J. Mater. Sci. Technol., Vol.25 No.

4, 2009

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Aluminizing Low Carbon Steel at Lower Temperatures

This study reports the signicantly enhanced aluminizing behaviors of a low carbon steel at temperatures far below the austenitizing temperature, with a nanostructured surface layer produced by surface mechanical attrition treatment (SMAT). A much thicker iron aluminide compound layer with a much enhanced growth kinetics of -Fe2 Al5 in the SMAT sample has been observed relative to the coarse-grained steel sample. Compared to the coarse-grained sample, a weakened texture is formed in the aluminide layer in the SMAT sample. The aluminizing kinetics is analyzed in terms of promoted diusivity and nucleation frequency in the nanostructured surface layer. KEY WORDS: Nanostructured materials; Surface mechanical attrition treatment; Aluminizing;
Diusion; Nucleation

1. Introduction Aluminizing is an eective surface modication process for improving corrosion resistance of steels. Various aluminizing processes have been developed by enriching the surface layer of steels with a high concentration of Al to form iron aluminide diusion coatings, so that the ability to form impervious and tenacious alumina scale is enhanced in corrosive media[13] . Nevertheless, as limited by the involved diusion of Al and reaction kinetics between Al and Fe, eective aluminizing is normally performed at high temperatures with austenite phase. An iron aluminide coating can only be achieved on steels at temperatures above 900 C with a duration of several to dozens hours for the pack aluminizing process that is most commonly used in industry. Holding at such high temperatures might induce serious distortion of workpieces, carbide precipitation and grain coarsening of the steel matrix, hence, degradation of mechanical properties. Apparently, lowering the aluminizing temperatures of steels is of great signicance for minimizing these negative eects and widening the application of aluminizing techniques. More specically, aluminizing steels in the ferrite state at a temperature below 700 C would be very much desired[4] . By means of a recently developed surface nanocrystallization technique, surface mechanical attrition treatment (SMAT)[5,6] , lowering the aluminizing temperature of steels becomes feasible. SMAT enables to substantially rene grains in the surface layer of various steels into the nanometer scale via repeated and multidirectional plastic deformation[510] . Due to the signicantly enhanced diusion and chemical reactivity of the nanostructured surface layer produced by SMAT, gaseous nitriding has been successfully carried out on a Fe plate at 300 C[11] , evidently lower than conventional gaseous nitriding temperatures (550 C). In addition, a much thicker chromized surface layer has been obtained on an SMAT low carbon steel sample than that on the coarse-grained counterpart after the same pack
Corresponding author. Senior Engineer; Tel.: 23971882; E-mail address: [email protected] (X. Si). +86 24

chromizing treatment[12] . In the present work, we demonstrate the possibility of lowering aluminizing temperature by SMAT in a commercial low carbon steel plate, which is among the most broadly used steels. The microstructure, hardness, chemical and phase compositions of the aluminized SMAT surface layer were investigated in comparison with those of the coarse-grained one after the same treatment. 2. Experimental A commercial low carbon steel, with compositions (wt pct) of Fe, 0.11C, 0.01Si, 0.39Mn, 0.024S (max), 0.01P (max), was used in the present work. The sample was annealed at 950 C for 120 min in vacuum to eliminate the eect of mechanical deformation and to obtain homogeneous coarse grains. A plate sample (100 mm100 mm4.0 mm in size) was subjected to SMAT, of which the set-up and procedure have been described previously[6,12] . In brief, a large number of hardened steel balls (8 mm in diameter) were placed at the bottom of a cylinder-shaped vacuum chamber vibrated for 60 min by a generator at a frequency of 50 Hz at ambient temperature. The as-annealed sample was xed at the upper side of the chamber and impacted by ying balls repeatedly and multidirectionally. Because the sample surface was plastically deformed with high strains and high strain rates, grains in the surface layer were eectively rened. The SMAT sample and the coarse-grained one were aluminized under same conditions, i.e., at two temperatures (500 and 600 C, respectively) for 8 h in a packed powder mixture of 50Al, 2NH4 Cl and 48Al2 O3 (in wt pct) in a double container designed by Meier et al.[13] . After aluminizing treatment, the samples were wire-brushed and ultrasonically cleaned to remove adhering packed materials. Cross-sectional observations of the as-SMAT and the aluminized samples were performed on a Nova Nano-SEM 430 scanning electron microscope (SEM). Al distribution in the aluminized surface layer was monitored by using a fully quantitative (Oxford Programs) X-ray energy dispersive spectroscope (EDS).

