Corrosion Science 48 (2006) 19391959 www.elsevier.

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Inuence of anodising current on the corrosion resistance of anodised AZ91D magnesium alloy
Zhiming Shi, Guangling Song *, Andrej Atrens
CRC for Cast Metals Manufacturing (CAST), Materials Engineering, School of Engineering, The University of Queensland, St. Lucia, Brisbane, Qld 4072, Australia Received 18 August 2004; accepted 9 August 2005 Available online 28 September 2005

Abstract The thickness, chemical composition and microstructure of anodised coatings formed on magnesium alloy AZ91D at various anodising current densities were measured. It was found that all these parameters could be aected by anodising current density, and hence the coatings formed at dierent anodising current densities had dierent corrosion resistances. This suggests that the corrosion performance of an anodised coating could be improved if a properly designed current waveform is used for anodising. In addition, based on the experimental results, some physical, chemical and electrochemical reactions involved in the anodising process were proposed to explain the anodising behaviour in this paper. 2005 Elsevier Ltd. All rights reserved.
Keywords: A. Magnesium; B. SEM; C. Anodic lm

1. Introduction Corrosion, particularly galvanic corrosion, is a complicated and serious problem in applications of magnesium alloys [19]. Coating is an eective solution to the problem [1012]. So far, various anodised coatings have been developed, such as HAE, DOW17, Tagnite, ANOMAG, MGZ and Keronite. These coatings not only serve as a corrosion resistant layer, but also provide a good base for paint coatings.
*

Corresponding author. Tel.: +61 7 33 65 41 97; fax: +61 7 33 65 38 88. E-mail address: g.song@minmet.uq.edu.au (G. Song).

0010-938X/$ - see front matter 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2005.08.004

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Anodising magnesium alloys normally requires high voltages and high current densities applied, which can usually cause sparking in anodising. Various anodising current densities that can result in dierent anodising behaviours have been tried. For example, Barton and John [13] anodised AZ91 magnesium alloy with a slowly increasing anodising cellvoltage before sparking began, then adjusted the cell-voltage to maintain a constant sparking until the cell-voltage reached 90 V. Sometimes, Barton also tried even higher cell voltages (e.g. 170350 V [14]) for anodising. Other researchers, such as Zozulin and Bartak [15], Sharma et al. [16] and Khaselev et al. [17], anodised magnesium alloys using a constant current density. The anodic behaviour of Mg and Mg alloys in NaOH or KOH solutions over a wide voltage range has been described by Evangelides [27], Huber [28] and Emley [29]. An anodising process can normally be divided into several stages [29,30]. For example, Khaselev and Yahalom [31] divided the anodising of MgAl alloys in KOH-aluminate solution into four dierent regions based on the polarisation curve: (1) primary passivity, (2) breakdown of primary passivity and metal dissolution, (3) secondary passivity, and (4) the breakdown of the secondary passivity. Khaselev and Yahalom [32] reported that the current density in the passive state decreased with an increase in the aluminate content in the solution and/or the aluminium content in the alloy. It is believed [15] that sparking occurs in anodising when the applied voltage is greater than the dielectric breakdown voltage of the layer produced in the pre-treatment process. In addition, it was found that the breakdown of lm associated with the sparking process was controlled by the interface of lm and electrolyte solution [37]. Although the previous investigations have indicated that anodising current density can signicantly inuence the corrosion performance of an anodised magnesium alloy, no systematic study has been carried out to reveal the mechanism. So far, it is not well understood how the anodising current density or cell voltage inuences the corrosion performance of an anodised coating. This paper aims to understand the anodising mechanism and to reveal the inuence of the anodising current density on an anodised coating in terms of its corrosion performance. 2. Experimental Specimens were cut from an AZ91D ingot. The AZ91D alloy contained 8.96% aluminium, 0.77% zinc, 0.23% manganese, <0.005% iron and balance magnesium. The specimens were abraded with 1200 grit SiC paper, washed with ethanol, degreased in 12%NaOH + 12%Na4B2O7. 10H2O + 9%Na2SiO3 solution at about 75 C for 25 min (which produced a thin chemical conversion lm on the surface), then washed again in demineralised water and nally placed in an anodising bath for anodising. The anodising bath solution was 1%KOH + 1.6%K2SiO3. Potassium hydroxide and potassium silicate are the most commonly used components of the anodising solutions for magnesium alloys [15,18,19]. Anodisation was performed using a controlled anodising current provided by a power supply whose maximum current and voltage can be preset. The specimen was the anode in anodising. The bath container was 304 stainless steel, containing about 700 ml of the bath solution. The steel container also acted as a cathode in anodising. The bath solution was cooled by owing tap water outside the steel container. To maintain a uniform distribution of temperature, the bath solution was also stirred by a magnetic stirrer in the steel container.

