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Materials Science and Engineering A xxx (2006) xxxxxx

Interaction of steel with pure Al, Al7Si and A356 alloys


Teng-Shih Shih , Shu-Hao Tu
Department of Mechanical Engineering, National Central University Chung-Li, Taiwan 32001, Taiwan, ROC Received 19 April 2006; received in revised form 6 November 2006; accepted 6 November 2006

Abstract Carbon steel bars were dipped in aluminum alloy melts for different periods of time. A reactive ironaluminum intermetallic layer grew at the interface between the melt and the steel substrate. This reactive layer was mainly composed of intermetallic FeAl (Fe2 Al5 ) and its thickness was inuenced by dipping time (360 min), surface roughness (0.74 m versus 0.07 m) and carbon content (0.20.4 wt%) of the steel bars and the elements (mainly Si and Mg) added in the aluminum alloys. An oxide lm, which existed at the interface between steel bar and melt, hampered the AlFe reaction. In comparison with a pure Al melt, the thickness of the reactive layer of the Al7Si alloy melt decreased after a very short dipping time (3 min), increased following an increase in the dipping time (10 min) then decreased after a long dipping time (>20 min). The thickness of the reactive layer of a 1040 steel bar dipped in an A356 alloy (Al7Si0.4Mg) melt for a given dipping time at 973 K, was the narrowest among all melts studied; including pure Al, Al7Si, Al1Mg and Al7Si0.4Mg alloys. 2006 Elsevier B.V. All rights reserved.
Keywords: Oxide lm; Reactive layer; Intermetallics

1. Introduction In the casting process aluminum alloys are poured or injected into the mold cavity to make the parts. The die set is preheated to reduce the temperature drop that occurs during the lling of the melt. The molten metal must be overheated (>Tm ; melting point) to enhancing its uidity during lling. Therefore, metal dies that come into contact with the molten aluminum are subjected to a high temperature for a period of time. The die material often contains 0.20.45 wt% carbon associated with some amount of the alloys, such as Mo, Cr, Mn, etc., to improve the heat and/or wear resistance. When a molten aluminum alloy comes into contact with a die, a reactive layer develops between the interface of the aluminum alloy and die substrate. Once die soldering occurs at the interface, it is difcult to strip the cast parts from the die cavity, resulting in both increased labor cost for removing the casting from the die cavity and deterioration of the surface quality of the casting. In an equilibrious state, Fe can react with Al to form Fe3 Al, FeAl, FeAl2 , Fe2 Al5 and FeAl3 phases [1]. However, not all of these intermetallic compounds occur during the dipping test; only the phases of Fe2 Al5 and FeAl3 have been conrmed [2].

Corresponding author. Tel.: +886 3 4267317; fax: +886 3 4254501. E-mail address: t330001@cc.ncu.edu.tw (T.-S. Shih).

Sundqvist and Hogmark found that three intermetallic phases of FeAl, FeAl2 , Fe2 Al5 and FeAl3 formed on the surface of steel during dipping tests [3]. Shankar and Apelian observed a reaction at the interface between molten aluminum alloy and tool steel. They found that phases of -(Al, Fe, Si), FeAl3 , Fe2 Al5 formed, in that order, toward the tool steel matrix [4]. Wang et al. described a crystalline Fe2 Al5 orthorhombic structure that contained 30% voids along the C-axis which made the Al diffuse much more rapidly into the diffusion front. Consequently one can see that the, Fe2 Al5 phase favors a rapid inux of aluminum atoms to the growth front of the crystal, resulting in the occurrence of a serrated interface, or tongue morphology between the reactive layer and steel substrate [2]. Kobayashi and Yakou found that Fe2 Al5 mainly formed when the diffusion temperature was less than 1073 K, but it might also occur when the immersion temperature is as high as 1173 K for 300 s. Increasing the diffusion temperature to 1273 K causes Fe3 Al, FeAl and Fe2 Al5 phases to grow, in that order, in conjunction with steel substrate [5]. Sundqvist and Hogmark also found that adding silicon to an aluminum alloy hampered the growth of the Fe2 Al5 phase in the hot dip aluminizing process. When the surface of the H-13 tool steel specimen was protected by an oxide layer the initiation and growth of the intermetallic phases was limited to some area where the oxide layer was decient [3]. The effect of silicon hampering the reaction rate of the intermetallic phases is denite

