Electrochimica Acta 51 (2006) 28452850

Effect of microcrystallization on corrosion resistance of AZ91D alloy

Ying Li , Tao Zhang, Fuhui Wang
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Wencui RD 62, Shenyang 110016, China
Received 25 February 2005; received in revised form 11 August 2005; accepted 11 August 2005
Available online 15 September 2005

Abstract
Corrosion behavior of cast, homogenized (T4) and microcystallized (mc) AZ91D alloy was investigated in NaCl aqueous solution by gas
collection and electrochemical measurement. The capacitance property of the product films formed on mc alloy and cast alloy was studied by
Mott-Schottky approach. The results implied that the grain size have a significant influence on the corrosion resistance of AZ91D alloy as well as
phase. The product films behaved as P-type semiconductor with the increasing of anodic potential. TEM observation indicated that the particle
size of the product film on the mc alloy (<10 nm) was far smaller than that on the cast alloy (200 nm), which might be beneficial to the widening
of energy band and the decreasing of acceptor concentration in the product film on mc alloy.
2005 Elsevier Ltd. All rights reserved.
Keywords: Magnesium alloy; Microcrystallization; Sputtering; Corrosion; TEM

1. Introduction
Magnetron sputtering has attracted considerable attention in
recent years as an environmentally friendly alternative to produce coatings with superior resistance to corrosion [110]. The
sputtering alloys, due to their chemical homogeneity and amorphous or microcrystalline (mc)/nanocrystalline (nc) structure,
may be of superior anticorrosive ability when compared to their
conventional crystalline counterparts.
Magnesium and its alloy are a kind of significant interesting material due to their lightness, higher strength and stiffness
[11]. But poor corrosion resistance is one important reason why
magnesium alloy is not widely used. During the last several
years, some investigations were carried out to study the corrosion resistance of sputtering magnesium and its alloy [1214].
The mc/nc structure and the change of constituent phases should
be the main factors responsible for the improvement of corrosion
resistance of sputtering AZ91D alloy. However, no systematic
study has been reported on the reason why corrosion resistance
of magnesium and its alloy was improved till now.
In the present study, microcrystallized AZ91D film was prepared on glass slide through magnetron sputtering technology.
The electrochemical corrosion behavior of mc AZ91D alloy in

Corresponding author. Tel.: +86 24 2392 5323; fax: +86 24 2389 3624.
E-mail address: liying@imr.ac.cn (Y. Li).

0013-4686/$ see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2005.08.023

NaCl aqueous solution was investigated by means of hydrogen

collection and electrochemical measurement. The capacitance
properties of the product film on AZ91D alloy and on mc
alloy were discussed. The homogenized specimens (T4) were
of AZ91D also employed as counterparts.
2. Experimental
2.1. Materials
The mc AZ91D film was deposited on glass by means of
dc magnetron sputtering system (SBH-5115D). The sputtering
target with dimensions of 380 126 mm, was AZ91D alloy
whose main compositions were: 8.59.5% Al, 0.450.9% Zn,
0.170.5% Mn, <0.05% Si, <0.004% Fe, <0.001% Ni, <0.015%
Cu, <515 ppm Be. The sputtering parameters were listed in
Table 1. Homogenized heat treatment (T4) was performed at
410 C for 16 h, following by quenching in water.
The test solution was 1 N NaCl with pH 7.0 prepared by
analysis grade chemicals and distilled water.
2.2. Microstructure analysis
The grain size of mc alloy was obtained by transmission electron microscope (TEM). The morphology of the above alloys
was observed by Philips-XL30 scanning electron microscope

