Materials Science Forum Vols. 519-521 (2006) pp. 1871-1875 online at http://www.scientific.net (2006) Trans Tech Publications, Switzerland Observations of Intermetallic Compound Formation of Hot Dip Aluminized Kee-Hyun, Kim 1, a, Van-Daele, Benny 2, b, Van-Tendeloo, Gustaaf 2, c and Jong-Kyu, Yoon 1, d 1 Material Science and Engineering, Seoul National University, Seoul, 151-742, South Korea 2 EMAT, University of Antwerp, Groenenborgerlaan 171, B-2020 Antwerpen, Belgium a kpsky2@gmail.com, b Benny.VanDaele@ua.ac.be, c staf.vantendeloo@ua.ac.be, d jkyoon@snu.ac.kr Keywords: hot dip aluminizing process, intermetallic compound, dissolution, diffusion, interface. Abstract. A hot dip aluminizing process to simulate the continuous galvanizing line (CGL) was carried out in three successive steps by a hot dip simulator: the pre-treatment for removing scales on the 200 250 mm 2 and 1mm in thickness cold rolled steel sheet, the dipping in 660 C Al-Si melt for 3s and the cooling. In a pre-treatment, the steel specimen was partly coated by Au to confirm the mechanism of intermetallic compound (IMC) formation. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) analyses were followed to observe the cross-section and the distribution of the elements. The specimen was analyzed in the boundary of the dipped-undipped part to see the formation mechanism of the aluminized steel. An intermetallic compound (IMC) is rapidly developed and grown in the steel-liquid interface. It has been usually reported that the IMC was formed by the dissolution of iron in the steel substrate toward the melt and the diffusion of aluminum in an opposite direction. The specimen is covered with aluminum-10 wt.% silicon, forms the IMC in the part that was not Au coated. However, IMC is not formed in the Au-coated part. The interface of the dipped-undipped is also analyzed by EDX. At the interface of the steel-imc, it is clearly shown that the IMC is only formed in the dipped part and exists in the steel substrate as well, and contributes by iron, aluminum and silicon. The result clearly shows that only aluminum diffuses into the steel substrate without the dissolution of iron and forms the IMC between the steel substrate and the melt. Au coating and the short dipping time prevent the iron from dissolving into the aluminum melt. By TEM combined with focused ion beam (FIB) sample preparation, the IMC is confirmed as Fe 2 SiAl 8, a hexagonal structure with space group P6 3 /mmc. Introduction The combination of steel and aluminum provides superior properties: good formability, corrosion resistance, coating brightness and long service life [1]. Hot dip aluminizing process is a technology to use steel sheet that has the properties. The aluminized steel is widely used in such applications as automotive exhaust system parts, heat reflector plates etc. [2]. The hot dip aluminizing process consists of degreasing and descaling the surface of steel, dipping the steel sheet into an aluminum-silicon melt and cooling the coated steel. When the steel was withdrawn from the melt, a thin film of liquid coating adheres to and subsequently solidifies on the alloy layer. The solidified film bonds the outer lustrous coating to the underlying steel substrate, and forms intermetallic compounds (IMC) between the steel substrate and the melt [3]. The IMC affects the mechanical properties and the surface quality of the Al-coated steel. The IMC control the growth rate of the alloy layer during dipping. Besides, a thick IMC leads to coating cracking and delamination on subsequent fabrication of the material [3]. To manufacture the application products, one needs the exact analysis and accurate understanding of the formation mechanism of this IMC. It is usually reported that the IMC is formed by the dissolution of iron in the steel substrate towards the melt and the diffusion of aluminum in the opposite direction [4]. Other All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of the publisher: Trans Tech Publications Ltd, Switzerland, www.ttp.net. (ID: 143.129.150.92-21/11/06,10:00:08)
1872 Aluminium Alloys 2006 researchers contend that the diffusion reaction is principally governed by the interdiffusion of the reactants forming the alloy layer [3]. Reaction diffusion proceeds between the iron of the steel substrate and the Al-Si melt, and forms a layer of hard brittle IMC such as Fe-Al or Fe-Al-Si. But, there are few theoretical and phenomenological descriptions of solid-liquid diffusion reaction phenomena, particularly where the formation of IMC is involved. Studies have been performed over widely different ranges of dip times and temperatures and occasionally with melts containing unspecified elements with different explanations of the mechanisms of the alloy formation [3]. The major reason for the difficulty to obtain a theoretical description and the confusion of mechanism is the absence of an appropriate understanding and analysis of the IMC. In this study, with the help of several analysis equipments, the IMC between the steel and the melt has been explicitly analyzed and observed as the primary diffusing species in the aluminizing process. This study can lay a foundation of a theoretical approach and a full understanding of the hot dip aluminizing process. Experimental The composition of steel used in the hot dip aluminizing is shown in Table 1. The surface of the steel was degreased and descaled to provide a fresh surface to contact the Al-10wt.% Si (type I). The addition of Si is to reduce the alloy layer growth, improve formability, and increase the dissolution rate of the alloy layer between steel substrate and melt. The steel specimen was dipped into the Al Si melt in a hot-dip simulator to simulate the continuous galvanizing line. The dipping was executed at 660 C for 3s, the pressure of the air knife to control the thickness of the coating layer was 0.3 MPa and the dew point of the atmosphere (N 2 with 25 % H 2 gas) was 56.0 C. The specimen was dipped only three quarts in the melt. For the observation of the IMC formation mechanism, in a pre-treatment, the steel specimen was partly coated by Au. The Au coating condition was 5mA current for 5min. Scanning electron microscopy (SEM) and Energy dispersive X-ray spectroscopy (EDX) were used to identify and line-profile the phases of the IMC. In this study, EDX analysis combined with transmission electron microscopy (TEM) together with focused ion beam (FIB) sample preparation were used. Table 1. Composition of steel substrate used in hot dip aluminizing element C Si Mn P S Ni Cr Cu Al N O mass%. 0.038 0.025 0.291 0.011 0.005 0.029 0.034 0.079 0.064 0.007 0.003 Result and discussion Figure 1 shows a surface observation of the steel substrate, IMC, and Al coating layer. and IMC layer are exposed by NaOH solution etching for 10s. IMC is clearly observed between the steel and the Al melt. The composition of respective layers was also quantified by using the INCA software (in atomic %). In order to confirm the primary diffusing species in aluminizing, SEM and EDX analysis is used. The cross section of the partly dipped specimen is shown in figure 2. Aluminum is only coated in the dipped part, and IMC is formed in the dipped part as well. In the line profile by EDX, the boundary of steel and IMC is obviously shown.