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The applied anodising current waveforms were as follows: (1) G0: the anodising current density was 20 mA/cm2 for 10 min. (2) G1: the anodising current density was 15 mA/cm2 for 20 min. (3) G2: the anodising current density was 20 mA/cm2 for 7 min, 15 mA/cm2 for 7 min and 10 mA/cm2 for 7 min. (4) G3: the anodising current density was 25 mA/cm2 for 7 min, 20 mA/cm2 for 4 min and 15 mA/cm2 for 7 min. (5) G4: the anodising current density was 20 mA/cm2 for 5 min. (6) G5: the anodising current density was 20 mA/cm2 for 10 min, 10 mA/cm2 for 10 min and 5 mA/cm2 for 10 min. (7) G6: the anodising current density was 20 mA/cm2 for 1 min. The waveforms of the above anodising current densities are schematically illustrated in Fig. 1. Apart from the waveforms of the anodising current densities, some specimens were also anodised by constant current densities 10, 15, 20 and 25 mA/cm2, respectively, in order to investigate the inuence of anodising current density on the coating performance. In addition, a polarisation curve of AZ91D was measured in the bath solution using (a) the DC power supply and (b) a potentiostat with a saturated silver/silver chloride electrode as reference. The dierence in potential between a saturated silver/silver chloride electrode and the stainless steel container was 255 mV, which is negligible compared with the anodising cell voltage. Nevertheless, in the study, the potentials relative to the saturated silver/silver chloride electrode measured by the potentiostat were converted into the cell voltages. The

30 20 10 0 30 20 10 0 30 20 10 0 30 20 10 0 30 20 10 0 30 20 10 0 30 20 10 0 0 4 8 12 16 20 24

G6 G5 G4 G3 G2 G1 G0
28

Current density (mA/cm2)

Time (min)
Fig. 1. Waveforms of controlled anodising current densities.

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other potentials or voltages presented in this paper if not specied are the cell voltages relative to the 304 stainless steel container. Oxygen evolution from the specimens during anodising was measured using a burette to evaluate the eciency of the anodisation. The burette, initially full of the bath solution, was mounted over a funnel that covered the AZ91D electrode being anodised. This setup is similar to that one used by Song et al. [2024] in measuring hydrogen evolution from Mg alloys and proven to be convenient and reliable [1,12,25]. After being anodised, the specimens were washed with demineralised water and dried for the following measurements. The microstructures of the anodised coatings were analysed using a Philips XL30 scanning electron microscope (SEM) and EDAX was used to determine the compositions of the anodised coatings in the same time. The elemental compositions were determined by X-ray photon spectroscopy (XPS) after the coating surface was cleaned by argon-ion-etching for 1 min. The corrosion performance of the anodised coatings was evaluated by immersion in 5% NaCl solution. The appearance of the samples after immersion was recorded. 3. Results and discussion 3.1. Anodising behaviours The variations of the cell voltages of the specimens anodised by various waveforms of anodising current are presented in Fig. 2. Fig. 3 shows the results of similar experiments that used the same total charge for the anodising experiments at dierent applied current densities. The increasing cell voltages indicate the growth of the anodised coatings. According to the dierences in cell voltage (Fig. 2), sparking behaviour and oxygen evolution, an anodisation process can be divided into three stages. In the initial stage, when

G3
400

G2
300

Cell voltage (Volts)

G0
200

G1 G4
100

G0 G1 G2 G3 G4

0 0 2 4 6 8 10 12 14 16 18 20 22 24

Time (min)
Fig. 2. The cell voltage response curves of AZ91D under dierent waveforms of current densities.

Z. Shi et al. / Corrosion Science 48 (2006) 19391959

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25 mA/cm
400 150

20 mA/cm

15 mA/cm

Cell voltage (Volts)

100

25 mA/cm 2 20 mA/cm 2 15 mA/cm 2 10 mA/cm Stage II

Cell voltage (Volts)

300

10 mA/cm Stage III

200

50 100

Stage I
0 0 50 100 150 200 250 300 0

(a)

Time (seconds)

(b)

400

800

1200

1600

2000

Time (seconds)

Fig. 3. The cell voltage response curves of AZ91D anodised by dierent current densities with the same amount of electric charge (18 C/cm2). (a) Early stages and (b) whole anodising process.

the cell voltage was lower than 10 V, there was no sparking and oxygen evolution was not signicant, either. In the second stage (cell voltage between 10 V and 190 V), there was no sparking but oxygen evolution was more signicant. In the third stage, sparking arcs were visible. The cell voltage was higher than 190 V and oxygen evolution became vigorous. It should be noted that in the initial and second stages, the cell voltage increased more quickly at a higher anodising current density. For example, when the current density increased from 15 mA/cm2 to 25 mA/cm2 (curves G1, G2 and G3 in Fig. 2), it took a shorter time for the cell voltage to climb up to the sparking voltage range. The cell voltage during the anodisation process was approximately proportional to the coating thickness. Therefore, the increase of cell voltage in the initial stage corresponded to the formation and thickening of an anodised lm on the AZ91D surface. For a constant-current, a higher current density resulted in faster lm formation and hence the cell voltage increased more quickly. In the third stage, the cell voltage increased slowly with anodising time. Sparking and oxygen evolution were the major phenomena. Under a given anodising current density, the cell voltage gradually approached a stable value. The sparking intensity can be controlled by the anodising current density. In experiments, a higher current density caused a more intensive sparking process and resulted in a coarser anodised coating. The eciency of anodisation or anodising current is determined by the formation rates of the coating and the by-products involved in the anodising process. The evolved oxygen is one of the most important by-products. So, a higher rate of oxygen evolution means a lower eciency of anodisation. Fig. 4(a) presents the volume of oxygen evolved in G0 to G4 anodising processes. To clearly reveal the oxygen evolution during anodising, a typical oxygen evolution curve and the corresponding cell voltage curve are presented in Fig. 4(b). The volume of oxygen increased more rapidly for G2 at 20 mA/cm2 than for G1 at 15 mA/ cm2. This indicates that in the same anodising stage, the eciency of anodisation was dependent on current density. The current eciency can be dened by g IF 100% IT 1

