Trans. Nonferrous Met. Soc.

China 23(2013) 2551−2559

Anodizing of 2024-T3 aluminum alloy in

sulfuric−boric−phosphoric acids and its corrosion behavior

M. SAEEDIKHANI, M. JAVIDI, A. YAZDANI

Department of Materials science and Engineering, School of Engineering, Shiraz University, Shiraz 7134851154, Iran
Received 28 August 2012; accepted 27 November 2012

Abstract: The corrosion resistance of 2024-T3 aluminum alloy was improved by anodizing treatment in a mixed electrolyte
containing 10% sulfuric acid, 5% boric acid and 2% phosphoric acid. Electrochemical impedance spectroscopy (EIS) technique was
used to study the corrosion behavior of the anodized alloy. Using Tafel plot and salt spray techniques, it is revealed that the anodizing
treatment of 2024-T3 aluminum alloy in sulfuric−boric−phosphoric acids provides better corrosion resistance and durability in
comparison with the anodizing treatment in phosphoric acid or sulfuric−boric acids. This electrolyte can be a suitable alternative for
chromate baths which are generally used in the anodizing of aluminum alloys.
Key words: anodizing; 2024-T3 aluminum alloy; mixed electrolyte; EIS

process and the properties of the anodic films are

1 Introduction obviously influenced by the alloying elements [14]. The
intermetallic particles that give strength to these alloys
The application of an anodic polarization to an can result in the susceptibility of the alloys to galvanic
aluminum alloy sample which is immersed in an corrosion [15]. The corrosion resistance of the anodized
appropriate electrolyte leads to anodic oxide film growth alloy is enhanced to some extent by a hydrothermal
[1]. The anodic oxide film is characterized by a duplex treatment named sealing. This treatment is necessary for
structure composed of inner thin barrier layer and thick the porous surface layer [3]. Many authors reported
outer porous layer [2−4]. Anodizing in chromic acid different sealing methods for aluminum anodic films.
electrolyte is an effective way to produce oxide films The sealing of anodic films in boiling water effectively
with excellent corrosion resistance. However, the use of prevents the risk of pitting corrosion even in the high
Cr(VI) is prohibited since it is toxic and carcinogenic [5]. corrosive environments. The main role of sealing process
In order to eliminate Cr(VI) from anodizing process, is the blockage of pores due to the formation of hydrated
several studies have been realized [6,7]. There is not a alumina [6]. Electrochemical impedance spectroscopy
singular candidate for the replacement of chromium and (EIS) technique has been used to study the corrosion
the aim of most researches has focused on the resistance of anodized aluminum alloys [4]. EIS
combination of different techniques to improve the technique can characterize the properties of the barrier
corrosion resistance of oxide film such as using layer and the sealed porous layer by fitting the
mixed-acid-electrolytes like boric−sulfuric acids and impedance spectra to an appropriate electrical equivalent
nitric−sulfuric acids [8−10]. This study proposed a circuit. EIS technique can also measure the thickness of
mixed bath containing sulfuric−boric−phosphoric acids oxide film [4,16].
for the anodizing of 2024-T3 aluminum alloy. Aluminum This study was conducted to improve the corrosion
alloys containing copper (2000 series) exhibit high resistance of the 2024-T3 aluminum alloy by anodizing
strength and are widely used but generally have low in sulfuric−boric−phosphoric mixed-acid-bath followed
corrosion resistance [11] and are susceptible to localized by sealing treatment carried out in boiling water. The
corrosion [5,12]. Thus, these alloys are mostly anodized corrosion behavior of the anodized alloy and also the
to improve their corrosion resistance [13]. The anodizing degradation of oxide films were studied in an aggressive

Corresponding author: M. JAVIDI; Tel: +98-711-6133266; Fax: +98-711-2307293; E-mail: [email protected]

