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Intermetallics 19 (2011) 1455 e 1460 Contents lists available at ScienceDirect Intermetallics journal homepage:

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Intermetallics

journal homepage: www.elsevi er.com/locate/intermet Effect of silicon on the formation of intermetallic phases

Effect of silicon on the formation of intermetallic phases in aluminide coating on mild steel

Wei-Jen Cheng * , Chaur-Jeng Wang

Department of Mechanical Engineering, National Taiwan University of Science and Technology, No. 43, Sector 4, Keelung Road, Taipei 10607, Taiwan, ROC

article info

Article history:

Received 27 December 2010 Received in revised form 17 May 2011 Accepted 18 May 2011 Available online 12 June 2011

Keywords:

A. Aluminides, miscellaneous

A. Multiphase intermetallics

B. Phase identi cation

C. Coatings, intermetallic and otherwise

abstract

Mild steel was coated by hot-dipping into molten baths containing pure aluminum, Al e 0.5Si, Al e 2.5Si, Al e 5Si and Al e 10Si (wt.%) at 700 C for 180 s. Silicon s effect on the formation of the intermetallic phase in the aluminide layer was investigated by using a combination of scanning electron microscope (SEM), energy dispersive X-ray spectroscopy (EDS) and electron backscatter diffraction (EBSD). The micrograph observation showed that the aluminide layer resulting from hot-dipping in pure aluminum possesses the thickest intermetallic layer and a rough interface between intermetallic layer and steel substrate. As the silicon content in the molten bath increased, the thickness of the intermetallic layer decreased substantially and the interface between the intermetallic layer and the steel substrate became at. On the other hand, EDS and EBSD observation revealed the aluminide layer resulting from hot-dipping in Al e 2.5Si not only possessed FeAl 3 and Fe 2 Al 5 , but also formed cubic s 5(C) -Al 7 (Fe,M) 2 Si (M ¼ Mn, Cr or Cu) above the FeAl 3 and scattered s 1 -(Al,Si) 5 Fe 3 in the Fe 2 Al 5 . However, as the content of silicon in the molten aluminum bath increased, s 5(C) -Al 7 (Fe,M) 2 Si began to be replaced by hexagonal s 5(H) -Al 7 Fe 2 Si and

s 6 -Al 4 FeSi.

2011 Elsevier Ltd. All rights reserved.

1. Introduction

Hot-dip aluminizing has been proven as one of the effective coating techniques to plate an aluminide layer on steels in order to improve the oxidation resistance of steels [1,2] . During the hot-dip aluminizing process, steels are immersed into a molten aluminum bath for a period of time to form an intermetallic layer over the surface of steels by atomic inter-diffusion between the dipped steels and the molten aluminum bath. Then the residual aluminum liquid on the steels will form an aluminum topcoat with the same composition as the aluminum bath after removal from the bath. According to the composition of the molten aluminum bath, hot-dip aluminizing can be classi ed as hot-dipping in pure aluminum or in aluminum e silicon [3] . In the aluminide layer of mild steel hot- dipped in pure aluminum, the intermetallic layer is composed of a thick, brittle Al-rich intermetallic phase. This is, in practical terms, unformable. It renders deformation of the aluminide steel by deep drawing, bending or edging impossible [4] . Several studies [5 e7] , have reported that the failure of the aluminide layer can be attrib- uted to the formation of cracks in the layer. When the aluminide steel undergoes thermal shock or thermal cycling, the thermal

* Corresponding author. Tel.: þ 886 2 2733 3141x7309; fax: þ 886 2 2737 6460. E-mail address: d9603505@mail.ntust.edu.tw (W.-J. Cheng).

