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Surface & Coatings Technology 202 (2008) 2616 2622 www.elsevier.com/locate/surfcoat

High temperature oxidation resistance of 1.25cr0.5mo wt.% steels by zirconia coating

Y.S. Baron , A. Ruiz, G. Navas
Departamento de Ciencias de los Materiales, Universidad Simn Bolvar, Caracas, Venezuela Received 29 April 2007; accepted in revised form 20 September 2007 Available online 4 October 2007

Abstract A zirconia coating was applied to improve the oxidation resistance of 1.25Cr0.5 Mo wt.% steels. A 8 wt.% yttria-stabilized zirconia coating was deposited by solgel technique. One problem with this method is that the hydrolysis of the organometallic precursors is faster than condensation, and the formation of precipitates is favored. Ethyl acetate was used to slow the hydrolysis rate in order to obtain a more continuous layer. The air oxidation behavior of the coating was studied at 600 C and 700 C by the continuous measurement of the weight gain. The microstructural characterization was performed by optical and scanning electron microscopy, and the composition was determined by energy dispersive spectroscopy (EDS). The weight gain of the 1.25Cr0.5 Mo wt.% was diminished by about 70% compared to uncoated samples. 2007 Elsevier B.V. All rights reserved.
Keywords: Oxidation; Solgel coating; Partially stabilized zirconia (PSZ)

1. Introduction Zirconia coatings improve the high temperature oxidation behavior of steels. Because of their low thermal conductivity (0.05 cal/C s cm) and their thermal expansion coefficient (similar to most metals) they can be use as a thermal barrier; however, they have poor thermal shock properties [1]. 69% yttria stabilized zirconia, improves the properties of the coating, exhibiting high fracture strength and fracture toughness due to a stress-induced phase transformation of the tetragonal phase to the monoclinic form [25]. An easy way to obtain yttria-stabilized zirconia coatings is the solgel process [1,68]. Organometallic compounds are usually the precursors of the sol. The gel is a rigid network built through the polymerization of the sol. One problem with these kinds of precursors (alkoxides) is that the hydrolysis is much faster than condensation, and therefore the formation of

Corresponding author. E-mail addresses: ylianabaron@usb.ve (Y.S. Baron), aruiz@usb.ve (A. Ruiz), gnavas@usb.ve (G. Navas). 0257-8972/$ - see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.surfcoat.2007.09.038

particles is favored. If the hydrolysis rate were diminished, a continuous coating could be obtained [1]. H. Li [9] used zirconium n-propoxide as the precursor of the solgel coating on a mild steel substrate (AISI 1008). He obtained a single-layer coating composed of zirconia particles that reduced the oxidation of the steel. The thickness of the coating is a critical parameter; with the use of a six layer coating the oxide growth is retarded [9]. To slow the hydrolysis rate of the precursors in the solgel process, the nature of the organic group could be changed (nbutoxides are more stable than isopropoxides). Also compounds such as acetylacetone, ethylacetate or allylacetate, can be used to increase the hydrolytic stability of the precursors [1011]. K. Izumi et al., [12] used various zirconium compounds as precursors in order to observe the influences of their chemical properties on the zirconia coatings. Among the alkoxides evaluated, they found that the stability of zirconium tetra-n-butoxide was better than that of zirconium tetraisopropoxide. Their results indicated that the stability of the solution depended upon the hydrolysis rate of the precursors. However, the film of ZrO2 obtained was discontinuous and had weak adhesive properties [12]. M. Shane and M. Mecartney [1] used zirconium tetrabutoxide and yttrium acetate as the precursors for the solgel, and