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Z. Shi et al. / Corrosion Science 48 (2006) 19391959

400 0.8

2.0

Volume of O2 (ml/cm )

G0 G1 G2 G3 G4

350 300

Cell voltage Volume of O2

0.6

G3

Volume of O 2 (ml/cm )

1.5

Cell Voltage (V)

250 200 150 100 50

III
0.4

1.0

II
0.2

0.5

G0 G4

G2 G1

I
0 0.0 0 2 4 6 8 10 12 14 16 18 20 22 24
4 8 12 16 20 24

0.0 0

Time(min)

b
0.25

Time (min)

Derivative of oxygen evolution (ml/min. cm )

100

50

Efficiency of current (%)

G0 G1 G2 G3 G4

0.20

G0 G1 G2 G3 G4

0.15

-50

0.10

-100

-150

0.05

-200 -2 0 2 4 6 8 10 12 14 16 18 20 22

0.00 0 4 8 12 16 20

Time (min)

Time (min)

Fig. 4. (a) The oxygen evolution curves, (b) the cell voltage and oxygen evolution curves (G1), (c) the curves of current eciency and (d) the derivative of oxygen evolution of AZ91D ingot during anodising processes.

where IT is the total applied current and IF is the current resulting in lm formation. If it is assumed that the only by-product is oxygen generated by reaction: 4OH 2H2 O O2 4e then IF can be estimated by I F I T I O2 3 where I O2 is the current density used for the electrochemical production (2) of oxygen, which can be estimated from the amount of the measured gas. Thus, the current eciency can be calculated (see Appendix 1): g I T I O2 100% IT 4 2

It should be noted that the current eciency as dened by Eq. (4) could lead to a negative value if there is a sucient amount of gas generated by a non-electrochemical reaction. In the initial stage, the evolved oxygen volume was very small (see Fig. 4(a) and (b)), which means that almost all of the applied current was used for coating formation. In the second stage, the evolved oxygen volume increased gradually (Fig. 4(a) and (b)), which can be interpreted as a gradual decrease in current eciency. In the third stage, the rate of

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oxygen evolution increased dramatically (Fig. 4(a) and (b)). Fig. 4(c) presents the current eciency calculated according to Eq. (4). The eciency varied with time in anodising. The current eciency became low and even negative in the third stage (see curves G1, G2 and G3 in Fig. 4(c)). The negative eciency could be due to the thermal decomposition of water during anodising, which will be analysed later. Fig. 4(d) shows the derivative of the evolved oxygen volume standing for the oxygen evolution rate. It also varied in anodising, corresponding well to the variation of current eciency (Fig. 4(c)). In the rst stage, the oxygen evolution rate was low. In the second stage, the oxygen evolution rate became higher. The derivative of the oxygen evolution exhibited complicated tendencies in the third stage. The oxygen evolution rate did not simply increase or decrease with time. Similar to the strange negative current eciency, the complicated oxygen evolution in this stage could also be associated with a non-electrochemical reaction. Fig. 5(a) shows that under a constant electric charge, the total amount of the measured gas (over the whole anodisation process) increased with increasing current density, and the total current eciency decreased with increasing current density. Fig. 5(b) shows how the oxygen evolution increased and the current eciency decreased with an increasing cell voltage at dierent current densities. It implies that the evolved oxygen volume is dependent on the cell voltage. The growth of the anodised coating should be proportional to the electrical charge used in coating formation, which is proportional to the total electrical charge used during anodisation minus the charge used for oxygen evolution. The electrical charges and the measured thicknesses of the coatings are listed in Table 1. It is clearly shown that the measured thicknesses of the anodised coatings were proportional to the applied densities of electrical charges, which is further illustrated in Fig. 6(a). Fig. 6(a) also shows that the nal cell voltage was proportional to the density of electricity charge. To further conrm this, the data from Fig. 6(a) are re-plotted in Fig. 6(c). It can be seen that there is a linear relationship between the nal cell voltage and the thickness of the coating. This is understandable as the nal cell voltage is closely associated with the thickness of an anodised coating. Fig. 6(b) shows that the measured total current eciency decreases with

Current density (mA/cm )

90 0.20

10 10

15 15

20 20

25 25
100

O2 evolution
3

0.18

85

Efficiency
Oxygen evolution (ml/cm )
2

O 2 evolution (ml/cm .C)

-100 2 -200

0.16 80 0.14

Efficiency
75

O2 evolution

-300

0.12

-400 0 -500 0 100 200 300 400

0.10 8 12 16 20
2

70 24 28

Current density (mA/cm )

2

Potential (volts)

Fig. 5. Under a constant electric charge (18 C/cm ) (a) total amount of oxygen evolved and current eciency vs. current density and (b) oxygen evolution and current eciency vs. cell voltage.