0966-9795/$ e see front matter 2011 Elsevier Ltd. All rights reserved. doi: 10.1016/j.intermet.2011.05.013

expansion coef cient (TEC) mismatch between the Al-rich inter- metallic layer and the steel substrate can result in cracking in the layer. On the other hand, an irregular interface between the inter- metallic layer and the steel substrate can be observed in the alu- minide layer of mild steel hot-dipped in pure aluminum. This irregular interface acts as a stress concentrator within the aluminide layer. This may cause an aluminide layer with a rough intermetallic layer/steel substrate interface to crack more easily than a at intermetallic layer/steel substrate interface when external loads are applied to the aluminide steel during assembly procedures at room temperature [4] . Since good workability of aluminide steel is an important condition for a wide number of applications, silicon is often added into the aluminum bath in order to diminish the thickness of the intermetallic layer and atten the interface between the intermetallic layer and the steel substrate [3,4,8] . Studies [3,9] concerning the microstructure of mild steel hot- dipped in aluminum e silicon indicate that the thickness of the intermetallic layer when mild steel is hot-dipped in alumi- num e 2.5 wt.% silicon decreases to approximately half the thickness of the intermetallic layer when mild steel is hot-dipped in pure aluminum. Although the thickness of the intermetallic layer keeps reducing as the silicon content in the aluminum bath increases, the tendency to diminish the thickness of the intermetallic layer will slow down when the hot-dip aluminum bath contains more than 10 wt.% silicon. Therefore, aluminum containing 10 wt.% silicon is

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W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460

also the most common composition of molten aluminum bath for hot-dipping aluminum e silicon. However, the formation of Fe e Al e Si ternary intermetallic phases in the aluminide layer of mild steel hot-dipped in an aluminum bath with 10 wt.% silicon

causes complicated phase transformations, leading to multiple voids and cracks forming in the aluminide layer during use in high- temperature situations, after completion of hot-dipping. This leads to reduction of the useful lifetime of aluminide steel [2,10] . Based on the above characterization about hot-dip aluminide steel, it can be concluded that the phase constitution of the aluminide layer

in uences the layer s ability to resist high-temperature oxidation.

Unfortunately, the complex crystal structures and narrow range of composition of the Al-rich Fe e Al e Si ternary phases make phase identi cation dif cult [11] . Electron backscatter diffraction (EBSD) is a technique for crystallographic analysis of crystalline materials in a scanning electron microscope. It provides crystallographic information regardless of the content of materials by analyzing Kikuchi patterns or electron backscattered diffraction patterns (EBSPs). EBSPs are constructed by an extensive network of Kikuchi lines that join together at various zone axes. Each Kikuchi line and zone axis represent a speci c crystallographic plane and direction within the crystal, respectively. Thus, EBSD has been widely used for phase identi cation in many multiphase materials. In this study, the EBSD technique was employed to analyze the effect of silicon addition in the aluminum baths on the phase constitution of alu-

minide layers on specimens of hot-dipped mild steel.

2. Experimental procedures

A commercial AISI 1005 steel was used as the substrate material in this study. The chemical composition of the adopted steel is

Fe e 0.05C e 0.24Mn e 0.01P e 0.01S (wt.%). The specimens for hot- dipping were immersed in the pure aluminum, Al e 0.5Si, Al e 2.5Si,

Al e 5Si and Al e 10Si (wt.%) molten baths at 700 C for 180 s and then

cooled down to room temperature in static air. Each bath also con-

tained trace amounts of manganese, chromium and copper totaling to about 1 wt.%. Details of the preparation of the hot-dipped spec- imen have been described in our previous study [12] . Cross-sectional aluminide layers were prepared for metallographic examination using standard grinding and polishing procedures. Specimens were examined using an optical microscope (OM) and a eld emission gun-scanning electron microscope (FEG-SEM) in backscattered electron mode (BSE) to reveal atomic number contrast images to distinguish phases by their chemical composition difference. The chemical composition of the phases observed from SEM/BSE micrographs was revealed by energy-dispersive spectrometry (EDS) in the FEG-SEM system. Specimens were analyzed using EBSD for

a further veri cation of the crystallographic structure of the phases that formed in the aluminide layers. For EBSD analysis, the FEG-SEM, operating at 20 kV, attached to an OXFORD EBSD acquisition system with INCA Crystal software, was used to record the EBSPs. The experimental EBSPs were further indexed by INCA Crystal software through comparison with the simulated EBSPs which were created according to the crystallographic structures from the Inorganic Crystal Structure Database (ICSD). 6 Kikuchi lines and 1.5 angular tolerance were employed to index the EBSPs to decrease misiden-

ti cation. Also, the mapping function in EBSD was used to expose the

phase distribution in the aluminide layers.