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Fig. 1 (a) Cross-sectional SEM morphology and (b) a typical bright-eld TEM image of the top surface layer of the SMAT low carbon steel sample. The insert in (b) shows the corresponding selected area electron diraction pattern

A protective layer of pure Ni of 50 m in thickness was electrodeposited onto the sample surface for preparing the cross-sectional samples. Microstructure of the top surface layer of the SMAT sample was also observed by using a Philip EM-420 transmission electron microscope (TEM). In addition, X-ray diraction (XRD) analysis of the surface layer was carried out to identify the phase information in the aluminized surface layer, by using a Rigaku D/max 2400 X-ray diractometer with Cu K radiation. The microhardness variation along depth from the aluminized surface was measured on cross-sectional samples by using a Nano Indenter XPTM (Nano instruments) tted with a Berkovich indenter. The maximum load for each measurement was 9 mN with duration of 5 s, and the distance between any two neighboring indentations was at least 10 m. The load-displacement data obtained during the rst unloading were analyzed using the Oliver-Pharr method to determine hardness[14] . 3. Results and Discussion 3.1 Microstructures of the SMAT surface layer Clear evidences of plastic deformation have been observed in the SMAT surface layer of 200 m in thickness, as shown in the cross-sectional SEM morphologies in Fig. 1(a). Grains in the surface layer are signicantly rened and the microstructure diers markedly from that in the coarse-grained matrix (see the bottom part in Fig. 1(a)). The degree of deformation increases with decreasing depth from the topmost treated surface, so that it is dicult to distinguish the microstructure in the top surface layer of 100 m by SEM. TEM observations in the top surface layer of the SMAT sample (as shown in Fig. 1(b)) reveal that the microstructure is characterized by ultrane equiaxed ferrite grains with random crystallographic

orientations, as indicated by the selected area electron diraction (SAED) pattern (inset in Fig. 1(b)). The mean grain size obtained from a number of TEM images indicates that it has been rened from 50 m to 9 nm in the top surface layer by SMAT. Detailed microstructural characterizations of the SMAT surface layer by XRD and TEM show that the grain size increases with increasing depth and it reaches 100 nm at the depth of 18 m[12] . Ferrite grains are rened via sequential formation of dislocation cells in original grains, transformation of cell walls into subboundaries, and evolution of subboundaries into highly misoriented grain boundaries (GBs) separating the nanocrystallites[7,9,12] . When ferrite grains are rened to a critical size, plastic deformation occurs in carbide phase. Carbides in the steel are progressively rened into smaller particles and/or dissolved into the ferrite phase with increasing strain and strain rate[9,12] , so that no cementite is observed in the top surface layer in Fig. 1(b). 3.2 Aluminizing kinetics of the SMAT sample The cross-sectional SEM observations for the SMAT and the coarse-grained samples after the aluminizing treatment at 600 C for 8 h are shown in Fig. 2(a) and (b), respectively. It is clear that a continuous and dense aluminide surface layer (the dark layer) has been formed on both samples. Measured Al concentration proles (see Fig. 2(c)) indicate that the atomic concentration of Al is about 70% in the aluminide surface layers on both samples. In comparison with the aluminide coating formed on the coarsegrained sample (16 m in thickness), the coating on the SMAT sample (52 m) is much thicker after the same aluminizing treatment. A similar dierence has also been observed on the samples with and without SMAT after the aluminizing treatment at 500 C for 8 h, as listed in Table 1. The thickness of the alu-

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Fig. 2 Cross-sectional SEM morphologies of the SMAT (a) and the coarse-grained (b) low carbon steel samples after the aluminizing treatment at 600 C for 8 h. (c) and (d) show variations of Al concentration and hardness with the depth from the topmost surface, respectively

