and interdendritic regions Region Dendritic/Fe3 Al Interdendritic/Fe3 AlC0:69 Al-oxide (nm) 200 850 Fe-oxide (nm) 300 1150 Total thickness (nm) 500 2000 Al/Fe oxide thickness ratio 0.67 0.73

Nonetheless, it is interesting to note that iron aluminide gives rise to similar bilayer oxides at these two dierent temperatures, though the thickness of these oxides depends on the temperature of exposure. According to these authors [16], Fe2 O3 being an n-type conductor allows migration of oxygen ions, which react with aluminium on the surface of Fe3 Al to form a protective scale of Al2 O3 . In contrast to  formed on this, Natesan [21] reported high Al/O ratio in the oxide lm of 100 A Fe3 Al (Fe15.9 wt.%Al) when it was oxidised in air at 1000 C for 10 min. However,

2724

the presence of Fe2 O3 in the oxide layer has not been reported. Since Al content is compared to the total oxygen content of the oxide lm, a higher Al/O ratio reported by him does not support the possible presence of iron oxide in the oxide scale. The present work does not address the oxidation mechanism with respect to Fe3 Al phase, but it seems possible to explain the bilayer oxide formation based on the general nucleation and growth characteristics of an alloy system having two reacting elements. The high partial pressure of oxygen and high iron activity of iron aluminide enable simultaneous oxidation of iron and aluminium [22]. However, iron oxide has very high growth rate than that of aluminium oxide. As a result, iron oxide outgrows aluminium oxide during early stages of oxidation, leaving behind the islands of aluminium oxides. The oxidation of the substrate continues to occur, as oxygen ions migrate through, n-type Fe2 O3 , conductor, until the aluminide develops a continuous protective alumina scale over its surface. This leaves behind a duplex oxide scale with Fe2 O3 on the top and Al2 O3 at the bottom as has been observed in the present case. This explains why the Fe3 Al phase exhibits Fe2 O3 over Al2 O3 . The suggestion that O ions diuse through Fe2 O3 semiconductor is supported by the previous study on ferritic stainless steels [23]. These authors indicated that stainless steels form Fe-oxide layer on the alloy, through which oxygen diuses to the alloy oxide interface to form Cr-oxide, even when the stainless steel was oxidised at 520 C for 3 min. Bradford [24] reported that during prolonged oxidation Fe2 O3 converts into Al2 O3 by following reaction. Fe2 O3 Al Al2 O3 Fe The above reaction is possible because of the fact that Al2 O3 is thermodynamically a more stable species than Fe2 O3 . When Al comes into contact with Fe2 O3 the latter gets reduced to Fe and the former gets oxidised to Al2 O3 . Though such a mechanism can explain why Natesan [21] did not observe the presence of Fe2 O3 in the oxide layer formed at 1000 C on iron aluminide, the question arises as to how Al from the alloy would have access to Fe2 O3 when an Al2 O3 barrier lies between Fe2 O3 /alloy substrate exists. A possible explanation, why Natesan [21] did not observe Fe2 O3 on alloy oxidised at 1000 C even during shorter intervals of time, while Fe2 O3 was found on the iron aluminide oxidised at 300 C even for a longer duration of 15 h [16]. According to Renusch et al. [25] Fe2 O3 facilitates the growth of Al2 O3 by acting as a precursor template, making its presence important at low temperatures, when it is dicult for the latter to form. However, at 1000 C, Al diusion and its oxidation can be so rapid that Al2 O3 may not require Fe2 O3 as a precursor template and the former is formed exclusively. One of the important aspects of the present study is to examine the role of Fe3 AlC0:69 , one of the constituent phases, on the oxidation behaviour of carbon containing iron aluminide. The present data suggest that carbide phase forms four times thicker oxide than the matrix. Additional microscopy evidence for the higher oxidation tendency of Fe3 AlC than Fe3 Al arises from the cross-sectional image of the oxide scale after a prolonged oxidation of 1000 h (Fig. 11 in Ref. [13]), where thicker oxide scale is noticed on carbide than at matrix. It needs to be emphasized