3. Results

3.1. Microstructure of aluminide layers

The cross-sectional OM micrographs of aluminide layers on mild steel hot-dipped in aluminum baths with various silicon additions

are shown in Fig. 1. All of the aluminide layers were composed of an outer aluminum or aluminum e silicon topcoat and an inner continuous intermetallic layer, and possessed several intermetallic phases with different morphologies scattered in the aluminum or aluminum e silicon topcoat. As the silicon content in the aluminum bath increased and reached 10 wt.%, the thickness of the interme- tallic layer decreased from 130 mm when hot-dipped in pure aluminum to 3.5 mm when hot-dipped in Al e 10Si. A typical tongue- like morphology at the intermetallic layer/steel substrate interface can be found in the aluminide layer of hot-dip pure aluminum, but this transforms into a at morphology as the silicon content in the aluminum bath increases to more than 2.5 wt.%. Fig. 2 reveals the top-view OM micrographs of the aluminum or aluminum e silicon topcoats of mild steel hot-dipped in aluminum baths containing various silicon additions. The scattered interme- tallic phases possess the same needle-like morphology in both the aluminum and aluminum e silicon topcoats when hot-dipped in pure aluminum and in Al e 0.5Si, and granular and Chinese script morphologies in the aluminum e silicon topcoat when hot-dipped in Al e 2.5Si as shown in Fig. 2 (a) and (b). In the alumi- num e silicon topcoat, when hot-dipped in Al e 5Si, the scattered intermetallic phases formed not only polyhedral particles, but also plate-shaped morphologies, as shown in Fig. 2 (c). Fig. 2 (d) shows the top-view OM micrograph of the aluminum e silicon topcoat when hot-dipped in Al e 10Si. The scattered intermetallic phases possess the primary polyhedral particle morphology and a small amount of plate-shaped morphology.

3.2. Phase identi cation of intermetallic phase in aluminide layers

The cross-sectional BSE micrographs of the intermetallic layers between the topcoats and steel substrates of mild steel hot-dipped

the topcoats and steel substrates of mild steel hot-dipped Fig. 1. Cross-sectional OM micrographs of mild

Fig. 1. Cross-sectional OM micrographs of mild steel after hot-dipping in (a) pure aluminum, (b) Al e0.5Si, (c) Al e2.5Si, (d) Al e5Si and (e) Al e10Si molten baths at 700 C for 180 s.

W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460

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C.-J. Wang / Intermetallics 19 (2011) 1455 e 1460 1457 Fig. 2. Top-view OM micrographs of

Fig. 2. Top-view OM micrographs of intermetallic phases with different morphologies in outer aluminum or aluminume silicon topcoat of mild steel after hot-dipping in (ae b) Al e 2.5Si, (c) Ale 5Si and (d) Al e10Si molten baths at 700 C for 180 s. Matrix, gray phase and black phase are aluminum, intermetallic phase and silicon, respec- tively; G, H, P and L represent granular, Chinese script, polyhedral and plate-shaped intermetallic phases, respectively.

in the aluminum baths with various silicon additions and the cor- responding chemical compositional results determined by EDS revealed that the intermetallic layers in the all of the aluminide layers were composed of four phases with different compositions (A e D phases) as shown in Fig. 3 and Table 1. Fig. 4 (a e c) is the experimental EBSPs and their indexed results of the A, B and C phases in the intermetallic layers. It reveals that the crystallo- graphic structures of the A, B and C phases are monoclinic FeAl 3 (space group C 2/ M , a ¼ 1.549, b ¼ 0.808 and c ¼ 1.247 nm, b ¼ 108 )