DOI: 10.1016/S1003-6326(13)62767-3
2552 M. SAEEDIKHANI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 2551−2559
media using EIS technique. Tafel plot and salt spray samples were compared. Sealing treatment was carried
techniques were used to compare the corrosion resistance out in boiling deionized water for 30 min. Finally, the
and durability of the alloys anodized in phosphoric acid, samples were rinsed and air dried.
sulfuric−boric acids and sulfuric−boric−phosphoric acids.
2.4 Electrochemical tests
2 Experimental In order to investigate the corrosion behavior of
anodized alloys in the sulfuric−boric−phosphoric acids,
2.1 Materials EIS technique was used with three-electrode
The investigated material in this research was configuration cell. An Ag/AgCl electrode as reference
2024-T3 aluminum alloy. The chemical composition of electrode, a platinum rod as auxiliary electrode and an
the bulk material was evaluated by the use of optical anodized sample as working electrode were employed.
emission spectrometer (OES) technique. Scanning The electrochemical test cell was open to air at room
electron microscopy (SEM) and energy dispersive X-ray temperature containing aqueous electrolyte of 3.5%
spectroscopy (EDS) methods (VEGA II TESCAN) were NaCl. The samples anodized in sulfuric−boric−
used to study the surface of the alloy before and after phosphoric acids were dipped in aqueous media of 3.5%
surface preparation both prior anodizing process. NaCl for 1, 2, 10, 24 and 48 h to investigate the extent of
degradation of the oxide film using EIS. Impedance
2.2 Surface preparation measurements were taken over a frequency range of 105
The surfaces of the samples were ground using SiC down to 10−2 Hz using a 10 mV single sine wave. Data
abrasive papers up to number 800, and cleaned with were shown as Nyquist plots. In addition, Tafel plot
deionized water and acetone. The samples were alkaline technique was used to compare the corrosion resistance
cleaned, chemically polished and finally de-smuted. of phosphoric, sulfuric−boric and sulfuric−boric−
After each step, the samples were rinsed with deionized phosphoric acids anodized alloys. The potential scanning
water and air dried. Table 1 lists the chemical rate for Tafel plot was 1 mV/s. The equipment for
composition of the solutions used for surface preparation electrochemical tests was μAutolab type III with the
and the holding time and temperature. frequency response analyzer (FRA) and general purpose
electrochemical system (GPES) softwares for analyzing
Table 1 Chemical composition of solutions used for surface the resulted EIS and Tafel plot data, respectively.
preparation and holding time and temperature
Surface Chemical composition Temperature/ Time/ 2.5 Salt spray test
preparation of solution °C min Neutral salt spray test was performed according to
ASTM B117 standard [17]. Anodized samples in
Alkaline
12 g NaOH+100 mL H2O 60 3 different electrolytes of phosphoric, sulfuric−boric and
cleaning
sulfuric−boric−phosphoric acids were exposed to 3.5%
54 mL H3PO4 (85%)+
Chemical 2 mL HNO3 (66.4%)+ NaCl solution at 35 °C.
90 4
polishing 15 mL CH3COOH (99%)+
13 mL H2O 3 Results and discussion
35 mL HNO3 (66.4%)+
Deoxidizing 26 2 3.1 Surface preparation
65 mL H2O
The bulk chemical composition of the investigated
alloy is listed in Table 2.
2.3 Anodizing and sealing
A simple rectifier with a maximum power of 40 V
Table 2 Bulk chemical composition of 2024-T3 aluminum
and 4 A was used for applying anodic polarization. A
alloy (mass fraction, %)
large enough lead sheet was used as cathode. The anode
electrode was 2024-T3 aluminum alloy. Anodizing was Cu Mg Mn Fe Zn Si Others Al
carried out at room temperature in a mixed electrolyte 4.62 1.55 0.57 0.18 0.15 0.1 0.04 Bal.
composed of 10% sulfuric acid, 5% boric acid and 2%
phosphoric acid under current density of 1 mA/cm2 for Copper is one of the most important alloying
20 min. Also one sample was anodized in electrolyte of elements for 2024-T3 alloy due to its strengthening
10% phosphoric acid under current density of 4 mA/cm2 effect. In addition, 2024-T3 alloy contains other alloying
for 20 min. Another sample was anodized in electrolyte elements which lead to the presence of several
of 5% sulfuric acid and 0.8% boric acid under current intermetallic phases [2]. The SEM micrograph of the
density of 3.5 mA/cm2 for 20 min according to the work surface of 2024-T3 alloy is shown in Fig. 1, which
by ZHANG et al [7]. Sealed and unsealed anodized presents different phases.
 M. SAEEDIKHANI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 2551−2559 2553
composition of the alloy remained unchanged during
chemical polishing. Table 3 lists the bulk chemical
composition of the alloy after surface treatment, resulted
from OES technique. It can be seen that there is no
evident change in the bulk chemical composition of the
alloy.