2725

that the despite having low-Al content in the carbide phase, the Al-oxide layer in the carbide phase is thicker than that of the matrix phase. This observation is somewhat similar to our previous nding, in which Al2 O3 oxide forms thicker layer in Fe8Al 1C alloy than Fe16Al1C alloy, in spite of having low-Al content in the former [14]. These ndings lead to the dictation that the formation of Al2 O3 in the FeAl alloys depends on the relative activity of Al at oxidation temperature rather than the total Al content in the alloy, which has been discussed in our previous communication [14]. Nevertheless, the formation of thick Al-oxide layer on the carbide phase despite its low-Al content is a matter of concern because Al reservoir in the carbide phase will become very less to subsequent maintain the protective Al2 O3 layer in case of spallation of the oxide scale. Since published literatures on the oxidation behaviour of carbon containing dual phase iron aluminides are sparse, it is worthwhile to compare the oxidation behaviour of the present alloy with that of cast stainless steels. Interdendritic region in cast stainless steels are known to be more prone to oxidation than that of dendrite region, in a way much similar to the behaviour of Fe16Al1C alloy. However, the higher oxidation tendency of interdendritic regions of cast stainless steel alloy is attributed to the accumulation of impurities such P, S, Mn. In the present alloy, no such impurities in the interdendritic region are enriched (Fig. 5b). Therefore, higher oxidation tendency of interdendritic region in iron aluminide can be attributed to the presence of carbide in this region. This is because Fe3 AlC0:69 has less Al (11 at.%) than the Fe3 Al matrix (18 at.%), as could be seen from Fig. 4a and b. The decrease in Al content of the carbide phase, which is responsible for forming protective Al2 O3 , makes the interdendritic zone more prone to oxidation. The other factor that can enhance the oxidation tendency of carbides is the presence of carbon. On oxidation, the carbide phases release CO/CO2 [26,27]. This makes the oxide porous, which is less protective and vulnerable to oxygen diusion. It is worthwhile to examine the oxide/metal interface. Simultaneous presence of elemental and oxidised states of Al and O in addition to the expected elemental Fe, over a small depth between the substrate and the oxide indicates that the oxide/metal interface is non-planar. A close examination of the shapes of Oinner , Alinner and Febulk proles of dendrite (Fig. 4a) and interdendritic region (Fig. 4b) further brings out the subtle dierence in the interface character on the carbides as compared to that of matrix. The oxide/matrix interface shows relatively sharp decay of Alinner and Oinner , while oxide/carbide interface seems to exhibit a sharp decay followed by a slow decay of these signals, indicating that this interface has higher O and Al content than that is found at the oxide/matrix interface. The concomitant presence of Alinner and Oinner at the interface means that Al could coexist as oxide along with metallic Fe and Al. This implies that carbide is prone to internal oxidation at this temperature. It could be due to relatively low-Al content of Fe3 AlC0:69 and/or higher permeability of oxygen in it in comparison with Fe3 Al. The O2 permeability in many intermetallics compound has been reported to be very low [28], while, no published data exists on the permeability of oxygen in Fe3 AlC. A detail microstructural and chemical analysis are required for an in depth understanding of the oxidation behaviour in the carbide. Besides the compositional dierence between Fe3 AlC0:69 and Fe3 Al, their dierence

2726

Fig. 6. Schematic of oxide layer formation in the dendritic and interdendritic regions presented based on Ref. [29].

in thermal stability at the oxidising temperatures also aect the overall oxidation behaviour of these materials [18]. One of the authors made a detailed analysis of the oxidation behaviour of FeAl C systems including carbon containing iron aluminide intermetallics [29]. A physical model was developed to explain a wide range of experimental results. From the above study a schematic diagram of the oxide layer formation over dendritic and interdendritic regions is shown in Fig. 6. The higher C present in the alloy gives rise to CO2 . The gaseous CO2 when escapes from the surface introduces pores and cracks, which become easy paths for O2 migration to the metal interface. In such a case the oxide needs to grow thick enough to oer an eective barrier for the migration of O2 . Since, more C is present in the interdendritic region than in the dendritic region, the oxide on the former will be more porous and thicker than that of the latter. In the model it is assumed that during initial stage of oxidation both the phases are oxidised independently, as the activity of the components (Al and C) diers widely in both the phases. However, to maintain thermodynamic equilibrium during oxidation process between elements and its ions; Al can diuse from the matrix phase, Fe3 Al, to the surrounding Fe3 AlC phase, similarly the C can diuse out of the carbide to the matrix phase as the solubility of C in the matrix increases with temperature. Both these processes enhance the oxidation resistance of carbides. Nevertheless, this will depend on temperatures and time of alloy exposure, lower temperature and shorter time being less eective.