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acetylacetone is used to slow the hydrolysis rate. Excellent adhesion at the interface was obtained due to significant coating substrate interfacial reactions. The crystallization of the films at different temperatures were evaluated. At 750 C the X-ray diffraction data showed that the peaks of the zirconia phase are fairly weak and broad, corresponding to small amounts of very tiny crystalline particles. At 950 C the zirconia peaks are once again present, however there are several extra peaks, FeCr2O4 and (Fe0.6Cr0.4)2O3, that increase the strengthening of the interface between the ceramic and substrate [1]. In this study partially stabilized zirconia (PSZ) coating on 1.25Cr0.5 Mo wt.% steel was prepared by solgel processing, where ethylacetate is used instead of acetylacetone as an alternative to control the hydrolysis rate. The protective effect of the PSZ coating during oxidation was investigated. 2. Experimental procedure 2.1. Substrate preparation Substrates of 1 x 1.5 x 0.3 cm3 of 1.25Cr0.5 Mo steel were used in this study. The substrates were grinded using 180 to 600 grit silicon carbide paper and polished with 1 and 0.3 m colloidal alumina. 2.2. Coating preparation Solutions of zirconium tetrabutoxide and yttrium acetate were prepared as procedure described by M. Shane and M. Mecartney [1]. Ethylacetate was used instead of acetylacetate to slow the hydrolysis rate. 2.3. Heat treatment The dip-coated samples were heated at 500 C for 15 min, because the decomposition of the organometallic compounds occurs at around 450 C. For multi-layer coating, the samples were heated after each dip. Additionally, multi-layer coatings were treated at 800 C for 30 min, to increase the coating density.

Table 1 EDS over the cross section of 1.25Cr0.5 Mo wt.% steel after oxidation at different temperatures Elements (atomic %) (Detection level N0.5 at.%) Fe Fig. 1 Fig. 2 Inner layer Outer layer Inner layer Intermediate layer 1 Intermediate layer 2 Outer layer Inner layer Intermediate layer Outer layer 59.72 62.66 46.17 43.42 45.88 38.79 55.07 69.89 64.70 O 35.19 37.34 51.91 56.10 54.12 61.21 43.06 28.99 34.03 Cr 1.90 1.92 0.48 1.51 0.23 0.18

Fig. 3

2.4. Oxidation test Isothermal weight gain measurements were obtained with a Cahn 100 thermobalance with an automatic data recorder (Iotech dakbook 216). The tests were carried out at 500 C, 600 C and 700C in air, for a period of 96 h. 2.5. Characterization The microstructural characterization was performed in a Philips XL 30 scanning electron microscope (SEM) operated at 25 kV. The composition was determined by energy dispersive spectroscopy (EDS) with a Philips spectrometer joint to the SEM. 3. Results and discussions 3.1. Uncoated samples Fig. 1 presents the SEM cross-section of one sample oxidized at 500 C. It shows the formation of two layers. The inner one is formed by iron and chromium spinel oxide as seen by EDS (Table 1). The outer layer is formed by hematite (Fe2O3). At temperatures below 570 C, the iron would be expected to form a two-layered scale of magnetite (Fe3O4) and

Fig. 1. SEM cross-section of 1.25Cr0.5 Mo wt.% steel oxidized at 500 C. It shows the formation of two layers of iron oxides. The presence of chromium oxides indicates the original superficies.

Fig. 2. SEM cross-section of 1.25Cr0.5 Mo wt.% after oxidation at 600 C. It shows the formation of different layers. The two inner layers are formed of iron and chromium oxides, the two outer layers of iron oxides.

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Fig. 3. SEM cross-section of 1.25Cr0.5 Mo wt.% steel oxidized at 700 C. It shows the formation of different layers and a porous zone.

Fe2O3, where the Fe3O4 is next to the metal [1318]. The presence of chromium in the inner layer is due to an internal oxidation of this element that does not form a continuous layer because of its low concentration in the metal. Fig. 2 presents the SEM cross-section of the sample after oxidation at 600 C. As in Fig. 1, it shows layers of different morphology. The inner layers are formed by iron and chromium spinel oxide (Table 1). At both temperatures, this spinel is the product of the reaction in solid state between the chromium oxide (Cr2O3), formed due to the internal oxidation of this element, and the iron oxide, formed during the process of thickening of the scale [18]. The outer layers are magnetite and hematite oxides with no significant amounts of chromium. These layers are formed by outward diffusion of iron cations, while the chromium was left behind and internally oxidized. Therefore, this border between oxides with chromium and the