Table 3 Chemical composition of 2024-T3 aluminum alloy

after surface treatment (mass fraction, %)
Cu Mg Mn Fe Zn Si Others Al
4.45 1.57 0.56 0.17 0.16 0.06 0.04 Bal.

Figure 2(a) shows the SEM micrograph of the

alloy after surface treatment. The EDS analysis of the
surface reveals that no other element is present on the
Point w(Cu)/% w(Mg)/%w(Mn)/% w(Fe)/% w(Si)/% w(Al)/% alloy surface except aluminum, as can be seen in
A 22.48 11.89 0.12 − − Bal. Fig. 2(b).

B 6.56 − 1.83 17.72 0.67 Bal.

Fig. 1 SEM micrograph (a) and EDS analysis (b) of surface of

2024-T3 aluminum alloy before surface treatment

The EDS analysis of the surface of 2024-T3 alloy

reveals that the dark areas are corresponding to
Al−Cu−Mg phase and the white areas are corresponding
to Al−Cu−Mn−Fe−Si phase. It can be seen from Fig. 1
that Al−Cu−Mg particles have relatively round shapes
and Al−Cu−Mn−Fe−Si particles have irregular shapes.
MOUTARLIER et al [2] reported that after treatment in
sulfuric medium, Al−Cu−Mg particles are severely
attacked and the matrix dissolves slightly over the whole
specimen; whereas the Al−Cu−Mn−Fe−Si particles seem
undamaged. Other studies [18,19] have indicated that
Al−Cu−Mg phases tend to be anodic relative to the
matrix; whereas Al−Cu−Mn−Fe−Si phases tend to be
cathodic relative to the matrix. It is obvious from Table 2
and Fig. 1 that copper exists in the surface microstructure
as well as in the bulk microstructure of the alloy.
Alkaline cleaning, chemical polishing and deoxidizing
solutions were employed to treat the surface of the alloy
before anodizing. During alkaline cleaning, lots of gas
was emitted from alloy, and the alloy surface was Fig. 2 SEM micrograph (a) and EDS analysis (b) of 2024-T3
covered with black smuts after alkaline cleaning, which aluminum alloy after surface treatment
may be metal oxides or hydroxides, such as silicon dust
and copper dust. The smuts were completely removed It should be noted that copper can exist in two
during chemical polishing. After chemical polishing, a valence states of Cu+ and Cu2+, thus possibly permitting
thin layer with cuprous color formed on the alloy surface, electron switching. Its presence in oxide film
probably due to leaching of copper from the surface of substantially increases the electronic conductivity of the
the alloy. This layer was easily removed by deionized oxide film [20]. Thus, eliminating copper (or
water stream. After chemical polishing, deoxidizing intermetallic phases which contain copper) from the
process was performed. The surface treated alloy was alloy surface before anodizing decreases the probability
chemically analyzed to ensure that the chemical of the presence of copper in the oxide film.
2554 M. SAEEDIKHANI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 2551−2559
3.2 EIS study of anodized alloys barrier layer capacitance. Because of the presence of
The oxide film obtained from sulfuric−boric− inhomogeneities in barrier and porous layers, their
phosphoric electrolyte becomes white, uniform and capacitive behavior is better simulated by constant phase
relatively smooth. As stated in the introduction, the elements (CPE) than by a simple capacitance (C) [6].
anodic oxide film consists of an inner thin barrier layer The use of CPE usually increases the goodness of the fit
and a thick outer porous layer. Also, the porous part is [24] and in studies of corroding systems, CPE are most
composed of pores and walls of hexagonal cells. In order often used to describe the frequency dependence of
to realize the EIS parameters of the anodic film, barrier non-ideal capacitive behavior [6]. The impedance of a
and porous layers are separated into two oxide phases CPE is given by Eq. (1) [6].
and are considered independent of each other. The
ZCPE =1/(C(jω)n) (1)
electronic and dielectric properties of each oxide phase
can be realized by an electrical equivalent circuit where w is the angular frequency, parameter n is
composed of parallel and series resistances and frequency dispersion factor which depends on different
capacitances. According to the work of HITZIG et al factors such as surface roughness [6]. The more
[21], each part of the aluminum oxide film (i. e. pore, homogeneous the surface is, the smoother the surface is.
barrier layer and wall of hexagonal cells) has both Parameter n varies from 1 to 0. When n is equal to 1,
capacitive and resistive behavior and the oxide film can parameters C1 and C2 can be considered ideal
be modeled by a circuit shown in Fig. 3. The curves capacitances.
schematically show the limit of each part including pore,
barrier layer and wall of hexagonal cells of aluminum
oxide film, which are used to describe the cross section
of the aluminum oxide film.