2727

4. Conclusions The oxide lm formed on the dendritic and interdendritic regions during early stage of oxidation consists of iron oxide in the outer layer and Al oxide in the inner layer. The over all oxide lm formed on the interdendritic phase is much thicker than on the dendritic region. This is because presence of low-Al content carbides, in the interdendritic region. Acknowledgements The authors V. Shankar Rao and V.S. Raja thank Dr. R.G. Baligidad for providing the materials and Dr. D. Banerjee, Director, Defence Metallurgical Research Laboratory, India, for his keen interest in this work. References
[1] R.G. Baligidad, U. Prakash, A. Radhakrishna, V. Ramakrishna Rao, P.K. Rao, N.B. Ballal, Scripta Mater. 36 (1997) 667. [2] R.G. Baligidad, U. Prakash, A. Radhakrishna, V. Ramakrishna Rao, P.K. Rao, N.B. Ballal, Scripta Mater. 36 (1997) 105. [3] R.G. Baligidad, U. Prakash, V. Ramakrishna Rao, P.K. Rao, N.B. Ballal, ISIJ Int. 36 (1996) 1448. [4] A. Radhakrishna, R.G. Baligidad, D.S. Sharma, Scripta Mater. 45 (2001) 1077. [5] K.S. Kumar, L. Pang, Mater. Sci. Eng. A 258 (1998) 153. [6] L. Pang, K.S. Kumar, Mater. Sci. Eng. A 258 (1998) 161. [7] M. Palm, G. Inden, Intermetallics 3 (1995) 443. [8] W. Sanders, G. Sautho, Intermetallics 5 (1997) 361. [9] P.F. Tortorelli, K. Natesan, Mater. Sci. Eng. A 258 (1998) 115. [10] P.F. Tortorelli, J.H. De Van, Mater. Sci. Eng. A 153 (1992) 573. [11] I. Kim, W.D. Cho, H.J. Kim, J. Mater. Sci. 35 (2000) 4695. [12] J.H. Devan, in: T. Grobstein (Ed.), Oxidation of High Temperature Intermetallics, TMS, Warrendale, PA, 1989, p. 107. [13] V. Shankar Rao, V.S. Raja, R.G. Baligidad, Oxid. Met. 57 (2002) 449. [14] V. Shankar Rao, R.G. Baligidad, V.S. Raja, Intermetallics 10 (2002) 73. [15] V. Shankar Rao, V.S. Raja, High Temp. Mater. Process. 21 (2002) 143. [16] A. Velon, I. Olefjord, Oxid. Met. 56 (2001) 425. [17] V. Raghavan, Phase Diagram of Ternary Iron Alloys, part-1, ASM International, Metals Park, OH, USA, 1987, p. 89. [18] P. Villars, A. Prince, H. Okamoto, Handbook of Ternary Alloy Phase diagrams, vol. 3, ASM International, 1997, p. 2850. [19] I. Olefjord, H.J. Mathieu, P. Marcus, Surf. Interf. Anal. 15 (1990) 681. [20] P.Y. Hou, J. Ackeman, Appl. Surf. Sci. 178 (2001) 156. [21] K. Natesan, Mater. Sci. Eng. A 258 (1998) 126. [22] F. Gesmundo, B. Glesson, Oxid. Met. 44 (2002) 211. [23] K. Ishiguro, T. Homma, in: R.A. Rapp (Ed.), High Temperature Corrosion, NACE-6, Houston, TX, 1983, p. 28. [24] S.A. Bradford, Fundamentals of Corrosion in Gases, 9th Ed., ASM Handbook, vol. 13, ASM International, 1992, pp. 6176. [25] D. Renusch et al., in: D.A. Shores, R.A. Rapp, P.Y. Hou (Eds.), Fundamental Aspects of HighTemperature Corrosion, The Electrochemical Society, Pennington, NJ, 1996, pp. 6273.

2728 [26] [27] [28] [29] C.H. Kao, C.M. Wan, J. Mater. Sci. 23 (1988) 1943. W.E. Boggs, J. Electrochem. Soc. 118 (1971) 906. G.H. Meier, F.S. Pettit, Mater. Sci. Eng. A 153 (1992) 548. V.S. Raja, High temperature oxidation behaviour of carbon containing two phase iron aluminides and FeAl alloys, Proc. of Environmental Degradation of Engineering Materials, Bordeaux, France, 2003 (in press).