1.549, b ¼ 0.808 and c ¼ 1.247 nm, b ¼ 108 ) Fig. 3. Cross-sectional

Fig. 3. Cross-sectional BEI micrographs of intermetallic layers between topcoats and steel substrates of mild steel after hot-dipping in (a) pure aluminum, (b) Al e 0.5Si, (c) Ale 2.5Si, (d) Al e5Si and (e) Al e10Si molten baths at 700 C for 180 s. Micrographs were taken from entire intermetallic layer except for those hot-dipped in pure aluminum and Al e0.5Si which were taken on topcoat/intermetallic layer interface. A, B, C and D represent different intermetallic phases according to the atomic number contrast and EDS compositional results.

Table 1 Phase identi cation results of intermetallic phases with different morphologies examined by EDS and EBSD.

Types of aluminum bath

Morphologies of intermetallic phases

EDS identi cation (at.%)

 

EBSPs identi cation

 

Al

Fe

Si

Pure aluminum

Needle-like Continuous IMC layer A Continuous IMC layer B

84.3

15.7

e

 

FeAl FeAl Fe 2 Al 5

3

3

76.1

23.9

e

72.4

27.6

e

Al

e

0.5Si

Needle-like Continuous IMC layer A Continuous IMC layer B

84.8

13.6

1.6

 

FeAl FeAl Fe 2 Al 5

3

3

 

76.2

22.8

1.0

71.7

27.4

0.9

Al

e

2.5Si

Granular Chinese script Continuous IMC layer A Continuous IMC layer B Continuous IMC layer C Continuous IMC layer D

74.7

15.9

9.4

s

5(C)

5(C)

-Al 7 (Fe,M) 2 Si -Al 7 (Fe,M) 2 Si

 

73.3

16.9

9.8

s

74.2

23.3

2.5

FeAl 3 Fe 2 Al 5 s 1 -(Al,Si) 5 Fe 3

70.4

26.5

3.1

47.3

32.4

20.3

74.7

17.2

8.1

s

5(C)

-Al 7 (Fe,M) 2 Si

Al

e

5Si

Polyhedral Plate-shaped Continuous IMC layer A Continuous IMC layer B Continuous IMC layer C Continuous IMC layer D

74.8

16.9

8.3

s

5(C)

-Al 7 (Fe,M) 2 Si

 

69.9

14.9

15.2

s 6 -Al 4 FeSi FeAl 3 Fe 2 Al 5

73.6

23.3

3.1

69.1

27.8

3.1

46.7

33.3

20.0

s 1 -(Al,Si) 5 Fe 3 s 5(C) -Al 7 (Fe,M) 2 Si and

73.5

18.2

8.3

 

s

5(H)

-Al 7 Fe 2 Si

Al e 10Si

Polyhedral Plate-shaped Continuous IMC layer A Continuous IMC layer B Continuous IMC layer C Continuous IMC layer D

68.4

20.3

11.3

s

5(H)

-Al 7 Fe 2 Si

68.8

16.3

14.9

s 6 -Al 4 FeSi FeAl 3 Fe 2 Al 5 s 1 -(Al,Si) 5 Fe 3 s 5(H) -Al 7 Fe 2 Si

67.7

25.1

7.2

66.7

28.6

4.7

44.1

32.3

23.6

68.2

20.6

11.2

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W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460

Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455 e 1460 Fig. 4. Indexed EBSPs of (a)

Fig. 4. Indexed EBSPs of (a) FeAl 3 , (b) Fe 2 Al 5 , (c) s 1 -(Al,Si) 5 Fe 3 , (d) s 5(C) -Al 7 (Fe,M) 2 Si, (e) s 5(H) -Al 7 Fe 2 Si and (f) s 6 -Al 4 FeSi. In the simulated EBSPs, the yellow, purple and red lines represent that the intensity of Kikuchi line are > 0.6, >0.25 and 0.25, respectively. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