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but the reasons why silicon retards the growth of reacted layer are controversial. Nicholls explains that silicon changes the diffusion conditions of the Fe2 Al5 phase, resulting in slower solid state growth [6]. Komatsu et al. found that silicon accelerated the velocity of iron enrichment in initially iron-free aluminum melts [7]. Eggeler et al. used low carbon steel (0.18 wt% C) and Al + 2 wt% Si alloys to study the inuence of silicon on the growth of the intermetallic layer during hot dip aluminizing. They found that silicon acts on the solid state side and reduces thickness of the layer after hot dip aluminizing [8]. Shankar and Apelian found that silicon precipitates within the Fe2 Al5 phase and at the interfacial boundary between Fe2 Al5 and the ternary (Fe, Al, Si) phase layer [4]. Few researchers have focused on the initial transient interactions occurring at the interface between the steel substrate and molten aluminum alloys. Thus, in this study we measured the reactive layers thickness and discuss the progressive development of the interface between the steel substrate and the reactive layer based on microstructural observation and description of the phenomenon. The discussion covers both the effects of oxide layer decomposition and its interaction with silicon and magnesium during growth of the reactive phase (Fe2 Al5 ).

alloy. The steel bar might become partially bonded with the coated aluminum or aluminum alloys if the dipping time was not long enough to generate a reactive layer (AlFe Intermetallic phases). Once the bars surface was partially bonded, the coated aluminum could be detached from the steel bar during sample preparation and no reactive layer thickness would be recorded. The thickness of the reactive layer of the sectioned sample was measured for at least three observations to get a range of reactive layer thicknesses. 3. Results and discussion After the dipping test, the steel bars were sectioned and removed for microscopic observation. The thickness of the reactive layers between the aluminum alloy melt and the steel was measured; see Table 2. 3.1. Interaction of 1040 carbon steel and pure aluminum 3.1.1. Effect of dipping time Fig. 1ad shows the progressive development of the 1040 steel substrate, reactive layer and the interface between the steel and the pure Al, for dipping times of 10, 20, 40 and 60 min, respectively. When the dipping time was short, the thickness of the reactive layer thickness varied signicantly and the interface was bumpy. Some areas displayed a thicker reactive layer, but in some locations it was very narrow, as shown in Fig. 1a. Increasing the dipping time caused the interface to become more ragged and show a tongue morphology; see Fig. 1b. Further increasing the dipping time caused the ragged interface to become smoother but pores were generated in the reactive layer as shown in Fig. 1c. The interface again becomes bumpy when the dipping time is extended to 60 min; see Fig. 1d. The morphology of the interface between the reactive layer and the steel substrate varies depending on the dipping time (or reaction rate) and is affected by carbon diffusion in the substrate, aluminum diffusion in the reactive layer and their interaction. 3.1.2. Effect of surface roughness Highly polished 1040 steel bars (Ra = 0.07 m) are rst dipped in pure Al melt for different time periods, and the reactive layer thicknesses measured and listed in Table 2. A comparison of the thickness of the reactive layers on 1040 steel bars with different surface roughnesses showed that the highly polished samples had a wider layer of thickness when the dipping time was less than 10 min; see Table 2 for a comparison.

2. Experimental procedure In the hot dipping test, 1020 and 1040 carbon steel samples 16 mm in diameter and 50 mm in length were used; they were 0.20.4 wt% C, 0.450.9 wt% Mn. Before dipping, the steel bars were polished by abrasive papers to remove any surface oxide. The bars surface roughness remained at about 0.74 m (Ra) to assess the effects of the carbon contents of different melts on the reactive layer. A ne surface roughness of 0.07 m was adopted for a comparison of the effects of the surface roughness on the forming of the reactive layer. The alloys were prepared from pure commercial-grade aluminum (99.86 wt%), Al2 wt% Mg, Al50 wt% Si and A356 alloy (Al7 wt% Si0.4 wt% Mg). The different alloy melts are listed in Table 1. The pure Al and aluminum alloys were melted in a mufe furnace and held at a temperature 973 K. The steel bars were preheated at 523 K for 10 min then dipped in the melts for different dipping time periods: 360 min. After dipping for a giving time, the steel bars were pulled out from the melt, quenched in water then removed for sectioning and sample preparation. The samples were then observed by an optical microscope, and a scanning electron micrograph (SEM) equipped with an EDS analyzer. After dipping, the surface of steel bar was coated with a layer of aluminum or aluminum
Table 1 Materials used in this study Alloy Composition (wt%) Al Al7Si Al1Mg A356.2 Bal. Bal. Bal. Cr Cu 0.10 Fe 0.098 0.10 0.12