Table 1 Comparisons of the average thicknesses (in m) of aluminide surface layers on the SMAT and the coarse-grained (CG) low carbon steel samples after the aluminizing treatments at 500 and 600 C for 8 h, respectively. m is the ratio of k (see Eq. (1)) on the SMAT sample to that on the CG sample Temp./ C 500 600 SMAT sample 10.91.8 52.59.3 CG sample 2.40.5 16.34.3 m 20.6 10.4

minide coating on the SMAT sample aluminized at 500 C is comparable with that on the coarse-grained sample aluminized at 600 C. Formation of an obvious aluminide coating is dicult at temperatures below 500 C, due to the limited deposition rate of Al onto the sample surface. Because a large content (50 wt pct) of Al is contained in the pack powder mixture, a constant Al concentration in the source might be expected during the aluminizing procedure at a xed temperature and the growth kinetics of the aluminide layer can be represented by a parabolic rate equation of the form[3,15] , y 2 = kt (1)

where y is the thickness of the aluminide layer after treating duration of t and k is the mean growth rate. Therefore, the ratios (m) of k on the SMAT sample to the one on the coarse-grained sample are derived for the aluminizing treatments at 500 and 600 C, respectively, as shown in Table 1. It is indicated that the growth kinetics of the aluminide layer on the SMAT steel is about 10 times higher than that on the coarsegrained sample at 600 C, and the m value is doubled at 500 C. The much enhanced aluminizing kinetics in the SMAT low carbon steel is expected to result from the

formation of a nanostructured surface layer, in which a considerable volume fraction of GBs (30 vol. pct for an average grain size of 10 nm[16] ) act as numerous fast diusion channels for Al. In addition, a higher energy state of GBs induced by SMAT relative to the conventional GBs is expected to further increase the diusivity of Al in the nanostructured surface layer[17,18] . The lower m value at 600 C than at 500 C in Table 1 might be induced by a faster grain growth at the higher temperature. This is because the fraction and the excess energy of GBs may decrease and result in a reduction of growth kinetics of the aluminide coating on SMAT sample, accompanying the grain growth at temperatures above 500 C[12] . A previous work[19] revealed that the growth kinetics of aluminide diusion coating on an alloyed steel was enhanced by shot peening at temperatures below 667 C and the enhancement eect progressively diminished as temperature increased. This work also suggests a positive eect of microstructure renement on the aluminizing kinetics at lower temperatures. The variation of hardness along depth in the SMAT sample aluminized at 600 C was compared with that in the aluminized coarse-grained counterpart in Fig. 2(d). The hardness values of both surface layers are 15 GPa after the aluminizing treatment, while the matrix is about 3 GPa. However, the hardened surface layer on the SMAT sample is much thicker than that on the coarse-grained sample after the same aluminizing treatment. This dierence is consistent with the measured thicknesses of aluminide surface layers on the samples. It is clear that surface hardness of the aluminized samples has been promoted by the formation of iron aluminide coatings. 3.3 Phase evolution in the aluminide layer XRD patterns (as shown in Fig. 3) demonstrate

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grains might catch each other and stop growing at an earlier stage. It was discussed that the nucleation frequency might be increased by an order of about 106 with a reduction of grain size from 40 m to 40 nm[12] .
(a)