[13] , orthorhombic Fe 2 Al 5 (space group CMCM, a ¼ 0.768, b ¼ 0.640

and c ¼ 0.420 nm) [14] and triclinic s 1 -(Al,Si) 5 Fe 3 (space group P-1,

a ¼ 0.465, b ¼ 0.633 and c ¼ 0.750 nm, a ¼ 101 , b ¼ 106 and

g ¼ 101 ) [15] , respectively. However, D phase in the intermetallic layers when hot-dipped in Al e 2.5Si and in Al e 10Si were identi ed as cubic s 5(C) -Al 7 (Fe,M) 2 Si (M ¼ Mn, Cr or Cu; space group PM -3,

a ¼ 1.256) [16] and hexagonal s 5(H) -Al 7 Fe 2 Si (space group P 63/ MMC ,

a ¼ 1.240 and c ¼ 2.623 nm) [17] , respectively as shown in Fig. 4 (d)

and (e). However, D phase in the intermetallic layer, when hot- dipped in Al e 5Si, was composed of both s 5(C) -Al 7 (Fe,M) 2 Si and s 5(H) -Al 7 Fe 2 Si phases. In order to fully understand the phase distribution of s 5(C) -Al 7 (Fe,M) 2 Si and s 5(H) -Al 7 Fe 2 Si phases in the intermetallic layer when hot-dipped in Al e 5Si, the mapping func-

tion in EBSD was used to expose the crystallographic information in the intermetallic layer. It can be discovered that the D phase in the intermetallic layer when hot-dipped in Al e 5Si comprised not only the primary s 5(C) -Al 7 (Fe,M) 2 Si phase, but also a small amount of

s 5(H) -Al 7 Fe 2 Si phase in the inner part of the D phase as shown in Fig. 5 . Although the compositions of s 5(C) -Al 7 (Fe,M) 2 Si and s 5(H) -

Al 7 Fe 2 Si phases are similar, s 5(C) -Al 7 (Fe,M) 2 Si possesses 0.5 e1.3 at.%

of manganese, chromium and copper. In the aluminum and aluminum e silicon topcoats of mild steel hot-dipped in pure aluminum and Al e 0.5Si, although the EDS composition of the needle-like intermetallic phase does not match with any Fe e Al or Fe e Al e Si intermetallic phase, EBSD analysis still can reveal that the needle-like intermetallic phase in these two topcoats is FeAl 3 . The reason that EDS cannot expose the correct composition of the needle-like intermetallic phase is that the small phase area of the needle-like intermetallic phase caused the elec- tron beam of FE-SEM to hit both the needle-like intermetallic phase and the matrix of the topcoat during EDS analysis. On the other hand, EDS and EBSD analyses of the scattered intermetallic phases in the aluminum and aluminum e silicon topcoats con rmed that the granular and Chinese script intermetallic phases in specimen hot-dipped in Al e 2.5Si and the polyhedral intermetallic phase in specimen hot-dipped in Al e 5Si are all the same s 5(C) -Al 7 (Fe,M) 2 Si phase. However, the polyhedral intermetallic phase in the alumi- num e silicon topcoat of specimen hot-dipped in Al e 10Si was

identi ed as s 5(H) -Al 7 Fe 2 Si phase. Also, the plate-shaped interme- tallic phase in specimens hot-dipped in Al e 5Si and in Al e 10Si was identi ed as monoclinic s 6 -Al 4 FeSi (space group C 2/ C , a ¼ 0.618, b ¼ 0.617 and c ¼ 2.081 nm, b ¼ 91 ) [18] as shown in Fig. 4 (f).

2.081 nm, b ¼ 91 ) [18] as shown in Fig. 4 (f). Fig. 5. (a)

Fig. 5. (a) Cross-sectional BSE micrograph and (b) corresponding EBSD phase distri- bution map of intermetallic layer on mild steel after hot-dipping in Al e5Si molten bath at 700 C for 180 s.