Mg 0.95 0.30.45

Mn 0.05

Si 7.67 0.09 6.77.5

Ti 0.007 0.20

Zn 0.05

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Table 2 Measured reactive layer thickness (m) for 1020 and 1040 steel bars dipped in different Al alloy melts, including pure Al, Al7Si, Al1Mg and A356 alloys; dipping times ranged from 3 to 60 min Time (min) Parameters 1020 Pure Al abrasive P80 (Ra: 0.74) 3 10 20 40 60 NA 82136 91200 200318 291336 1040 Pure Al abrasive P80 (Ra: 0.74) 1622a 4550 114136 227236 264282 1040 Pure Al abrasive P1 000 (Ra: 0.07) 3037 4570 77148 186210 214257 1040 Al7Si abrasive P80 (Ra: 0.74) 34 4776 6694c 8096c 90136c 1040 Al1Mg abrasive P80 (Ra: 0.74) 3446a,b 4862 7195 119152 210229 1040 A356 abrasive P80 (Ra: 0.74) NA 3040 3550 4560c 90100

Ra indicates the measured surface roughness of the polished steel bar (unit: m). a Partial bond. b Spalled intermetallic compounds from layer. c Film between the interfaces steel/intermetallic compounds.

Fig. 2 shows the interfacial and reactive layers of a highly polished 1040 steel bar dipped in pure Al melt for 3 min. When the steel bar was dipped in the aluminum melt, air trapped in the surface notches would react with aluminum to form alumina. The ne surface of the steel bar possesses ne notches, allowing more ne oxide particles at the interface than for the rough surface sample. These particles are potential sites for carbon

diffusion and lead to a higher extent of carbon depletion zones ahead of the melt. A carbon depletion zone is dened as an area of ferrite with few tiny spherical carbide particles. Consequently a thicker reactive layer is produced on the ne steel bar than on the rough steel bar when the dipping time is short, i.e., 3 min. Sundqvist and Hogmark describes that the initiation and growth of the intermetallic phases noting that they are affected by the

Fig. 1. Progressive development of reactive layer and interface between 1040 steel and pure Al after different dipping time periods: (a) 10 min; (b) 20 min; (c) 40 min; (d) 60 min; the surface roughness of 1040 steel bar is Ra = 0.74 m.

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Fig. 2. SEM micrograph showing the interface and reactive layer of 1040 steel bar (Ra = 0.07 m) dipped in pure Al melt for 3 min at 973 K; EDS analyses at points 1 to 7 are also included.

oxide and limited to a few locations [3]. Both ne notches, which offer more contacts for AlFe reaction, and a higher extent of carbon depletion zones are benecial for producing a thicker reactive layer. Wang et al. described that during aluminizing, Al reacts with cementite. Carbon reduced from the cementite combines with the iron to form FeAl intermetallics [2]. Fig. 2 shows that lamellar cementite becomes spherical at a holding temperature 973 K. The carbide particles are reduced in size by decomposition and carbon diffusion. A comparison of the carbon concentrations detected at different positions, from points 1 to 7 shows that the carbon in the reactive layer is more soluble than in the ferrite substrate. The area from point 1 to point 3 is covered by a carbon depletion zone although the carbide particles at point 3 are slightly coarser than at point 2 or point 1. The lower twintongue tip shows a small piece of extruded reactive phase into steel substrate (or carbon depletion zone), as shown at A. EDS analysis conrms that the reactive layer is indeed mainly composed of mainly Fe2 Al5 as detected by Kobayashi and Yakou [5]. Burkhardt et al. describe the three-dimensional framework of Fe and Al1 atoms in the Fe2 Al5 structure and outline the interatomic distance between the atoms building the framework. The channels that form in the Fe2 Al5 structure are shaped like pentagonal antiprisms [9]. Carbon gradually decomposes from