2846

Y. Li et al. / Electrochimica Acta 51 (2006) 28452850

Table 1
The sputtering parameters of magnesium alloy coating
Power

Pressure of argon

Temperature of substrate

Substrate condition

Sputtering time

Pre-sputtering

1450 W

0.26 Pa

No heating

Fixed

180 min

15 min

(SEM) equipped with EDAX and X-ray diffractometer with Cu

K radiation.
2.3. Electrochemical measurement
The electrochemical tests using both dc (polarization curves)
and ac techniques (EIS) were carried out in the above solution. For all experiments a three-electrode cell was used, with
an Ag/AgCl electrode being used as a reference electrode and
a platinum counter electrode (20 20 mm). The polarization
curves were obtained by PAR 273 potentiostat, with a potential scanning rate of 1 mV/s. The impedance measurement was
carried out using a frequency response analyzer coupled with
the potentiostat. The perturbing ac amplitude was of 5 mV and
the capacitance of the interface was measured at constant frequency of 1 KHz. The EIS measurements were performed with
variable anodic overpotential from 0 to 300 mV at a scan rate of
20 mV/min. All the experiments were controlled by PC, which
was also used for the acquisition, storage and plotting of data.
A hydrogen evolution method was used to determine the corrosion rate of the specimens [15]. The evolved hydrogen of
the specimen in the course of immersion in the experimental
solution was collected by a funnel just above the specimen,
and then went into a burette and gradually displaced the test
solution in the burette. In this way, the volume of the evolved
hydrogen can be easily measured by reading the height of the
test solution level in the burette. In this study, the specimens
were immersed for 24 h and the hydrogen volume was measured
every hour.
Fig. 1. SEM image of AZ91D magnesium alloy (a) cast; (b) T4 treatment.

3. Results and discussion

3.1. Microstructure
In the cast condition (Fig. 1a), aluminum presents both in
solid solution with phase and in phase which precipitates
mainly along grain boundaries of phase. For homogenized heat
treatment (T4 treatment), phase dissolves in phase, which
can be visualized in Fig. 1b. The bright particles in Fig. 1b are the
phase in the AlMnFe series, which was verified by the result
of EDAX. Fig. 1 indicated that the grain sizes of the above alloys
were more than 50 m. The surface morphology of sputtering
alloy was shown in Fig. 2. The TEM of the sputtering film is
shown in Fig. 3, which indicated that the grain size of sputtering
alloy is about 300 nm and the diffraction pattern confirmed that
crystal grain has (hcp) phase structure.
The XRD results of mc, T4 and cast Mg alloys were shown
in Fig. 4, which suggested that there was no phase in the mc
and T4 alloys.

Fig. 2. SEM image of sputtering AZ91D magnesium alloy film.

Y. Li et al. / Electrochimica Acta 51 (2006) 28452850

2847

This means that the dissolution of one mole magnesium atom

generates one mole hydrogen gas. So, in theory, measuring the
volume of hydrogen evolved is equivalent to measuring the
weight-loss of magnesium dissolved and the measured hydrogen evolution rate is equal to the weight-loss rate if both of them
have been converted into the same unit. Therefore, the corrosion
rate of the Mg alloys can be evaluated by the volume of hydrogen
evolution from them in situ. Fig. 5 gives the hydrogen evolution

Fig. 3. TEM image of sputtering AZ91D alloy film.

Fig. 4. XRD patterns of mc, T4 and cast alloys.

3.2. Corrosion performance

It is well known that the overall corrosion reaction of magnesium in aqueous solution at its corrosion potential can be
expressed as follows:
Mg + 2H2 O = Mg2+ + 2OH + H2

(1)

Fig. 5. volume of hydrogen evolution of cast , mc and T4 alloys in NaCl aqueous

solution.

Fig. 6. SEM image of cast, T4 and mc alloys after 24 h immersion: (a) cast alloy;
(b) T4 alloy; (c) mc alloy.

2848

Y. Li et al. / Electrochimica Acta 51 (2006) 28452850

The corrosion of cast and T4 alloys initiated in the form of pits

at several locations and then spread over the surface in a cellular
fashion (Fig. 6a and b), while there was a feather-shaped product
film covered mc alloy surface (Fig. 6c) in the same condition.
The polarization curves of mc alloy, T4 alloy and cast AZ91D
alloy in NaCl aqueous solution after immersed for B time were
measured, respectively, and showed in Fig. 7. It can be seen that
at B time, the corrosion rate of all the specimens should be ranked
as: mc alloy ( phase) < cast alloy ( + phase) < T4 alloy
( phase). The result agreed with that of hydrogen evolution
measurement. Hydrogen evolution measurement and potentiodynamic polarization curves for AZ91D alloys illustrated that
the phase change has a significant influence on the corrosion
resistance of Mg alloy. We can confirmed that the corrosion resis-

Fig. 7. polarization curves of cast , mc and T4 alloys in NaCl aqueous solution

after 24 h immersion.

from mc alloy, cast AZ91Dalloy and T4 alloy in NaCl aqueous

solution as function of immersion time. All the measurements
were duplicated for three times with a good reproducibility. We
can claim that at the beginning (time A), the corrosion rate of
all the specimens can be ranked as an increasing series: cast
alloy ( + phase) < mc alloy ( phase) < T4 alloy ( phase).
However, with immersion time increasing, the corrosion rate of
mc alloy was lower than that of cast alloy gradually. At time B,
the corrosion rate of all the specimens should be ranked as: mc
alloy ( phase) < cast alloy ( + phase) < T4 alloy ( phase).
According to previous works [1618], there should be a product
film formed on the alloy surface in NaCl aqueous solution. But
for the cast alloy and T4 alloy, the hydrogen evolution volume
increased lineally with time, which implied the product film on
alloy surface was less protective. On the other hand, for the mc
alloy, the hydrogen evolution rate decreased with time and the
hydrogen evolution volume approached to a maximum in the
end. A protective product film formed on the mc alloy surface
might be the proper reason why the hydrogen evolution rate
decreased obviously. At time B, two different types of surface
morphologies for the above specimens were illustrated by SEM.