Materials Science Forum Vols. 519-521 1873 Al Si Fe steel 0 0 100 IMC 63-64 9-10 26-28 Al 94-97 2-5 0.5-2.5 a) b) Fig. 1. The surface of aluminized steel etched (a) and compositions of respective layer (b) IMC Al layer a) b) Figure 2. Cross section of a specimen dipped only three quarts; a) micrographs of specimen (left side is the dipped part, right is the undipped), b) line profile of the red dot line in a) by EDX Figure 3 is the cross section of the steel specimen, partly coated by Au. IMC is only formed on the steel part that was not coated by Au. For manufacturing of the hot dip aluminized steel, one needs to confirm the formation mechanism of IMC. From figure 2 and 3, it can be seen that IMC is not formed in the melt side that many researchers alleged but in the steel substrate side. This also means that the primary diffusing species in the hot dip aluminizing (3s dipping time and 660 C dipping temperature) is aluminum. This result is in agreement with Kurakin s assertion that the main diffusing species in the aluminizing with Al-10%Si would be aluminum [5].
1874 Aluminium Alloys 2006 Al layer Au layer IMC Figure 3. Cross section of the hot dip aluminized steel partly coated by Au in pre-treatment It is observed that the diffusion of aluminum in the melt to the steel side forms the IMC. The aluminum with approx. 10% silicon forms a thin AlFeSi alloy between the steel substrate and the aluminum alloy. It has been reported that the AlFeSi compound prevents brittle FeAl phases from developing excessively and provides good adhesion and formability of the coating [1]. In the AlFeSi system, numerous compounds with only slight differences in composition are formed [3, 6-7]. Consequently, EDX is insufficient to confirm exactly the thin complex IMC. To overcome this difficulty, TEM related with focused ion beam (FIB) sample preparation was used in this study. Figure 4 shows the diffraction pattern of a TEM sample, prepared with focused ion beam (FIB). In other literature, the experiment procedure and result about the focused ion beam (FIB) sample preparation are explained in detail [8]. The IMC is Fe 2 Si Al 8 with a hexagonal unit cell (space group P6 3 /mmc). (01-1-1) (10-11) (0000) (1-102) Figure 4. Electron diffraction pattern of a focused ion beam (FIB) prepared sample
Materials Science Forum Vols. 519-521 1875 Summary A hot dip aluminizing process to simulate the continuous galvanizing line was carried out in 660 C melt for 3s. In a pre-treatment, the steel specimen was partly coated by Au. SEM, EDX and TEM phenomenologically confirmed the formation of an IMC. The IMC is rapidly developed and grows between the steel and the melt. Only aluminum diffuses into the steel substrate without the dissolution of iron at the interface of the steel-intermetallic compound. The primary diffusing species of the hot dip aluminizing process in this study is aluminum. Au coating on the steel and the short dipping time prevent the iron from dissolving into the aluminum melt. The IMC is confirmed to be Fe 2 SiAl 8 with a hexagonal unit cell (space group P6 3 /mmc). Acknowledgements This work and sample preparation was supported by the Technical Research Lab. of DongBu Co. Ltd, Incheon, Korea. References [1] Wilhelm Warnecke, Jürgen Froeber and Rolf Bode: SAE technical paper series 1999-01-0022 (1999), p. 1 [2] Yasutaka Kawaguchi, Kyosuke Ohasi, Susumu Yasuhara: Proceedings- Electrochemical Society PV (1993), p. 106 [3] R.W. Richards, R.D. Jones, P.D. Clements, H. Clarke: Int. Mater. Rev. 39 (1994), p. 191 [4] Marie-Laurence Giorgi, Jean-Bernard Guillot: Galvatech 04 Conference Proceedings, April 4-7 (2004), Chicago, USA, p. 703 [5] A. K. Kurakin: Fiz. Met. Metalloved., 30 (1970), p. 430 [6] Sung-Ha Hwang, Jin-Hwa Song, Yong-Suk Kim: Mater. Sci. Eng. A390 (2005), P. 437 [7] S. Murali, T. Sritharan, P. Hing: Intermetallics 11 (2003), p. 279 [8] Kee-Hyun Kim, et al.: Proceeding of THERMEC 2006, Vancouver, Canada, in press