other without chromium, could be taken as the original metal/ gas interface. Fig. 3 presents the cross-section of 1.25Cr0.5 Mo wt.% steel oxidized at 700 C. It shows two layers. The inner layer is formed by iron and chromium oxides (Table 1), and has similar dimensions as the cross section of Fig. 2. The outer layer could be hematite. We can explain the formation of these two layers as the result of two processes. At the beginning, there is formation of chromium oxides due to internal oxidation process, and the formation of wustite (FeO), Fe3O4 and Fe2O3 due to the outward cation diffusion of iron. As in the sample oxidized at 600 C, there is reaction in solid state between the chromium oxide and the iron oxide formed during the thickness of the scale. However the hematite in the outer layer continues its growth process due to cationic diffusion and destabilizes the layers beneath, forming a layer of magnetite. As a result of the destabilization of the inner layers, the iron can change from Fe2+ to Fe3+and create metallic vacancies. Thus, the porous zone can be attributed to the diffusion and coalescence of these vacancies. The oxidation kinetics for 1.25Cr0.5 Mo wt.% steel in air is illustrated in Fig. 4. It shows a linear dependence between the square of the weight gain, (m/S)2 , versus the time of exposition at 500 C and 600 C, indicating that the transport of the ions across the scale is the rate controlling process [18 21]. At 700 C, there are two linear behaviors for (m/S)2 vs time. During the firsts 30 h, there is oxidation and development of the characteristics scales (parabolic rate constant kp = 98.64 mg2/cm4s), with predominance of FeO; at longer times the oxidation rate decreases, as a result of the formation of more protective scales (kp = 42.96 mg2/cm4s) of Fe3O4 and Fe2O3, and the presence of a porous zone. The porous zone reduces the cationic diffusion of iron from the inner layer and, therefore, reduces the weight gain of the sample.

Fig. 4. Oxidation kinetics for 1.25Cr0.5 Mo wt %steel in air at different temperatures.

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3.2. Coated samples Fig. 5 shows the SEM micrograph of the zirconia coating on 1.25Cr0.5 Mo wt.%. The single layer coating is formed of clusters (Table 2) having an average diameter of about 5 m (Fig. 5a). The three-layer coating is formed of bigger clusters (30 m) that cover a larger area of the metal surface (Fig. 5b). The coating is mainly formed by tetragonal zirconia, as seen on the XRD of Fig. 6. The presence of these clusters may be an indication that there was hydrolysis of the precursors of the sol gel process. The oxidation kinetics curves at 600 C, were presented in Fig. 7 for coated and uncoated 1.25Cr0.5 Mo wt.% steel. It shows that all samples demonstrate a parabolic dependence between the square of the weight gain versus the time of exposition at 600 C. For the uncoated samples, the deviation from the linear behavior at the first 20 h can be attributed to the rapid formation of wustite as explained before. For coated samples, although there is no formation of a continuous layer of the zirconia coating, the oxidation of the 1.25Cr0.5 Mo wt.% steel at 600 C is reduced due to the zirconia coating. A single layer coating decreases the oxidation rate by about 40%, and a threelayer coating decreases it by 80%. The same mechanism were carried out in the experiment for formation of the oxide scale with zirconia coating as per results obtained by F. Czerwinski and J. Szpunar [22]. They proposed that CeO2 coatings decrease the oxidation rate of chromia former steels, because the Ce4+cations form pairs with cationic vacancies in oxide grain boundaries, blocking these fast ionic paths. As a parallel system, the same mechanism could be occurring in this case. There is formation of the oxide scale with the zirconia coating in it. The ZrO2 coating can react with the oxide

Fig. 5. SEM micrograph of the zirconia coating on 1.25Cr0.5 Mo wt.%. (a) Single layer coating. (b) Three-layer coating. The presence of particles may be an indicative that there was hydrolysis of the precursors of the solgel process.

Fig. 6. XRD of the surface of an oxidized and coated sample. It presents iron oxides and tetragonal zirconia. The iron oxides are due to the oxidation of the steel at 700 C that promotes the spalling of the coating.