Fig. 8. Mott-Schottky plots of product films on cast and mc alloys in NaCl

aqueous solution.

Fig. 9. TEM image of the product film on cast and mc alloys: (a) cast alloy; (b)
mc alloy.

Y. Li et al. / Electrochimica Acta 51 (2006) 28452850

tance would deteriorate with the absence of phase because the

corrosion rate of T4 alloy with only phase was much higher
than that of the cast alloy with both and phases. On the
other hands, the grain size of alloy also plays a big role in the
corrosion resistance of Mg alloy. The corrosion rate of mc alloy
is much lower than that of T4 alloy, which has the same phase
and the grain size is different. It seems that changing grain size
is more effective than changing phase to improve the corrosion
resistance of Mg alloy because the corrosion rate of mc alloy
was reduced to lower than that of cast alloy when the grain size
is lowed down to nanoscale even through no phase exists in it.
3.3. Property of the protective product lm on mc alloy
surface
Polarization curves (Fig. 7) also meant that the anodic process
of mc alloy was inhibited. It attributed to a protective product
film formed on mc alloy surface. Therefore, for well understanding microcrystallization effect on corrosion resistance of AZ91D
alloy, it is necessary to study the nature of the corrosion product
film on mc alloy.
It is well known that the corrosion product film on most alloys
exhibit semiconductive behavior [19,20]. The most common, in
situ method for probing the electronic properties of corrosion
product film is Mott-Schottky (M-S) analysis. In the M-S experiment reported here, the specimens of cast and mc alloy were
immersed for 24 h. The imaginary part of impedance (Z ), measured at a frequency of 1 KHz, was recorded as a function of
the external applied potential. The interfacial capacitance, C, is
obtained from C = 1/Z . Assuming that the capacitance of
Helmholtz layer can be neglected, the measured capacitance C
is equal to the space charge capacitance, Csc . According to
Mott-Schottky theory [20], the space charge capacitance of a
P-type semiconductor is given by Eq. (1):
2
1
(V Vfb kT/e)
C2 0 eNA

(2)

2849

where 0 is the vacuum permittivity, , the dielectric constant

of the product film, NA , the acceptor concentration in the product film, V, the applied potential, Vfb , the flat band potential, e,
the charge of an electron, and k is Boltzmann constant. Thus,
for a P-type semiconductor, C2 versus V should be linear with
a negative slope that is inversely proportional to the acceptor
concentration.
The C2 versus V profile for films formed at different anodic
over-potential was presented in Fig. 8, which indicated that
both cast alloy and mc alloy formed P-type semiconductor film.
The slope of mc alloy was bigger than that of cast alloy, suggesting the acceptor concentration in the product film of mc
alloy is lower than that of cast alloy. The less the acceptor
the product film has, the more difficult the electrochemical
reaction proceeds. In another word, the corrosion resistance
of mc alloy was higher than that of cast alloy, which was
consistent with the results of gas collection and polarization
curve.
The results of TEM (see Fig. 9) showed the grain size of the
product film scaled off from cast alloy was about 200 nm, while
that of mc alloy was less than 10 nm. The diffraction pattern
confirmed that there was a MgO film (fcc) formed on both cast
alloy and mc alloy.
Fig. 10 described the electronic energy band model for a
semiconductor film formed on AZ91D alloy in NaCl aqueous
solution. The proposed model has two interfaces: (I) substrate
alloy/film and (II) film/electrolyte. At interface (I), with the
increasing of anodic potential, the energy band slopes in the
semiconductor film descended toward the film/substrate interface. At interface (II), electronic transition was carried out from
valence band to Fermi level and vacancies were generated in
valence band, implying that both outward migration of cations
and inward migration of anions were possible, which suggested
a product film might continue to grow under high electric fields.
Several investigations had demonstrated that the energy shift in
the band gap, E, as a function of particle size can be predicted
by the three-dimensional confinement model based on the effec-

Fig. 10. Schematic presentation of the electronic band structure of product films formed on cast alloy and mc alloy in NaCl aqueous solution.