Fig. 3. SEM micrograph along with line scanning of Al, O, Mn, Fe elements across the valley of the reactive layer from point A to point B for a 1040 steel bar (Ra = 0.07 m) dipped in the pure Al melt for 3 min at 973 K.

spherical carbides to diffuse into the reactive layer via the channel. This can be partly conrmed by the tested carbon contents from point 4 to point 7. Fig. 3 shows the line scanning of Al, C, Mn and Fe from point A to point B for the highly polished 1040 sample dipped in pure Al melt for 20 min. The aluminum and iron proles show a gradual transition near the interface where transition phases, such as FeAl may develop. Maritra and Gupta used a diffusion couple experiment with pure Fe and a high purity AlSi eutectic alloy. They found that Fe2 Al5 was the only reactive phase at a temperature of 873 K but that FeAl and Fe2 Al5 phases were

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observed at 1073 K [10]. If reactive phase AlFe did occur, it should be minor and lie between the Fe2 Al5 phase and the ferrite substrate as depicted by the Al and Fe proles in Fig. 3. A cavity (or pore) on the valley of the reactive layer is shown in Fig. 2. After the steel bar comes into contact with the melt, oxide particles form and/or the oxide lm fractures, which provides potential sites for carbon diffusion and generates a carbon depletion zone in the nearby substrate. Aluminum reacts with Fe to form the reactive phase, Fe2 Al5 . The reactive phase protrudes into the steel substrate. The preferred orientation develops into the so-called tongue structure. Oxide particles (with carbon) may be trapped in the reactive layer or pushed into the valley of the reactive layer. The reactive phase grows preferentially in a direction perpendicular to the steel substrate but also normal to the side-wall, depending on the carbon depletion zone developed ahead of the interface. The reactive layer grows side-walls which seal as a gate when the two walls make contact. A piece of carbon depletion zone is therefore trapped in the reactive layer, as shown in area above point A in Fig. 2. Carbon persistently diffuses into the reactive layer, decreasing the extent of the carbon depletion zone, to nally become an entrapped pore, as indicated by the arrow in Fig. 2. 3.1.3. Effect of carbon content Decreasing the carbon content of the steel bar increases the thickness of the reactive interfacial layer both for short and long dipping times. A comparison of 1020 with 1040 steel is shown in Table 2. The 1020 steel bar possesses both lower carbon content and a higher fraction of ferrite than does the 1040 steel bar. Therefore, when the 1020 steel bar was dipped in the pure Al melt, the reactive layer increased its thickness, because more ferrite was available at the interface to react with the Al melt. The reactive layer would advance more quickly into the steel substrate when there was more ferrite located ahead of the interface front. In addition, the reactive phase shows favorable growth into the steel substrate via the ferrite grain boundaries. The tongue morphology therefore becomes much more apparent comparing with the 1040 steel bar dipped in the pure Al melt. 3.1.4. Reactions that occurred at the steel substrate ahead of the interface Fig. 4a shows the tongue morphologies of the reactive layer after 1020 steel was dipped in the pure Al melt for 20 min. The Fe, C and Al concentrations in the area ahead of the tip of the tongue were measured by EPMA; see Fig. 4b. The carbon content is relatively higher at the grain boundaries (both at A and B) than within the grain. The aluminum concentration prole displays a peak at the grain boundary A ahead of the tip of the reactive phase. The interdiffusion coefcients of the intermetallics, FeAl3 and Fe2 Al5 , at 1073 K, are 9.2 106 and 1.84 104 cm2 s1 , respectively [11]. The diffusion coefcient of carbon in ferrite at 973 K is about 1.8 106 cm2 s1 [12]. Aluminum diffuses through the intermetallics toward the ferrite grains but along the ferrite boundaries ahead of the tip of the reactive phase. Aluminum reacts with carbon (4Al + 3 C Al4 C3 ; Gf = 163.16 kJ/mol at 1000 K) to form aluminum carbide at the grain boundaries, as at point A of

Fig. 4. SEM micrograph along with line scanning of C, Fe and Al elements indicating the protruding reactive phases, entrapped aluminum carbide + carbon and side-wall growth of reactive phases for a 1020 steel bar dipped in pure Al for 20 min.