W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460

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Fig. 6 shows the comparison of the intermetallic layer thickness of mild steel hot-dipped in aluminum baths with various silicon additions. As the silicon content in the aluminum bath increased to 5 wt.%, the thickness of the intermetallic layer substantially decreased, by about 85% from that of hot-dipping in pure aluminum. The intermetallic layers are composed mainly of Fe e Al intermetallic layers while the silicon contents in the aluminum baths are 2.5 and 5 wt.%, and the amounts of Fe e Al e Si intermetallic layers become greater than the Fe e Al intermetallic layers when the silicon content in the aluminum bath is increased to 10 wt.%.

4. Discussion

In summary, from the characterization of microstructure and phase constitution in the aluminide layers on mild steel hot-dipped in aluminum baths with various silicon additions as shown in Table 1, it can be concluded that the intermetallic layers, when hot-

dipped in aluminum baths containing less than 0.5 wt.% silicon, comprise an outer minor FeAl 3 layer and an inner major Fe 2 Al 5 layer. Also, FeAl 3 and Fe 2 Al 5 layers still can be observed co-existing with

Fe e Al e Si intermetallic phases when the silicon content in the

aluminum baths exceeds 2.5 wt.%. The Fe e Al e Si intermetallic phases identi ed in this study, ranked by aluminum content, were s 5(C) -Al 7 (Fe,M) 2 Si, s 6 -Al 4 FeSi, s 5(H) -Al 7 Fe 2 Si and s 1 -(Al,Si) 5 Fe 3 pha- ses. Among the Fe e Al e Si ternary intermetallic phases, the hexag- onal structure of the s 5(H) -Al 7 Fe 2 Si phase was rst reported in 1953 by Robson and Black [19] . On the other hand, several studies [20] have reported that s 5(H) -Al 7 Fe 2 Si phase would transform into

a cubic structure of s 5(C) -Al 7 (Fe,M) 2 Si phase when trace amounts (about 0.3 wt. %) of dissolved transition metals, such as manganese, chromium and copper, are added into the aluminum e iron e silicon alloy. In this study, the total amount of these elements in the aluminum baths with various silicon additions is about 1 wt.%, which leads to the formation of cubic s 5(C) -Al 7 (Fe,M) 2 Si phase. Although the s 5(C) -Al 7 (Fe,M) 2 Si and s 5(H) -Al 7 Fe 2 Si phases are two different phases, many studies have proposed that the reaction and formation mechanisms for these two phases are the same [21 e23] . Moreover, the formation of the intermetallic phases in the alumi- nide layers is controlled by the inter-diffusion between molten aluminum baths and mild steel substrate, in which aluminum and silicon diffused inward to the steel substrate and iron migrated outward to the molten baths. As a result, the formation of the s 5(C) -

Al 7 (Fe,M) 2 Si and s 5(H) -Al 7 Fe 2 Si phases located above the FeAl 3 phase

7 Fe 2 Si phases located above the FeAl 3 phase Fig. 6. Comparison of thickness

Fig. 6. Comparison of thickness of intermetallic layers after mild steel is hot-dipped in aluminum baths with various silicon additions at 700 C for 180 s.

in the intermetallic layer may be attributed to the monovariant peritectic reaction Liquid þ FeAl 3 4 s 5(C) -Al 7 (Fe,M) 2 Si/s 5(H) -Al 7 Fe 2 Si or the quasi-peritectic reaction U10 (Liquid þ FeAl 3 4 (Al) þ s 5(C) -