2850

Y. Li et al. / Electrochimica Acta 51 (2006) 28452850

tive mass approximation [2123]:


h2 2 1 1
1.786e2
E =

0.248ERY

2R
me mh
R

(3)

where R is the grain size, me and mh , the effective masses for

electrons and holes, , the dielectric constant, and ERY is the
effective Rydberg energy given as e4 /22 h2 (1/me + 1/mh ). So,
the energy shift in the band gap was:
Egnc > Egbulk

(4)

This indicated:
Egnc > Egbulk

(5)

Therefore, it could be expected that the energy band of the product film on mc AZ91D alloy increased, suggesting that it became
difficult for electronic transition from valence band to Fermi
level (see Fig. 10), which might be the proper explanation for
the decreasing of acceptor concentration of the product film on
mc alloy.
4. Summary
From the above results and discussions, we can confirmed that
the phase change did not appear to have a significant influence,
but the grain size of alloy plays a key role on the corrosion
resistance. Mott-Schottky analysis showed that the capacitance
properties of the product films formed on mc and cast alloys
were different. There was a P-type semiconductor product film
formed on the AZ91D alloy. The acceptor concentration of the
product film on mc alloy was less than that on cast alloy, which
induced a higher protectiveness of the product film on mc alloy.
The main reason for the less acceptor concentration might be
attributed to the smaller grain size of the product film on mc
alloy, which was favorable to the widening of energy band.
Acknowledgements
The project is supported by the National Natural Science Foundation of China under the contract Nos. 50001013,

59971052 and 59625103. The authors are also pleased to show

their deep thanks to Prof. Wu Weitao for his careful reading the
article.
References
[1] M. Mehmood, B.-P. Zhang, E. Akiyama, H. Habazaki, A. Kawashima,
K. Asami, K. Hashimoto, Corros. Sci. 40 (1998) 1.
[2] M. Mehmood, E. Akiyama, H. Habazaki, A. Kawashima, K. Asami, K.
Hashimoto, Corros. Sci. 42 (2000) 361.
[3] M. Mehmood, E. Akiyama, H. Habazaki, A. Kawashima, K. Asami, K.
Hashimoto, Corros. Sci. 41 (1999) 1871.
[4] M. Mehmood, E. Akiyama, H. Habazaki, A. Kawashima, K. Asami, K.
Hashimoto, Corros. Sci. 41 (1999) 477.
[5] A. Griguceviciene, K. Leinartas, R. Juskenas, E. Juzeliunas, J. Electroanal. Chem. 565 (2004) 203.
[6] Z.Y. Liu, W. Gao, K.L. Dahm, F. Wang, Acta Mater. 46 (1998)
1691.
[7] H. Lou, F. Wang, B. Xia, L. Zhang, Oxid. Met. 38 (1992) 299.
[8] F. Wang, Oxid. Met. 48 (1997) 215.
[9] A. Griguceviciene, K. Leinartas, R. Juskenas, E. Juzeliunas, Mater. Sci.
Eng. 394 (2003) 411.
[10] S. Geng, F. Wang, S. Zhu, W. Wu, Oxid. Met. 57 (2002) 549.
[11] D.A. Jones, Principles and Prevention of Corrosion, Prentice-Hall Inc.,
Upper Saddle River, 1996, NJ07458.
[12] A. Yamamoto, A. Watanabe, K. Sugahara, H. Tsubakino, S. Fukumoto,
Scripta Mater. 44 (2001) 1039.
[13] M.H. Lee, I.Y. Bae, K.J. Kim, K.M. Moon, T. Oki, Surf. Coatings
Technol. 169/170 (2003) 670.
[14] P.L. Miller, B.A. Shaw, R.G. Wendt, W.C. Moshier, Corros. Sci. 49
(1993) 947.
[15] G. Song, A. Atrens, D. St John, Magnesium technology, in: J. Hryn
(Ed.), The Minerals, Metals and Materials Society (TMS), 2001,
p. 255.
[16] G. Song, A. Atrens, D. St John, J. Nairn, Y. Li, Corros. Sci. 39 (1997)
855.
[17] G. Song, A. Atrens, X. Wu, B. Zhang, Corros. Sci. 40 (1998)
1769.
[18] G. Song, A. Atrens, D. St. John, X. Wu, Corros. Sci. 39 (1997)
1981.
[19] U. Stimming, Electrochem. Acta 31 (1986) 415.
[20] E. Sikora, D. Macdonald, Electrochem. Acta 48 (2002) 69.
[21] L.E. Brus, J. Chem. Phys. 79 (1983) 5566.
[22] L.E. Brus, J. Chem. Phys. 80 (1984) 4403.
[23] Y. Kayanuma, Phys. Rev. B 38 (1988) 9797.