Efficiency of current (%)

Efficiency (%)

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Table 1 Thickness of the anodised coatings G4 Density of charge mA min/cm2 C/cm2 Thickness (lm) (measured) Amount of O2 evolved (ml/cm2) Charge for evolved oxygen (C/cm2)a Charge used for coatinga (C/cm2) Eciency (%)a Final cell voltage (V)
a

G0 200 12 17 0.169 2.66 9.34 77.8 316

G1 300 18 1920 0.758 11.96 6 33.6 355

G2 315 18.9 1821 0.657 10.364 8.5 45.2 371

G3 340 20.4 2023 2.429 38.33 18.33 87.9 372

100 6 1011 0.063 0.995 5.0 83 252

Calculation based on the reaction 4OH 4e = 2H2O + O2.

increasing charge density, particularly at a high charge density. This is probably due to more electrical charge used in the third stage of anodising at a higher charge density. The data in Fig. 6(a) were replotted in Fig. 6(d) to show the relationship between the total applied charge and the measured thickness. The apparent linear relationship could be fortuitous, because only some of the total charge resulted in growth of the anodised lm and the other resulted in oxygen generation. To examine the charge used for oxygen evolution, the theoretical electrical charges used for the coating formation and oxygen evolution were calculated and presented in Fig. 6(d). It should be noted that in the calculation is based on the assumptions that (a) oxygen was the only gas produced and measured during anodising and (b) all the oxygen was produced by electrochemical reaction (2). It is found that (CTCgas) $ thickness is a curve (which is approximately a straight line when coating thickness is small) with a maximum followed by a steep decrease to negative values. The steep decrease and the negative charge values indicate that assumption (a) is not valid at high voltage for a thick coating. It is possible that the intense sparking caused thermal decomposition of water into 2H2 and O2 at a high temperature. Therefore, it is interesting to estimate the amount of thermolysis gas by analysing the dierence between CT and (CTCgas), which is denoted as thermolysis gas (O2 + H2) in Fig. 6(d). The dierence is quite signicant. The signicant amount of thermolysis gas (O2 + H2) in the third stage conrms the previous postulation about the occurrence of water thermo-decomposition caused by sparking. The composition of the anodised coating can also be roughly estimated based on the relationship between the coating thickness and the charge Cq used for generation of the coating. The curves of Cq that are obtained by assuming that the lm is MgO, Mg(OH)2 or MgSiO3 with 15% porosity are plotted in Fig. 6(d) (see Appendix 2). It can be seen that CT is located between Cq-MgO and C q-MgOH2 or C q-MgSiO3 . This suggests that the coating could be a mixture of MgO and Mg(OH)2, or a mixture of MgO and MgSiO3 or a mixture of MgO, Mg(OH)2 and MgSiO3. 3.2. Anodised coating The microstructures of the anodised coatings are shown in Fig. 7. The pores of coating G4 (20 mA/cm2 for 5 min) are generally smaller than 1 lm in diameter and those of the G0 (20 mA/cm2 for 10 min) coating are near 2 lm (see Fig. 7). These results indicate that in

Z. Shi et al. / Corrosion Science 48 (2006) 19391959

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400

1947

G2 G1 G0

G3
80

20

G3

16

G0
200

Current efficiency (%)

Thickness (m)

G4

Final cell voltage (Volts)

G2 G1

300

40

12

Final cell voltage Thickness

100

-40

G4
8
0

-80

12

18

24

Density of charge (C/cm2)

10

12

14

16

18

20

22

24

Density of charge (C/cm2)

380 360

Final cell voltage (Volts)

340 320 300 280 260 240 10 12 14 16 18 20 22

c
20 15 10

Thickness (m)

Porosity = 15%

Charge (C/cm2)

5 0 -5 -10 -15 -20

Thermolysis gas (O 2+H2 )

CT-Cgas CT Cq-MgO Cq-Mg(OH) 2 Cq-Mg SiO

3

12

16

20

Thickness (m)

Fig. 6. Relationships between coating thickness, nal cell voltage, and density of electrical charges. (a) Thickness and nal cell voltage vs. density of electrical charge, (b) current eciency vs. density of charge, (c) nal cell voltage vs. thickness and (d) dependence of theoretical electrical charges of MgO, Mg(OH)2 and MgSiO3. Charge COe associated with electrochemical oxygen and total charge CT on coating thickness.