Al 7 (Fe,M) 2 Si/ s 5(H) -Al 7 Fe 2 Si) at 620 C while cooling from the hot-dip

temperature [21]. The s 5(C) -Al 7 (Fe,M) 2 Si and s 5(H) -Al 7 Fe 2 Si phases scattered in the aluminum e silicon topcoats could form by the

eutectic reaction Liquid 4 (Al) þ s 5(C) -Al 7 (Fe,M) 2 Si/s 5(H) -Al 7 Fe 2 Si while cooling from the diffusion temperature [22,23] . On the other hand, it can be found that the s 5(C) -Al 7 (Fe,M) 2 Si phase transforms into a s 5(H) -Al 7 Fe 2 Si phase when the silicon content in the aluminum baths increases from 5 to 10 wt.%. Many studies concerning the formation of cubic s 5(C) -Al 7 (Fe,M) 2 Si and hexagonal s 5(H) -Al 7 Fe 2 Si phases [22] have indicated that the s 5(C) -Al 7 (Fe,M) 2 Si phase is

a metastable phase, which is only formed during fast solidication.

On the contrary, the s 5(H) -Al 7 Fe 2 Si phase formed preferentially at

a relatively slower solidi cation rate. In this study, the silicon

additions in the aluminum bath are 0.5, 2.5, 5 and 10 wt.%. As the silicon content in the aluminum bath increased and drew close to the eutectic point of aluminum and silicon (about 13 wt.% silicon), the liquidus line of the molten aluminum baths decreased from 660 C for pure aluminum to 600 C for Al e 10Si. This decrease of the liquidus line of the molten aluminum baths with more silicon added into the bath implies that the molten aluminum bath con- taining more silicon would possess a relatively slower solidi cation rate than a bath containing less silicon while these molten

aluminum baths were cooled from the same hot-dip temperature of 700 C to room temperature in static air. Consequently, the s 5(C) -

Al 7 (Fe,M) 2 Si phase formed in the aluminide layers by the traces of

manganese, chromium and copper in the aluminum baths tended to be replaced by the s 5(H) -Al 7 Fe 2 Si phase because the solidi cation rate of residual aluminum e silicon liquid on the surface of the steel

was slowed down as the silicon content in the aluminum baths increased. On the other hand, the s 1 -(Al,Si) 5 Fe 3 phases observed in this study all performed as precipitates in the Fe 2 Al 5 phase of the intermetallic layers or at the FeAl 3 /Fe 2 Al 5 interface. In all of the

Fe e Al e Si intermetallic phases, the s 1 -(Al,Si) 5 Fe 3 phase possesses

the highest iron content and a very high silicon content (about

30 at.% iron and 20 at.% silicon in this study), and the lower silicon content in the Fe 2 Al 5 phase shows that silicon is less soluble in the

Fe 2 Al 5 phase [24] . Therefore, when the amount of solid-solute

silicon in the Fe 2 Al 5 layers increased (from 0.9 to 4.7 at.%) as the silicon content in the aluminum baths increased, more s 1 -(Al,Si) 5 Fe 3 would be forced to precipitate in the Fe 2 Al 5 phase or at the FeAl 3 /Fe 2 Al 5 interface. Considering both microstructure and phase constitution of the

aluminide layers of mild steel hot-dipped in aluminum baths with various silicon additions, it can be found that the intermetallic layer of steel hot-dipped in pure aluminum not only composed of an outer minor FeAl 3 layer and an inner major Fe 2 Al 5 layer, but also possessed a tongue-like morphology at the Fe 2 Al 5 /steel substrate interface. A wealth of research [3,4,25] has claimed that the formation mechanism of this tongue-like Fe 2 Al 5 layer is due to the 30% vacancy rate in the c-axis of the crystal structure of Fe 2 Al 5 causing aluminum atoms to diffuse much more rapidly inward. Thus, Fe 2 Al 5 tends to be orientated by the xed c-axis of the crystal structure, and grows rapidly along the diffusion direction during hot-dipping. On the other hand, it can be observed that the thick- ness of the Fe 2 Al 5 layer decreased substantially, but the thickness of the FeAl 3 layer reduced slightly, as the silicon addition in the aluminum baths increased. Also, the Fe 2 Al 5 /steel substrate inter- face transformed from the tongue-like morphology into a at morphology as the silicon content in the aluminum baths has increased to more than 2.5 wt.%. The explanation of these effects is attributed to the silicon in the aluminum baths being incorporated into the intermetallic layer and then reducing the diffusion rate of