Fig. 4b. The carbon in the ferrite diffuses to the interface and the grain boundaries; see A and B. Ferrite reacts with the aluminums to form Fe2 Al5 via the following reactions: Fe + Al FeAl (11.09 kJ/mol), FeAl + Al FeAl2 (16.99 kJ/mol), FeAl2 + Al Fe2 Al5 (19.64 kJ/mol). The reactive product Fe2 Al5 protrudes into the ferrite substrate as shown in Fig. 2 below mark A. Aluminum carbide (or carbon) would move along the interface to approach the valley, to nally become a particle entrapped in the reactive layer. Fig. 4 shows that the reactive phase protrudes into ferrite substrate associated with aluminum carbide (or with carbon) trapped in the reactive layer. EDS analyses at the interface between the steel substrate and the reactive phase indeed conrms the existence of carbon. Side-wall growth also occurs in the reactive layer as indicated in Fig. 4. 3.2. Interaction of a 1040 steel bar with an Al7Si alloy Table 2 shows that when a 1040 steel bar is dipped into a Al7Si melt, after a short dipping time of 3 min the reactive layer is 310 m, which is far less than for the sample dipped in the pure Al melt which is 1622 m in thickness. However, increasing the dipping time to 10 min in the Al7Si alloy melt

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only causes the thickness of the reactive layer to be slightly greater than that dipped in the pure Al melt, i.e., 4776 m versus 4550 m. Extending the dipping time to longer than 20 min causes the reactive layer of the pure Al7Si alloy to be signicantly narrower than in pure Al. For a dipping time of 60 min, the thickness of the former is 90136 m and the latter is 264282 m. As explained previously, oxygen and/or an oxide lm exists in the surface notches of the steel bar when dipped in the aluminum melt. The oxide lm at the interface between the steel bar and aluminum melt tends to hamper the AlFe reaction and to decrease the thickness of the reactive layer for a given dipping time. The addition of silicon to the aluminum melt decreases the surface tension of the melt slightly. When silicon comes in contact with oxygen in the melt, the following reaction occurs [13]: 3{Si} + 3(O2 ) 3[SiO2 ] + 4{Al} 3{Si} + 2[Al2 O3 ], (1) where {}, () and [] represent the liquid, gas and solid states, respectively. Air trapped in the surface notches drives the above reaction leading to the decomposition of alumina at the interface between the steel bar and the Al7Si alloy melt. Fig. 5 shows the morphology of the reactive layer that formed between the 1040 steel bar and Al7Si alloy after 3 min of dipping time. The reactive layer varies its thickness from 3 m to about 10 m. The white spot in the layer contains carbon and indicates the possible existence particles of Al4 C3 , since no oxygen was detected. Optical observation shows that the interface between the reactive layer and the steel substrate becomes smoother after dipping time is increased. When the 1040 steel bar was dipped in the Al7Si alloy melt, oxide formed at interface. Carbon diffusing from the ferrite substrate into grain boundaries produced a carbon depletion zone for AlFe reaction. Aluminum carbide might also form at the interface. The reactive Fe2 Al5 layer is thin due to a mass decit of the Al content (93 wt% compared with pure Al) in the melt after a short 3 min dipping time. Increasing the dipping time to 10 min of the sample dipped in an Al7Si alloy melt leads to a slightly greater extent of the reactive layer, probably due to effect of silicon. The oxide is decomposed into ne particles which are pushed into valleys in the reactive layer or at the interface between the reactive layer and the steel substrate, in turn offering more sites for carbon diffusion. A carbon depletion zone can thus be readily formed ahead of the interface increasing the driving force needed to form Fe2 Al5 . Maritra and Gupta had studied an intermetallic compound in a FeAlSi ternary system to nd the solubility of Si in FeAl3 , Fe2 Al5 and Fe3 Al: it is in the range of 17 at% [10]. The solubility of silicon in the reactive layer, Fe2 Al5 , is partly conrmed by the EDS test results shown in Fig. 5. The capability of the reactive layer for aluminum diffusion as well as carbon diffusion is therefore greatly reduced. The driving force needed to form the reactive phase is greatly decreased. Table 2 shows that when the dipping time is longer than 20 min the extent of the reactive layer is greatly reduced; comparing the