the second stage before the cell voltage reached 190 V, the anodised coating was relatively compact with only few tiny pores. In anodising, only occasional tiny sparking was observed in this stage. The reason for the microstructure of the G0 coating coarser than that of the G4 coating is that the more vigorous sparking occurred during anodising, especially in the last period. The G1 (15 mA/cm2 for 20 min) coating is irregularly porous with tiny

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Fig. 7. The SEM images of anodised coatings on AZ91D ingot.

pores less than 12 lm in diameter. The G2 coating has some large pores near 3 lm in diameter. The G3 coating has a microstructure similar to that of G1 coating, but with more large pores. Fig. 8 shows the sealed pores in a local sparking spot on the G5 coating. It seems that localised sparking caused a bump or a ridge on the coating (such a bump can even be visualised by the naked eye). The EDAX analysis (see Table 2) shows that the composition of the coating at localised sparking spots is similar to that of the normal coating areas, except that the Mg content is slightly lower and the silicon level slightly higher in the localised sparking spots than in the normal coating areas. The image shown in Fig. 8 provides evidence to support that some pores can be sealed during the anodisation

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Fig. 8. The cross-section of a localised sparking spot on anodised AZ91D alloy under G5 anodising condition.

Table 2 Compositions of the normal coating areas and localised sparking spots analysed by EDAX At.% Normal coating areas Postion 1 C O Mg Al Si K 27.91 39.00 13.92 1.33 16.28 1.56 Position 2 28.10 39.9 14.62 0.96 15.64 1.58 Position 3 29.42 38.03 14.03 1.15 15.87 1.50 Localised sparking spots Spot 1 29.06 37.97 14.20 1.42 15.83 1.52 Spot 2 28.57 39.98 10.15 0.88 17.59 2.83 Spot 3 29.80 40.30 8.00 0.81 18.47 2.61

process. Smaller pores and sealed pores in an anodised coating should be benecial to the corrosion resistance of the coating. The sealing could be attributed to the lower current density applied in the nal anodising stage. With the same amount of electric charge (18 C/cm2), the inuence of the anodising current density on the microstructure is insignicant; the irregular porous microstructures of all these coatings formed at dierent anodising current densities are almost the same (see Fig. 9). Comparing the microstructures of the coatings formed by dierent waveforms of current densities, it is found that the microstructure of a coating is closely associated with the nal cell voltage. If the nal cell voltage is low, the coating is ne and compact. Otherwise, the coating is coarser and porous.

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Fig. 9. SEM images of AZ91D ingot anodised under dierent current densities with the same amount of total electric charge.

Z. Shi et al. / Corrosion Science 48 (2006) 19391959 Table 3 Chemical compositions of the anodised coatings by XPS Conditions Atomic concentration (%) C G0 G1 G2 G3 G4 G5 G6 0.69 8.725 3.01 4.44 3.98 4.42 21.05 O 56.16 64.51 65.38 69.10 65.36 63.64 53.11 Mg 7.89 5.1 2.62 2.83 10.10 12.38 8.62 Si 26.51 21.61 14.85 23.51 20.10 19.51 10.57 Na 5.66 0.00 8.67 0.12 0.39 0.05 2.32 B 3.09 0.07 5.48 0.00 0.07 0.00 4.34 Si/Mg 3.36 4.24 5.66 8.3 1.99 1.57 1.22

1951

The compositions of the anodised coatings are presented in Table 3. In this study, the XPS detected area was about 3 3 mm2. In this area of an anodised coating, there were plenty of pores. The coating is thin inside the pores and thick outside the pores. Therefore, the measured XPS should be the average information of the thick lm outside the pores and the thin lm inside the pores. Hence, the XPS results should represent the average composition of an anodised coating. The anodised coatings contain mainly magnesium, silicon, and oxygen. The content of oxygen is near 55%, the content of silicon is in the range between 23% and 35%, and the magnesium content is from 3% to 16%. The high content of silicon in the coating should result from the deposition of the potassium silicate from the bath electrolyte. Sodium and boron in the coatings may come from the pre-treatment electrolyte. The alloying elements aluminium and zinc could not be found in the coating by XPS. This is probably because Al only exists in the coating adjacent to the interface of substrate and coating. It has been reported [26] that the diusion of Al in the surface lm on a Mg alloy is much slower than Mg under normal oxidation conditions and Al was also be found mainly in the zone adjacent to the interface between oxide lm and substrate. Moreover, it should be noted that the anodised coatings were formed in an Al-free bath solution. Even if there was some Al from the substrate, it should exist in the coating next to the substrate/coating interface, completely covered by Al-free oxides and hydroxides. Therefore, it is not easy to detect the Al-containing compounds. For a low level of Al in the coating, it is unlikely to form some spinels, like Al2MgO4. Table 3 indicates that the general composition of the coatings can be expressed by (MgO)x (SiO2)y H2O. The coecients x and y changed with the waveform of the current density. It is to some extent equivalent to a mixture of MgO, Mg(OH)2 and MgSiO3 in chemical composition, which is consistent with the estimated composition based on the electrical charge analysis (Fig. 6(d)). For G2 and G3, x was low and y was high. That means that the ratio of MgO and SiO2 in the coating can change with the applied current density. The corrosion performance of the coating could change with the ratio of MgO and SiO2, because in corrosive environments SiO2 is more chemically stable than MgO. In order to explore the anodisation mechanism of the Mg alloy, the compositions of the anodised coatings formed in the dierent stages are also analysed (see Table 4). Table 4 shows that the atomic ratio of Si/Mg increases from 0.5 to 6, which means that the outer layer of the coating is silicate rich and the dierent anodising reactions could occur in the dierent stages. In the rst stage, the atomic ratio of Si/Mg was 0.5, which can be interpreted as an indication that the deposition rate of Mg(OH)2 was the same as that of