Fig. 4 Simplified model for equivalent circuit shown in Fig. 3

[21]

3.2.1 EIS study of unsealed anodized alloys

The Nyquist plot of unsealed sulfuric−boric−
phosphoric acid anodized alloys is shown in Fig. 5. The
samples were immersed in 3.5% NaCl aqueous solution
for 1, 2, 10, 24 and 48 h.

Fig. 3 Electrical equivalent circuit for modeling impedance

behavior of anodized aluminum films [21]: (a) Pores of porous
layer; C1 — Porous layer capacitance; R1 — Porous layer
resistance; (b) Barrier layer; C2—Barrier layer capacitance; R2
—Barrier layer resistance; (c) Walls of hexagonal cells; C3—
Hexagonal cell capacitance; R3—Hexagonal cell resistance

Several authors reported that this circuit

successfully explained the properties of both oxide parts
[22,23]. In this model, RS is the resistance of 3.5% NaCl
aqueous solution with the approximate extent of
15 Ω·cm2; R3 and C3 represent the walls of hexagonal
cells and they are eliminated from the circuit because Fig. 5 Nyquist plot of unsealed sulfuric−boric−phosphoric acid
they are extremely high and extremely low, respectively anodized alloys for different immersion times
[6]. So the passage of electrical current is prevented
through the wall of hexagonal cells and the model is Because of the high conductivity of the electrolyte
reduced, as shown in Fig. 4. through pores of the unsealed anodic layers, the porous
Thus the EIS parameters concerning anodic oxide layer properties could not be detected and one capacitive
films are R1 as porous layer resistance, C1 as porous layer loop is observed in the low frequency part which
capacitance, R2 as barrier layer resistance and C2 as corresponds to the characteristics of barrier layer [6].
 M. SAEEDIKHANI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 2551−2559 2555
Therefore, the electrical equivalent circuit of Fig. 4 is the sample immersed for 10 h, and the surrounded
reduced, as shown in Fig. 6. The parameters concerning deformation on the related Nyquist plot indicates pit
the electrochemical behavior of the unsealed anodic initiation.
films are R2, C2 and n2, as presented in Table 4. Pit initiation and growth on the alloy surface after
10 h immersion means electrolyte penetration through
barrier layer and this leads to new parameters and
modification of the circuit shown in Fig. 6. In order to
show electrolyte penetration through barrier layer, new
parameters θ, Rcorr and Cdl are introduced. The parameter
θ is the fraction of aluminum surface covered by oxide
film; Rcorr is the corrosion resistance of the aluminum
Fig. 6 Equivalent circuit for unsealed anodized films substrate, R2 or Rb is the barrier layer resistance and the
parameter Cdl corresponds to the double layer
Table 4 EIS parameters of barrier layer for unsealed anodic capacitance of the substrate. The modified model with
film for different immersion times these new parameters is presented in Fig. 7.
Immersion time/h R2/(Ω·cm2) C2/(μF·cm−2) n2
6
1 6.5×10 0.57 0.92
5
2 5.2×10 1.28 0.88
4
10 1.1×10 3.76 0.8
24 8×103 8.63 0.77
48 7×103 10.21 0.68