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W.-J. Cheng, C.-J. Wang / Intermetallics 19 (2011) 1455e1460

aluminum atoms in Fe 2 Al 5 , by occupying the vacancies in the c-axis of the crystal structure of Fe 2 Al 5 [26] . Previous studies about modi cations to hot-dipped aluminide steel, by adding silicon in the molten aluminum bath [3,9] , have proposed that the addition of 10 wt.% silicon can effectively decrease the thickness of the intermetallic layer and atten the intermetallic layer/steel substrate interface. Due to the fact that the thinner intermetallic layer is much more deformable and the at intermetallic layer/steel substrate interface has the ability to avoid the accumulation of stress during the assembly processes, this microstructure provides the aluminide layer on steel with better mechanical properties [4] . However, the fact that the Fe e Al e Si phase is the major intermetallic phase in this aluminide layer caused complicated phase transformations and was accompanied by several voids and the formation of cracks in the aluminide layer during use in high-temperature situations after completion of hot- dipping, resulting in the reduction of the useful lifetime of alumi- nide steel [2,10] . Considering both mechanical properties and useful lifetime of the hot-dipped aluminide steel, the optimal alu- minide layer should possess a thin intermetallic layer and a at intermetallic layer/steel substrate interface, but little or no forma- tion of Fe e Al e Si phases. In the comparisons of the microstructures and phase constitutions of the ve aluminide layers on mild steel resulting from hot-dipping in aluminum baths with various silicon contents in this study, it can be noted that the thickness of the intermetallic layer decreased signi cantly from 130 mm when steel was hot-dipped in pure aluminum to 17 mm after hot-dipping in a bath with 5 wt.% silicon. The tongue-like intermetallic layer/steel substrate interfaces were eliminated also, when the silicon addition in the aluminum bath increased to 5 wt.%. Also, the intermetallic phase in the aluminide layer when hot-dipped in Al e 5Si is still dominated by the Fe e Al phase. The useful lifetime of the ve alu- minide steels in the present study, however, needs further inves- tigations or tests with respect to their oxidation behaviors over extended periods, which we will undertake in the near future.

5. Conclusions

EBSD provides a rapid and accurate phase identication of Fe e Al and Fe e Ale Si intermetallic phases in the aluminide layers on mild steel hot-dipped in aluminum baths with various silicon additions. Silicon addition in the aluminum bath not only decreased the thickness of the intermetallic layer and eliminated the rough inter- metallic layer/steel substrate interface, but also altered the phase constitution of the aluminide layers. Fe e Ale Si intermetallic phases, s 5(C) -Al 7 (Fe,M) 2 Si, s 5(H) -Al 7 Fe 2 Si, s 6 -Al 4 FeSi and s 1 -(Al,Si) 5 Fe 3 , were found when the silicon addition in the aluminum baths exceeded 2.5 wt.%. The formation of the s 5(C) -Al 7 (Fe,M) 2 Si phase could be attributed to the traces of manganese, chromium and copper in the aluminum baths, which stabilized cubic symmetry, at the expense of the hexagonal structure of the s 5(H) -Al 7 Fe 2 Si phase. However, The s 5(C) -Al 7 (Fe,M) 2 Si phase tended to be replaced by the s 5(H) -Al 7 Fe 2 Si phase because the solidi cation rate of residual aluminum e silicon liquid on the surface of the steel was slowed down as the silicon content in the aluminum baths increased. Among the ve types of aluminide layers, the intermetallic layer resulting from hot-dipping in Al e 5Si is the thinnest layer still dominated by the Fe e Al phase. Al e 10Si, on the other hand, is dominated by Fe e Al e Si phase.

Acknowledgment

The authors are very grateful to the National Science Council of the Republic of China for funding support under Grant No. NSC 98-

2221-E-011-038.

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