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Table 4 Chemical compositions of the anodised coating formed in the anodisation dierent stages by XPS Anodising stage Anodising conditions Atomic composition (%) C Stage Stage Stage Stage Stage 1 1 1 2 3 2 V, 2 min 7 V, 2 min 12 V, 2 min 60 V, 2 min 370 V, 21 min (G2) 66.13 36.78 36.51 16.96 3.01 O 22.78 41.83 43.44 53.47 65.38 Mg 7.36 14.67 13.73 15.24 2.62 Si 3.73 6.71 6.31 14.33 14.85 Si/Mg 0.5 0.5 0.5 1 5.7

MgSiO3. In the second stage, the atomic ratio of Si/Mg was higher, suggesting that more silicate was deposited into the coating. The explanation for the high ratio of Si/Mg in stage 3 is that the amount of silicate deposited into the coating was much greater than Mg(OH)2. This could be attributed to the sparking induced thermo-decomposition of the bath solution (containing silicates) in this stage. In addition, a high content of carbon in these coatings is also noticed. This can be simply ascribed to the absorption of carbon dioxide from the atmosphere after anodising. In addition, high resolution XPS also exhibits a dierence in the binding energies between hydroxide and oxide, which conrmed the existence of hydroxyl in the coating. 3.3. Anodising process Based on the above results, a three stage anodising process of AZ91D under a constant current density can be proposed. (a) Initial stage: It is proposed that the reactions on the Mg anode include dissolution of Mg, deposition of Mg(OH)2 and MgSiO3 and oxygen evolution: 4OH 2H2 O O2 4e Mg Mg2 2e Mg Mg
2 2

2 5 6 7

2OH MgOH2 # SiO2 3 ! MgSiO3 #

Reaction (2) is the only side reaction, which is not signicant in this stage. Reactions (5) and (6) have been reported by Mizutani et al. [33] who believes that the lm on Mg alloys formed at a low cell voltage in alkaline solution consists of Mg(OH)2. The postulation of reaction (7) in this paper is inspired by Khaselev et al.s work [17] in which MgAl2O4 was found to be the composition of the anodised coating on Mg alloys in an aluminate containing solution. Most of the anodising current in this stage is consumed by the reaction (5). The formed coating in this stage is thin because the anodising time is short, less than 10 s and electrochemical reaction (5) is relatively slow, so chemical reaction (6) and (7) cannot be fast. The XPS results (Mg peak) of the coating formed in this stage suggest that the coating mainly contains Mg(OH)2 and MgSiO3. (b) Second stage: Evolution of some tiny oxygen bubbles can be observed. There is no sparking. The cell voltage increases rapidly from 10 V to 190 V (see Figs. 3 and 4(b)). Most of the current is

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used to form the anodised coating. It is postulated that the reactions include reaction (2), (5)(7) as well as Mg2 2OH MgOH2 MgO # H2 O 8

Mizutani et al. [33] reported that the anodised coating of Mg alloys formed at 60 V in an alkaline solution contained a mixture of magnesium hydroxide and magnesium oxide which can be conrmed by XRD analysis. Therefore, the involvement of reactions (5), (6) and (8) in this stage is reasonable. The evidence for reaction (7) is that magnesium silicate has been detected by XPS analysis in the anodised coating. Moreover, the limited oxygen evolution indicates that reaction (2) is still slow in the second stage (see Fig. 4(b)). The XPS results have indicated that the coating consisted of Mg(OH)2, MgO and MgSiO3 in this stage. The second stage usually lasts about 25 min depending on the applied current density (see Fig. 3(a)). The coating formed in this stage is compact and smooth. The thickness of the coating increases with anodising time. However, the maximum thickness of the coating is only several micrometers. With a coating on the surface, reaction (5) should be controlled by the mass-transfer processes in the coating. Under the circumstances, the cell voltage increases with the thickness of the coating in order to maintain the reaction rate. (c) Third stage: The obvious phenomena in this stage are sparking and vigorous oxygen evolution on the sample surface. The cell voltage continues to increase with anodising time but increasing rate becomes slow (see Figs. 2 and 3). In addition to reactions (2), (5)(8), the following reactions will occur at high temperatures in this stage. MgOH2 MgO # H2 O 2Mg O2 2MgO # MgO yMgSiO3 MgOx SiO2 y 2H2 O 2H2 " O2 " 9 10 11 12