The capacitance C2 can be connected to the barrier

layer thickness d2 by Eq. (2):
C2=ε0εrA/d2 (2)
where ε0=8.85×10−14 F/cm is the dielectric constant of Fig. 7 Equivalent circuit to model electrolyte penetration
vacuum, εr=10 is the relative constant for alumina [6] through unsealed anodic film [6]
and A is the electrode surface area. Equation (2) is
acceptable when parameter n is close to 1 [6], namely, When θ=1, barrier layer is not damaged and
the CPE is close to an ideal capacitance like for 1 h of parameters Rcorr and Cdl do not exist as can be seen in the
immersion, when the barrier layer is relatively case of 1 h immersion. With the immersion times up to
homogeneous. So, the value calculated from Eq. (2) is 48 h, θ decreases, namely, the barrier layer degrades and
15.53 nm for barrier layer formed in sulfuric−boric− pits appear after 24 h immersion. Thus, the two
phosphoric acids after an hour of immersion in NaCl capacitive loops appear at low frequencies, part of Fig. 5
aqueous solution. Phosphate can enhance the dissolution are related to R2, C2, Rcorr and Cdl parameters. However, it
of the oxide film and then increase the anodizing current is difficult to distinguish R2 from Rcorr and C2 from Cdl.
obviously in boric acid electrolyte, thus a thick anodic 3.2.2 EIS study of sealed anodized alloys
film could be formed on the surface of 2024 aluminum Figure 8 shows the Nyquist plots of sealed sulfuric−
alloy [14]. With immersion time up to 48 h, more boric−phosphoric acids anodized alloys immersed in
electrolytes penetrate through porous layer to attack 3.5% NaCl aqueous solution for 1, 2, 10, 24 and 48 h.
barrier layer, therefore, the barrier layer will be degraded Nyquist plots of sealed anodized alloys are characterized
with immersion time. Indeed, C2 value increases and R2 by two capacitive loops. Several authors reported that
and n2 values decrease with immersion time as it can be high and medium frequency ranges corresponds to sealed
seen from Table 4. After 24 h immersion, C2 values are porous layer properties (Fig. 8(a)) and the low frequency
very high (8.63 and 10.21 μF/cm2), n2 values are low range corresponds to barrier layer properties (Fig. 8(b))
(0.77 and 0.68) and R2 values are low (8 and 7 kΩ·cm2), [21,25]. In order to visualize both barrier and porous
indicating the degradation of barrier layer. Indeed, after layer spectra (to show both capacitive loops), the Nyquist
24 h immersion, pitting corrosion is seen on the anodized plot is broken down into two parts.
alloy surfaces, and surrounded deformations in Nyqiust 3.2.2.1 EIS parameters of barrier layer of sealed
plots of Fig. 5 are due to the pit growth on the alloy anodized alloys
surface. However, no pitting corrosion was observed on The electrochemical impedance spectroscopy
2556 M. SAEEDIKHANI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 2551−2559
parameters of the barrier layer for different immersion than the unsealed ones. This indicates that sealing
times are extracted from Fig. 8(b) and are reported in treatment has modified the barrier layer properties.
Table 5. Sealing consists of a general reduction of sectional area
of each pore with the formation of a ‘‘plug’’ in the pore
bottom [6], which improves the oxide resistance against
electrolyte penetration, therefore, the R2 values are
higher for sealed layers. Also sealing process increases
the barrier layer thickness, and according to Eq. (2),
higher thickness of the oxide layer leads to lower value
of C2. The decrease in n2 values with exposure time for
both sealed and unsealed layers is related to the
formation of flaws by electrolyte penetration which
increases the heterogeneity of the oxide film. It is
obvious from Tables 5 and 6 that n2 values are higher for
sealed anodic layers due to plugging the barrier layer
flaws by sealing treatment, which increases the
homogeneity.
Figure 9 shows the variation of R2 with immersion
time for barrier layer. The parameter R2 is determined
from the high and medium frequency parts of Fig .8.