Fig. 5. SEM micrograph showing the morphology of the reactive layer associated with EDS analyses of white spots (aluminum carbide) trapped in the reactive layer for a 1040 steel bar dipped in Al7Si alloy melt for 20 min.

results of the 1040 sample dipped in pure Al and in the Al7Si melt. Fig. 6a shows the morphologies of reactive phase after a 20 min dipping in the Al7Si melt Fig. 6bd show the EDS analyses at points B, C and D. The lm-like structure ahead of the interface contains mostly aluminum carbide, some silicon or silicon carbide, and carbon. The SiC formation energy is about 65.25 kJ/mol at 1000 K, which is lower than for forming Al4 C3 , but higher than for forming Fe2 Al5 . The two white spots detected in Fig. 6c and d are entrapped oxide. 3.3. Interaction of a 1040 steel bar with an Al1Mg alloy For short dipping times there is a big variation in the thickness of the reactive layer due to partial bonding and even peeling off of the coated layer during sample preparation. The thickness of the reactive layer is close to that of the sample dipped in the pure Al melt when the dipping time is 10 min; see Table 2. When Mg encounters oxygen and alumina, the following reaction occurs [13]:

(2)

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Fig. 6. (a) SEM micrograph showing the morphology of the interfacial and reactive phase; EDS analyses (b) at interface between steel substrate and reactive phase showing the existence of aluminum carbide and carbon; (c) oxide particle C; (d) oxide particle D for a 1040 steel bar dipped in Al7Si alloy melt for 20 min.

Shih and Liu also found that when the thermally formed alumina was in contact with the Al0.5Mg alloy melt it resulted in a thin lm of MgAl2 O4 forming at the interface between the oxide and the melt [14]. When the 1040 steel bar came in contact with the Al1Mg alloy melt, a lm of spinel (MgAl2 O4 ) formed at the surface of the steel bar. If the dipping time was short, the mass content of Mg was not enough to cover the whole surface of the steel bar. The reactive phase, Fe2 Al5 , was generated on part of the surface and part incorporated spinel. The measured data therefore show a big variation along with partial bonding (even peeling off). Increasing the dipping time caused the spinel to fracture and be trapped in the reactive layer. The tongue morphology shown is much more apparent than for the sample dipped in the Al7Si melt but is similar to that obtained after dipping in the pure Al melt. It is detected that Mg piled up in the area between the reactive phase and the melt ahead of the interface (1.22 wt%, average of three tests). There is no ternary AlFeMg intermetallic phase is in equilibrium with the aluminum-rich solid solution [15]. When the reaction layer increases in extent, Mg builds up ahead of the interface

between the reactive phase and the melt to form Mg2 Al3 . This binary intermetallic phase hampers the diffusion of aluminum atoms from the melt into the reacted phase and slows down the AlFe reaction reducing the thickness of the reactive layer; see Table 2. 3.4. Interaction of the 1040 steel bar with the A356 alloy The thickness of the reactive layer of the 1040 steel bar dipped in the A356 alloy melt is the minimum among all the alloys studied; see Table 2. EDS analysis conrmed that there was silicon in the reactive layer but no magnesium. Silicon has a smaller atomic size than magnesium and tends to diffuse into the reactive layer, greatly decreasing the capability of Al atoms to diffuse from the melt to react with the steel substrate. Magnesium accumulates at the interface between the reactive layer and the melt forming the binary intermetallic phase. The synergistic effects of silicon and magnesium in the A356 melt signicantly hampered the growth of the reactive phase Fe2 Al5 resulting in the minimum layer thickness.