4. Summary In conclusion, it has been demonstrated that aluminizing low carbon steels at a temperature far below the austenitizing temperature is possible by the formation of a nanostructured surface layer by SMAT. A surface layer consisted of -Fe2 Al5 phase, of 52 m in thickness, is formed on the SMAT sample after a pack aluminizing treatment at 600 C for 8 h, more than 3 times thicker than that on the aluminized coarse-grained counterpart. And the enhancement effect is doubled at 500 C. The enhanced aluminizing kinetics is expected to result from a much increased GB diusivity in the nanostructured surface layer. In addition, no obvious texture is detected in the Fe2 Al5 surface layer on the aluminized SMAT sample, due to the signicantly increased nucleation frequency of the Fe2 Al5 phase in the nanostructured surface layer.
Acknowledgements This work was nancially supported by the National Science Foundation of China (Nos. 50701044 and 50890171), and the Ministry of Science and Technology of China (No. 2005CB623604). REFERENCES [1 ] R. Mvrel, C. Duret and R. Pichoir: Mater. Sci. Teche nol., 1986, 2, 201. [2 ] K. Murakami, N. Nishida, K. Osamura, Y. Tomota and T. Suzuki: Acta Mater., 2004, 52, 2173. [3 ] R.W. Richards, R.D. Jones, P.D. Clements and H. Clarke: Int. Mater. Rev., 1994, 39, 191. [4 ] Z.D. Xiang and P.K. Datta: Acta Mater., 2006, 54, 4453. [5 ] K. Lu and J. Lu: J. Mater. Sci. Technol., 1999, 15, 193. [6 ] K. Lu and J. Lu: Mater. Sci. Eng. A, 2004, 375-377, 38. [7 ] N.R. Tao, Z.B. Wang, W.P. Tong, M.L. Sui, J. Lu and K. Lu: Acta Mater., 2002, 50, 4603. [8 ] H.W. Zhang, Z.K. Hei, G. Liu, J. Lu and K. Lu: Acta Mater., 2003, 51, 1871. [9 ] L. Zhou, G. Liu, X.L. Ma and K. Lu: Acta Mater., 2008, 56, 78. [10] W.L. Li, N.R. Tao and K. Lu: Scripta Mater., 2008, 59, 546. [11] W.P. Tong, N.R. Tao, Z.B. Wang, J. Lu and K. Lu: Science, 2003, 299, 686. [12] Z.B. Wang, J. Lu and K. Lu: Acta Mater., 2005, 53, 2081. [13] G.H. Meier, C. Cheng, R.A. Perkins and W. Bakker: Surf. Coat. Technol., 1989, 39-40, 53. [14] W.C. Oliver and G.M. Pharr: J. Mater. Res., 1992, 7, 1564. [15] P.N. Bindumadhavan, S. Makesh, N. Gowrishankar, H.K. Wah and O. Prabhakar: Surf. Coat. Technol., 2000, 127, 252. [16] C. Suryanarayana: Int. Mater. Rev., 1995, 40, 41. [17] Z.B. Wang, N.R. Tao, W.P. Tong, J. Lu and K. Lu: Acta Mater., 2003, 51, 4319. [18] Z.B. Wang, K. Lu, G. Wilde and S. Divinski: Appl. Phys. Lett., 2008, 93, 131904-1. [19] Z.D. Xiang and P.K. Datta: Scripta Mater., 2006, 55, 1151.

Intensity / a.u.

(b)

(002)

(130)

(c)
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-Fe Al
2

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(400)

(310)

(112)

20

30

40

50

60

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Fig. 3 XRD patterns of the SMAT (a) and the coarsegrained (b) samples after the aluminizing treatment at 600 C for 8 h. (c) shows an XRD pattern obtained from the reported powder diraction data (JCPD card No. 29-0043)

that aluminide coatings formed on the SMAT and coarse-grained samples aluminized at 600 C for 8 h consist almost exclusively of -Fe2 Al5 phase. Comparing with the XRD pattern for a standard powder specimen of -Fe2 Al5 (Fig. 3(c), JCPD card No. 290043), where (002) and (130) Brag diraction peaks show the highest diraction intensities, it is apparent that the iron aluminide coating on the aluminized coarse-grained sample is strongly textured because a much higher intensity of (002) peak is detected, while no obvious texture forms in the aluminized SMAT surface layer. According to the results of pole gure analyses in literature [2], where a similar XRD pattern was obtained, a brous texture is expected in the coarse-grained sample. From thermodynamic considerations, -FeAl3 phase possesses the lowest free energy of formation and it is expected to form preferentially in Fe-Al system. However, it is the -Fe2 Al5 phase that forms in most cases due to the higher growth rate and favored crystallographic orientation (c axis)[2,3,15] . For example, the growth rates of Fe2 Al5 and FeAl3 at 715 C were reported to be 220 and 21 m2 /s, respectively[15] . The (00l) planes of Fe2 Al5 phase are thought to be the most densely packed and smooth, giving the lowest surface energy[2] . In the coarsegrained sample, few Fe2 Al5 particles are expected to nucleate at the GBs at the early stage of aluminizing process and grow up with c axis aligned along the direction perpendicular to the interface between coating and matrix to minimize the surface energy. Therefore, a strong brous texture is developed after the aluminizing process. While a plenty of GBs in the nanostructured surface layer produced by SMAT signicantly increase the nucleation frequency of Fe2 Al5 , the texture is more dicult to be developed because

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