Fig. 8 Nyquist plots of sealed sulfuric−boric−phosphoric acids

anodized alloys immersed in 3.5% NaCl aqueous solution for 1,
2, 10, 24 and 48 h: (a) High and medium frequency parts of
impedance spectra related to sealed porous layer; (b) Low
frequency part of impedance spectra related to barrier layer Fig. 9 Variation of R2 with immersion time for barrier layer of
sealed anodized film
Table 5 EIS parameters of barrier layer for sealed anodized
alloys for different immersion time 3.2.2.2 EIS parameters of porous layer of sealed
Immersion time/h R2/(Ω·cm ) 2 −2
C2/(μF·cm ) n2 anodized alloys
7 The electrochemical impedance spectroscopy
1 3.3×10 0.45 0.95
parameters of the porous layer for sealed anodized films
2 3.3×107 0.98 0.92
at different immersion times are extracted from Fig. 8(a)
4
10 4.2×10 2.04 0.91 and reported in Table 6.
3
24 1×10 3.12 0.86
3
48 1×10 3.78 0.83 Table 6 EIS parameters of porous layer for sealed anodized
alloy at different immersion time
The thickness calculated from Eq. (2) is 19.67 nm Immersion time/h R1/(Ω·cm2) C1/(μF·cm−2) n1
for barrier layer formed in sulfuric−boric−phosphoric
1 10000 0.86 0.90
acids after sealing in boiling water and after 1 h
immersion in NaCl aqueous solution. This thickness is 2 8000 1.05 0.88
higher than that of the barrier layer of the unsealed 10 500 2.24 0.83
anodized alloy (15.53 nm). Also, comprising Tables 4 24 500 3.13 0.77
and 5, Figs. 5 and 8, it is revealed that sealed anodized
48 500 3.74 0.62
film shows lower values for C2 and higher values for R2
 M. SAEEDIKHANI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 2551−2559 2557
Parameter C1 in Table 6 is related to the capacitive electrolyte through the oxide film results in increasing C
behavior of the sealed pores. C1 depends on the oxide values and decreasing R values for both barrier and
film roughness, but not on the oxide film thickness [6]. porous layers, as it can be seen in Tables 5 and 6. Also, n
In this case, at 1 h immersion, the value of n2 is far from value decreases with immersion time, which shows
1, which means that the heterogeneity of porous layer is increasement in the heterogeneity of the oxide layer due
important. Porous layers can be contaminated by to electrolyte penetration.
alloying elements from substrate and from sulphate ions Figure 11 compares the evolution of C1 and C2 with
of sulfuric acid electrolyte [6] which affects their immersion time. It is obvious that in the first 10 h, the
homogeneity. Figure 10 shows the variation of R1 with increasing rate of C2 is slower than the increasing rate of
immersion time for porous layer. Parameter R1 is C1 and then the increasing rates of C1 and C2 are almost
determined from the high frequencies part of Fig. 8. the same up to 48 h immersion. Indeed, barrier layer
By considering Figs. 9 and 10, it can be seen that remains a better capacitor than porous layer in the first
the barrier layer resistance is higher than the associate 10 h immersion.
porous layer resistance, which means that barrier layer is
a much better resistor than its associate porous layer with
sealed pores, which shows easier electrolyte penetration
through porous layer. This can be due to the presence of
the pores in the porous layer microstructure which leads
to higher conductivity of this layer than barrier layer,
namely, pores cause easier electrolyte penetration
through porous layer and this phenomenon can increase
the conductivity of the film, which results in lower
values of resistance R1 than R2.

Fig. 11 Evolution of C1 and C2 with immersion time

Figure 12 compares the evolution of n1 and n2

values with time. It is obvious that decreasing rate of n2
is slower than the decreasing rate of n1, which means
after 48 h immersion, the barrier layer reserves its
homogeneity more than its associate porous layer with
sealed pores.

Fig. 10 Variation of R1 with immersion time for porous layer of

sealed anodized film

3.2.2.3 Immersion of sealed anodized alloys in NaCl

aqueous solution from 1 to 48 h
It is obvious from Table 5 that at 1 h immersion, the
resistance R2 for sealed anodized film is the highest for
the barrier layer with value of 3.3×107 Ω·cm2 and the
capacity of C2 is the lowest with the value of
0.45 μF/cm2. Also, from Table 6 it can be seen that at 1 h Fig. 12 Evolution of n1 and n2 with immersion time
immersion, the resistance R1 is the highest for porous
layer with the value of 104 Ω·cm2 and the capacity of C1 Generally, it can be concluded that the barrier layer
is the lowest with the value of 0.86 μF/cm2. Anodic oxide has more corrosion resistance than its associate sealed
films with relatively lower values of capacity and porous layer because the electrolyte penetration is
relatively higher values of resistance are more corrosion weaker through the barrier layer. Again, in order to
resistant at 1 h immersion. symbolize the electrolyte penetration through the oxide
With exposure time up to 48 h, the penetration of film, parameters θ, Rcorr and Cdl (Rcorr and Cdl are
2558 M. SAEEDIKHANI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 2551−2559
introduced as corrosion parameters) must be introduced occurring time of corroded spots on the samples. The
for immersion time from 2 to 48 h and the model of results of salt spray test are in good agreement with the
Fig. 5 is modified as the model shown in Fig. 13 [6]. As results obtained by Tafel plot. It is seen that after 264 h
no pits were observed on the oxide surface after 48 h holding time, some small etching pits appear on the
immersion and the oxide surface was not damaged. It can surface of the sulfuric−boric−phosphoric acids anodized
be concluded that the anodized alloy indicates good alloy, indicating a good corrosion resistance due to the
corrosion resistance and the parameter θ is close to 1 but relatively high thickness of the oxide film (19.67 nm for
not close to 0. Thus, Rcorr and Cdl are undetectable. barrier layer). It is obvious that the oxide layers with
relatively higher thickness have relatively higher
resistance against electrolyte penetration. By considering
the data reported in Table 7, it can be seen that the
corrosion resistance of sulfuric−boric acids anodized
alloy is similar to sulfuric−boric−phosphoric acids
anodized alloy but visual inspection shows that more
etching pits appear on the surface of the sulfuric−boric
acids oxide film after 264 h. Severe corrosion happens
on the surface of phosphoric acid anodized alloy for only
less than 12 h.