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Fig. 7. Oxidation kinetics curves at 600 C, for coated and uncoated 1.25Cr0.5 Mo wt.% steel. It shows that the use of the zirconia coating reduces the oxidation rate in 40% for one layer and 80% for a three layer coating.

and form pairs with vacancies Eq. (1). This pairs are formed due to coulombian attractive forces. 3ZrO2 Y 6OO 3Zr V jFe 1 Fe
2Fe2 O3

Although there is formation of a new vacancy of iron, there are three zirconia cations available to form pairs with the vacancies of iron from the oxide. Consequently the mobile vacancy concentration in the oxide decreases due to the formation of such pairs. Once this protective scale is formed, the ionic diffusion is slowed, decreasing the oxidation rate. Fig. 8 shows the surfaces of samples with one (Fig. 8a) and three layers (Fig. 8b) of the zirconia coating after oxidation at 600 C. The formation of fine grain oxides (Table 2) is observed that are the product of a slow grow with an increment of the protective behavior of the oxide layer. The oxidation kinetics curves at 700 C, for coated and uncoated 1.25Cr0.5Mo wt.% steel, are presented in Fig. 9. For uncoated samples, the behavior is linear for both curves of (m/ S)2 versus time. The first part of the curve (t b 30 h) corresponds to a transient stage characterized mainly by a rapid formation of wustite oxide and internal oxidation of chromium, and the last part (t N 30 h) characterized by the formation of hematite in the outer layer due to cationic diffusion [20]. For coated samples, the square weight gain versus time curves are the same for onelayer and three-layer zirconia coating, and the decrease of the uncoated sample weight gain is of the same magnitude for both coated samples. Additionally, the slope of the coated sample curve is the same as the slope of the last part of the uncoated sample curves, indicating that cationic diffusion through hematite is controlling the rate of the oxidation process. Fig. 10 shows the surfaces of samples with one (Fig. 10a) and three layers (Fig. 10b) of zirconia coating after oxidation at

Fig. 8. SEM of the surfaces of 1.25Cr0.5 Mo wt.% steel coated with the zirconia coating after oxidation at 600 C. (a) One layer coating. (b) Three layer coating. It can be seen the formation of fine particles that are mono-crystals of oxide, product of a very slow grow.

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Fig. 9. Oxidation kinetics curves at 700 C, for coated and uncoated 1.25Cr0.5 Mo wt.% steel. With the use of the zirconia coating (one layer and three layer) there is a decrease of the oxidation rate in a 30%, but the increase of the thickness of the coating doesn't decrease the oxidation rate.

700 C. These figures don't show the evidences of clusters (Table 2) seen previously (Fig. 5). This may indicate that, even though the coating acts in the first 30 h, for longer times there is spallation of the zirconia coating. Fig. 11 presents the SEM of the cross-section of a coated sample, oxidized at 700 C for 96 h. It shows the formation of two layers which are named as inner and external layer (outer). The inner layer is dense, and the external layer is formed by columnar grains separated from one another, which was produced by diffusion of cations. Comparing Fig. 10 with the Fig. 3, it can be seen that the thickness of the oxides layers formed on coated and uncoated samples after oxidation is almost same. However, there are differences between the weight gain of coated and uncoated samples. Based on these observations, it can be assumed that the coating makes possible the formation of vacancieszirconia cations pairs in the first

Table 2 EDS over the surfaces of 1.25Cr0.5Mo wt.% steel coated with zirconia. Elements (atomic %) (Detection level N0.5 at.%) Y Fig. 5a Fig. 5b Fig. 8a,b Fig. 10. SEM of the surfaces of 1.25Cr0.5 Mo wt.% steel with the zirconia coating after oxidation at 700 C. (a) One layer coating. (b) Three layer coating. It does not show evidence of the coating clusters. Fig. 10a Fig. 10b Cluster Base Cluster Base Clusters Oxide Oxide Oxide 23.04 0.46 15.34 15.34 0.33 0.32 0.27 Zr 35.76 0.41 16.82 16.82 0.22 0.36 0.20 Cr 0.91 1.44 1.29 0.58 0.22 0.19 0.18 Fe 39.82 96.99 30.72 85.67 30.72 48.73 51.04 50.86 O 36.08 11.48 36.08 49.84 47.78 47.89 Mn 0.46 0.66 0.31 0.61