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4. Summary and conclusions The interface between the reactive phase (Fe2 Al5 ) and the 1040 steel substrate grew from a tongue structure to a smooth structure to nally become ragged following the increasing dipping time in the pure Al melt. The tongue structure was much more apparent for the 1020 steel bar than for the 1040 steel bar. When the dipping temperature was 973 K, lamellar cementite in the steel substrate became spherical and gradually decomposed. Carbon diffused to the ferrite grain boundaries and to the interface between the steel substrate and the reactive phase, to react with the inward diffusion of Al to form Al4 C3 . The carbide particles associate with the oxide particles would be trapped in

the reactive layer and it would grow into the carbon depletion zone in the steel substrate. Fig. 7af schematically illustrate the development of oxides at the interface, the carbon diffusion, the formation of Al4 C3 , the entrapment of oxides and Al4 C3 + C, leading to the advancing and side-wall growth of the reactive phase. Dipping in the Al7Si alloy melt caused the silicon to react with the alumina oxide. The oxide fragments (ne particles) located at the interface provided potent sides for carbon diffusion, increasing the driving force for the formation of the reactive phase, if the dipping time was short. Silicon diffused into the reactive layer greatly reducing the Al and carbon diffusion capability and reducing the AlFe reaction rate, following the increase in dipping time. Dipping in the Al1Mg alloy melt caused spinel to form at the interface between the steel substrate and the reactive phase. Increasing the dipping time led to the fracturing of the spinel and the ne pieces of oxide particles stimulated carbon diffusion, increasing the AlFe reaction rate, for a short dipping time. Mg would gradually build up at the interface between the reactive layer and the melt, leading to the formation of a binary MgAl intermetallic phase. The AlFe reaction rate therefore decreased if the dipping time was long, decreasing the reacted layer thickness. Dipping in the A356 alloy melt caused the synergistic effects of: (a) Si being diffused into the matrix of reactive phase, which reduced the Al and carbon diffusion capability, and (b) Mg piled up at interface between the reactive phase and the melt. These effects greatly hampered the growth of the reactive phase resulting in the minimum layer thickness among all the alloys studied. References
[1] U.R. Kattner, in: T.B. Massalski (Ed.), Binary Alloy Phase Diagrams, ASM International, Materials Park, OH, 1990, p. 147. [2] Wang Deqing, Shi Ziyuan, Zou Longjiang, Appl. Surf. Sci. 214 (2003) 304311. [3] M. Sundqvist, S. Hogmark, Tribol. Int. 26 (1993) 129134. [4] S. Shankar, D. Apelian, Metall. Trans., B, Process Metall. 33 (2002) 465476. [5] S. Kobayashi, T. Yakou, Mater. Sci. Eng. A-Struct. Mater. Prop. Microstruct. Process. 338 (2002) 4453. [6] J.E. Nicholls, Corr. Technol. 11 (1964) 1621. [7] N. Komatsu, M. Nakamura, H. Fujita, J. Jpn. Inst. Met. 45 (1981) 416. [8] G. Eggeler, W. Auer, H. Kaesche, J. Mater. Sci. 21 (1986) 33483350. [9] U. Burkhardt, Yu. Grin, M. Ellner, K. Peters, Acta Cryst. B50 (1994) 313316. [10] T. Maritra, S.P. Gupta, Mater. Charact. 49 (2003) 293311. [11] K. Bouche, F. Barbier, A. Coulet, Mater. Sci. Eng. A-Struct. Mater. Prop. Microstruct. Process. 249 (1998) 167175. [12] J. Campbell, Casting, second ed., 2003, p. 13. [13] L. Yang, D. Zhu, C. Xu, J. Zhang, Metall. Trans., A, Phys. Metall. Mater. Sci. 27 (1996) 20942099. [14] T.S. Shih, Z.B. Liu, Mater. Trans. 46 (8) (2005) 18681876. [15] T. Lyman (Ed.), Metals Handbook, eighth ed., 1976, p. 392.

Fig. 7. Schematic illustrations showing the progressive development of: (a) contact between melt and steel substrate; (b) diffusion of carbon into ferrite grain boundaries and interface; (c) formation of carbon depletion zone in substrate and aluminum carbide at interface; (d) the reacted phase protruding into ferrite substrate along with Al diffusion inward to steel substrate; (e) formation of carbon depletion zone ahead of the tip of reactive phase; (f) morphologies of protruding reacted phase associated with side-wall growth and entrapment of oxide particles, aluminum carbide plus carbon for carbon steel dipped in pure Al.

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