Fig. 13 Equivalent circuit to model electrolyte penetration

Table 7 Results of salt spray tests for anodized samples
through sealed anodic film [6]
Occurring time of
Anodizing bath
corrosion spots/h
3.3 Tafel plot and salt spray tests
The results of Tafel plot for sulfuric−boric− Phosphoric acid <12
phosphoric acids, sulfuric−boric acids and phosphoric Sulfuric−boric acids 264
acid anodic films are shown in Fig. 14.
Sulfuric−boric−
264
phosphoric acids

4 Conclusions

1) The anodizing process of 2024-T3 aluminum

alloy was performed in 10% sulfuric acid bath containing
5% boric acid and 2% phosphoric acid, as a new
electrolyte, followed by sealing treatment.
2) The porous layers electrochemical parameters
were detected by sealing. The corrosion performance of
the anodic layer was studied by EIS technique in 3.5%
NaCl solution. The EIS technique was used to study the
corrosion behavior of the anodized alloy.
3) The electrolyte penetrats weaker through the
Fig. 14 Tafel plots of sulfuric−boric−phosphoric acids anodized
alloy (a), sulfuric−boric acids anodized alloy (b) and barrier layer than the porous layer. Therefore, the
phosphoric acid anodized alloy (c) evolution of electrochemical parameters of the barrier
layer is slower than the electrochemical parameters of
It can be seen from Fig. 14 that the current density the porous layer with exposure time, indicating that the
of anodic films increases in the order as sulfuric−boric− barrier layer has more corrosion resistance than its
phosphoric acids anodic film < sulfuric−boric acids associate sealed porous layer.
anodic film < phosphoric acid anodic film. The results 4) The anodizing in mixed acid followed by sealing
indicate that sulfuric−boric−phosphoric acids anodic film treatment improves the corrosion resistance of the
reveals better corrosion resistance in comparison with the 2024-T3 alloy.
anodic oxide films obtained from sulfuric−boric acids 5) The results of Tafel plot and salt spray tests are in
and phosphoric acid electrolytes. Furthermore, the results good agreement, indicating that the sulfuric−boric−
of the salt spray test are reported in Table 7. The phosphoric acids anodized alloy has better corrosion
corrosion resistance of the investigated materials was resistance than sulfuric−boric acids and phosphoric acid
studied during salt spray technique by monitoring the anodized alloys.
 M. SAEEDIKHANI, et al/Trans. Nonferrous Met. Soc. China 23(2013) 2551−2559 2559
[13] SON I J, NAKANO H, OUE S, KOBAYASHI S, FUKUSHIMA H,
HORITA Z. Effect of equal-channel angular pressing on pitting
References corrosion resistance of anodized aluminum-copper alloy [J].
Transactions of Nonferrous Metals Society of China, 2009, 19(4):
[1] PARKHUTIK V P, SHERSHULSKY V I. Theoretical modelling of 904−908.
porous oxide growth on aluminium [J]. Applied Physics, 1992, 25(8): [14] MA Song-jiang, LUO Peng, ZHOU Hai-hui, FU Chao-peng,
1258−1263. KUANG Ya-fei. Preparation of anodic films on 2024 aluminum alloy
[2] MOUTARLIER V, GIGANDET M P, PAGETTI J, NORMAND B. in boric acid-containing mixed electrolyte [J]. Transactions of
An electrochemical approach to the anodic oxidation of Al 2024 Nonferrous Metals Society of China, 2008, 18(4): 825−830.
alloy in sulfuric acid containing inhibitors [J]. Surface and Coatings [15] HELLER D K, FAHRENHOLTZ W G, O’KEEFE M J. The effect of