The sparking activity can lead to a high temperature at sparking areas. At high temperatures, magnesium hydroxide formed in the rst two stages could be dehydrated (reaction (9)) and magnesium can react with active oxygen to form magnesium oxide directly (reaction (10)). However, reaction (6) still continue in the non-sparking areas because the XPS results suggest that there is still magnesium hydroxide in the coating. In addition to the chemical changes, at the high temperatures, anodised lm can be melted and mixed together around the pores resulting from sparking (reaction (11)). Reaction (11) is conrmed by SEM (see Fig. 8), which shows a localised melted area. It seems that the coating deposited in the rst two stages is locally melted by sparking to form a thick and coarse coating. Due to sparking and local high temperature, thermal-decomposition of water (12) near the sparking area becomes possible. The thermal-decomposition temperature of water has been reported to range from 2000 C to 5500 C [34,35]. It has been reported that the high temperature at the sparking location was estimated to be above 1000 C [37]. The temperature could be much higher in the centre of a sparking ame, which could result in fusion of silicate, magnesium hydroxide and magnesium oxide onto the metal surface. The intensive gas evolution and the decrease in measured current eciency or a negative eciency can all be easily understood as a result of the thermo-decomposition (reaction (12)) of water in this stage.

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The three-stage anodising process can be further veried by a polarisation curve (potential-current density) for AZ91D in the bath solution (see Fig. 10). There are three regions corresponding to the dierent anodising stages on the curve. The rst stage of anodising corresponds to a peak in the polarisation curve and t very limited oxygen evolution. Oxygen evolution rate became slightly higher and anodic current density increased dramatically and achieved a maximum when the cell voltage exceeded 4 V. In the second stage, the cell voltage higher than 10 V, the anodising current density became lower than the peak of the rst stage, corresponding to deposition of magnesium hydroxide on the surface. With increasing cell voltage, the anodised coating continued growing and thickening and oxygen evolution also increased. After the cell voltage exceeded the dielectric breakdown voltage of the coating (in this study, round 150190 V), sparking occurred and the anodising system entered the third stage. The formation of the anodised coating continued through vigorous sparking induced breakdown of the coating and repairing the coating afterward at the broken areas. At the same time, intensive gas evolved from the sparking spots where thermo-decomposition of water occurred. 3.4. Corrosion resistance of anodised coating The corrosion of the coatings initiated from tiny pits, progressed into pitting corrosion and nally became localised or liform corrosion. The typical images are shown in Fig. 11. The corrosion specks and pits became visible after 16-h immersion. After 88-h immersion, the specks had become larger and developed into localised corrosion and liform corrosion. Based on the morphologies of the corroded specimens, the ratio of corroded area of the specimens after 88 h exposure testing can be obtained. The ratio of the corroded
Stage I
5

Stage III

(a)
Stage II
0.012

I (mA/cm2)

0.010

0.008

I (mA/cm )

0.006

0.004

(b)

0.002

0.000 -2 0 2 4 6 8 10 12

Cell voltage (volts)

100

200

300

400

Cell voltage (Volts)

Fig. 10. Polarisation curve of AZ91D in the anodising solution measured by high voltage DC power supply (b) measured by potentiostat with a saturated silver/silver chloride electrode as a reference (the potentials relative to the silver/silver chloride reference electrode has been converted into the cell voltages in this gure).

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Fig. 11. The corrosion images of the coatings after immersion in 5% NaCl solution for (a) 16 h and (b) 88 h.

specimens was 1620.1% for G0 coating, 24.9% for G1 coating, 3.17.0% for G2 coating, 0.410.1% for G3 coating and 3.022.4% for G4 coating. So, the rating of corrosion resistance of these coatings decreased in the following order: G1 > G2 > G3 > G0 > G4. According to the above discussion, the microstructure of the anodised coating should be dependent on the waveform of the current and the nal cell voltage. On the other hand, the corrosion resistance of the anodised coating is determined by the microstructure, composition and thickness of the coating. Therefore, the corrosion performance can be reasonably related to the anodising current density. This explains the corrosion performance of the coating as shown in Fig. 11. For a short time or low current density anodisation, when the coating is thin (like the G4 anodised coating in Stage I and Stage II), the thickness of the coating is the main factor aecting the corrosion resistance of the anodised coating. That is why the G4 coating shows a low corrosion resistance even if the microstructure of the coating looks very compact.