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Acknowledgments The authors wish to thank the Decanato de Estudios de Postgrado of the Universidad Simn Bolvar for the financial support offered to this project. References
[1] [2] [3] [4] [5] [6] [7] [8] M. Shane, M. Mecartney, J. of Mater. Sci. 25 (1990) 1537. K. Tsukama, J. Mater. Sci. Lett. 4 (1985) 857. T. Sato, S. Ohtaki, T. Endo, J. Am. Ceram. Soc. 68 (1985) C320. C.W. Kuo, Y.H. Lee, K.Z. Fung, M.C. Wang, J. Non-Cryst. Solids 351 (2005) 304. R. Garvie, P. Nicholson, J. Am. Ceram. Soc. 55 (1972) 303. M.J. Atik, J. Zarzycki, C. RKha, J. Mater. Sci. Lett. 13 (1994) 266. S.G. Kim, S.W. Nam, S.P. Yoon, S.H. Hyun, J. Han, T.H. Lim, S.A. Hong, J. Mat. Sci. 39 (2004) 2683. R. Pascual, M. Sayer, C.V. Kumar, L.C. Zou, J. Appl. Phys. 70 (1991) 2348. H.B. Li, K.M. Liang, L.F. Mei, S.R. Gu, Mater. Sci. Eng. A 341 (2003) 87. C. Sanchez, J. Livage, M. Henry, F. Babonneau, J. Non-Cryst. Solids 100 (1988) 65. M. Guglielmi, G. Carturan, J. Non-Cryst. Solids 100 (1988) 16. K. Izumi, M. Murakami, T. Deguchi, A. Morita, N. Tohge, T. Minami, J. Am. Ceram. Soc., 72 (1989) 1465. G.D. West, S. Birosca, R.L. Higginson, J. Microscopy 217 (2005) 122. J. West, Basic Corrosion and Oxidation, Ellis Horwood Limited, England, 1980. G.H. Meier, Mat. Sci. Eng. A 120 (1989) 1. O. Goncharov, Inorg. Mater. 40 (2004) 1295. P.A. Labun, J. Covington, K. Kuroda, G. Welsch, T.E. Mitchell, Metall. Trans. A 13 (1982) 2103. A.M. Huntz, J. Mater. Sci. Lett. 18 (1999) 1981. N. Birks, G. Meier, Introduction to High Temperature Oxidation of Metals, Edward Arnold, England, 1983. R. Chen, W. Yuen, Oxid. Met. 59 (2003) 433. A. Skalli, A. Galerie, M. Caillet, Solid State Ionics 25 (1987) 27. F. Czerwinski, J. Szpunar, Thin Solid Films 289 (1996) 213.

Fig. 11. SEM cross-section of 1.25Cr0.5 Mo wt.% steel coated with zirconia after oxidation at 700C. It shows the formation of two different layers.

30 h of oxidation. But, at longer times, the growing of the oxide layers promotes the spallation of the coating. 4. Conclusions At 500 C, 600 C and 700 C the oxidation process of the 1.25Cr0.5 Mo wt.% steel shows a parabolic relationship between the weight gain and time, indicating that the transport of the ions across the scale is the rate controlling process. The zirconia coating is formed by clusters, indicating that there was hydrolysis of the precursors of the solgel process. At 600 C, the oxidation rate of a 1.25Cr0.5 Mo wt.% steel decreases when coated with the zirconia coating. A single layer coating decreases the oxidation rate by about 40%, and a three-layer of coating decreases it by 80%. This indicates that this coating can be used to increase the temperature of operation of these steels to 600 C. The use of multilayered coating does not improve the resistance at 700C. Therefore, the coating is not effective at this temperature.

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