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In the third stage, the coating is relatively thick. The eect of the thickness becomes less important as the coatings become more porous due to sparking. In this case, other factors such as the composition of the coating should be considered. For example, the content of silicate can play an important role in the corrosion performance of the anodised coating. A compact and silicate rich coating can provide good corrosion resistance. It is found that the microstructure of G0 is similar to G3, but G3 is thicker and richer in silicate than G0, so the corrosion resistance of G3 is higher than that of G0. 3.5. Optimisation of anodising current density The above analyses suggest that the control of anodising current density is important. If the current density is very high after the anodised coating has already very thick, the anodised coating may break down in a relatively large area by intensive sparking, and the subsequent anodisation of the damaged area becomes dicult. A intensive localised plasma sparking process can cause a local breakdown of the lm and result in a bad quality anodised coating. Therefore, in the last stage after a thick anodised coating has been formed, anodising current density should be reduced to a suitable value to maintain a non-vigorous and uniform sparking process. However, before an anodised coating is formed, if a too low anodising current density is applied, then the formation of an anodised coating will become too slow or even unachievable. Therefore, selection of a suitable current density is critical for anodising. An ideal anodising current density should be like this. At the beginning of anodising, a high anodising current density is essential to obtain an initial anodised coating quickly. In the later stage while sparking becomes too intensive or too localised, a low current density will be appropriate, which can lead to a coating less porous. An optimised waveform of current density can improve the microstructure, surface appearance, and the nal quality of the coating and the eciency of the anodising reactions. Consequently, the resulting coating with suitable composition, microstructure and thickness will have a good corrosion resistance. For example, in anodising G0, the anodised coating formed quickly in the rst and second stages, but vigorous sparking occurred in the third stage. Hence, the anodised coating was coarse. Its corrosion resistance was bad. In anodising G2, the current density was decreased in the later stages. Therefore, the corrosion performance of the coating is better than the coating G0. For G3, the coating was formed quickly in the rst stage with higher current density. However, the current densities in the later stages were only slightly reduced, not suciently. Thus, its corrosion performance was not as good as coating G2. 4. Conclusions 1. Various reactions are involved in the anodisation of Mg alloy AZ91D in a hydroxide silicate solution at a constant applied current density: such as the deposition of Mg(OH)2 and MgSiO3 in the initial stage, the dehydration of Mg(OH)2 in the second stage and the vigorous gas evolution, sparking, deposition of MgO, thermal-decomposition of bath solution, oxidation of magnesium by active oxygen, melting and sealing of coating in the nal stage. 2. The thickness, composition and microstructure are dependent on the anodising current density and they can inuence the corrosion performance of the anodised coatings.

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Therefore, the corrosion performance of anodised coating can be adjusted by the anodising current density. 3. In order to improve the corrosion performance of an anodised coating, an optimised anodising current waveform should be applied. In earlier stages, a higher current density is essential for high production eciency, but in the later stages, a low current density can minimise or seal the pores and improve the corrosion resistance of an anodised coating.

Acknowledgement The research work was supported by UQIPRS and CAST scholarships. The Cooperative Research Centre for Cast Metals Manufacturing (CAST) was established and is supported by the Australian Governments Cooperative Research Centres Program. The authors would also like to acknowledge Ms. Ying Yus assistance in the SEM and EDX analyses in this study. Appendix 1. Calculation of the current eciency At time ti, if the volume of O2 is Vi and the total area of the specimen is A, then the rate (RO2 ) of O2 evolution per area at time ti can be expressed as: RO2 V i1 V i1 =ti1 ti1 =A If only the following electrochemical reaction is responsible for the oxygen evolution: 4OH 2H2 O O2 " 4e then the charge used for oxygen evolution C O2 can be calculated: C O2 xnF where x is the molar number of oxygen produced, n (number of electron of the above reaction) = 4, and F (Faradays constant) = 96485.3 C/M. In addition, x PV =RT 1 RO2 Dt=1000=8:2057 102 298 in which oxygen pressure P = 1, V is volume of oxygen, R = 8.2057 10 and absolute temperature T = 296 K. Hence: C O2 4xF 4 96500 x 15:783RO2 Dt and the current density I O2 used for O2 evolution should be I O2 C O2 =Dt 15:783RO2 Normally, the current eciency g can be dened as g I film =I T 100% where IT is the total anodising current density, which is equal to the applied anodising current density I, and Ilm is the current used to form the coating. Since I I T I film I O2 14
2

13 at l K
1

mol1,

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we have g I T I O2 =I T I 15:783RO2 =I T 100% Appendix 2. Calculation of the theoretical charge during anodising process It is assumed that the density (q) and porosity (d) of an anodised coating are constants. Reaction (5) is considered as the main electrochemical reaction during the anodising process. The amount of the coating in mole (mcoating) can be expressed as mcoating A h qcoating 1 d=M coating 15 in which A is the area (assumed to be 1 cm2), h is the thickness of coating (lm) and Mcoating is molar weight (g mol1). If the coating consists of MgO, Mg(OH)2 and MgSiO3 alone, the densities and molar weights of the coatings can be calculated and listed in the following table [36]. MgO q Mcoating 3.58 40.3 Mg(OH)2 2.36 58 MgSiO3 3.19 100

The charge used for the coating formation is C coating 2 mcoating F 2 1 h qcoating 1 dcoating F =M coating Based on the statistical estimation of the porosity of the anodised coating on AZ91D, dcoating was about 15% (estimated from the SEM images). Substitution of it in the above equation gives: C MgO 1:4573h C MgOH2 0:6675h C MgSiO3 0:5236h 16 17 18

The relationships between the charge and thickness of the coatings described by Eqs. (16) (18) are plotted in Fig. 6(d).

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