Technology, 2002, 161(2−3): 267−274. post-treatment time and temperature on cerium-based conversion
[3] ZUO Y, ZHAO P H, ZHAO J M. The influences of sealing methods coatings on Al 2024-T3 [J]. Corrosion Science, 2010, 52(2):
on corrosion behavior of anodized aluminum alloys in NaCl 360−368.
solutions [J]. Surface and Coatings Technology, 2003, 166(2−3): [16] ASTM B457: Standard test method for measurement of impedance of
237–242. anodic coaings on aluminum [S]. USA: ASTM Standards, 2003.
[4] HUANG Y, SHIH H, HUANG H, DAUGHERTY J, WUB S, [17] ASTM B117: Standard practice for operating salt spray (fog)
RAMANATHAN S, CHANG C, MANSFELD F. Evaluation of the apparatus [S]. USA: ASTM Standards, 2007.
corrosion resistance of anodized aluminum 6061 using [18] WEI R P, LIAO C M, GAO M. A transmission electron microscopy
electrochemical impedance spectroscopy (EIS) [J]. Corrosion study of constituent-particle-induced corrosion in 7075-T6 and
Science, 2008, 50(12): 3569–3575. 2024-T3 aluminum alloys [J]. Metallurgical and Materials
[5] LI Song-mei, ZHANG Hong-rui, LIU Jian-hua. Corrosion behavior Transactions A, 1998, 29(4): 1153–1160.
of aluminum alloy 2024-T3 by 8-hydroxy-quinoline and its [19] CAMPESTRINI P, Van WESTING E P M, ROOIJEN H W, de WIT J
derivative in 3.5% chloride solution [J]. Transactions of Nonferrous H W. Relation between microstructural aspects of Al 2024 and its
Metals Society of China, 2007, 17(2): 318−325. corrosion behaviour investigated using AFM scanning potential
[6] MOUTARLIER V, GIGANDET M P, NORMAND B, PAGETTI J. technique [J]. Corrosion Science, 2000, 42(11): 1853−1861.
EIS characterisation of anodic films formed on 2024 aluminium alloy [20] CROSSLAND A C, HABAZAKI H, SHUMIZU K, SKELDON P,
in sulphuric acid containing molybdate or permanganate species [J]. THOMPSON G E, WOOD G C, ZHOU X, SMITH C J E. Residual
Corrosion Science, 2005, 47(4): 937−951. flaws due to formation of oxygen bubbles in anodic alumina [J].
[7] ZHANG J S, ZHAO X H, ZUO Y, XIONG J P. The bonding strength Corrosion Science, 1999, 41(10): 1945−1954.
and corrosion resistance of aluminum alloy by anodizing treatment in [21] HITZIG J, JUNTTNER K, LORENTZ W J. AC-impedance
a phosphoric acid modified boric acid/sulfuric acid bath [J]. Surface measurements on corroded porous aluminum oxide films [J].
and Coatings Technology, 2008, 202(14): 3149−3156. Electrochemical Society, 1986, 133(5): 887−892.
[8] THOMPSON G E, ZHANG L, SMITH C J E, SKELDON P. [22] DASQUET J P C, CAILLARD D, CONFORTO E, BONINO J P,
Boric/sulfuric acid anodizing of aluminum alloys 2024 and 7075: BES R. Investigation of the anodic oxide layer on 1050 and 2024-T3
Film growth and corrosion resistance [J]. Corrosion Science, 1999, aluminium alloys by electron microscopy and electrochemical
55(11): 1052−1061. impedance spectroscopy [J]. Thin Solid Films, 2000, 371(1−2):
[9] EICHINGER E, OSBORNE J, van CLEAVE T. Hexavalent 183−190.
chromium elimination: An aerospace industry progress report [J]. [23] SOGNAN F, BLANC C, MANKOWSKI G, PEBERE N.
Metal Finishing, 1997, 95(3): 36,38,40−41. Characterization of sealed anodic films on 7050 T74 and 2214 T6
[10] COHEN S M. Replacements for chromium pretreatments on aluminium alloys [J]. Surface and Coatings Technology, 2002, 154(1):
aluminum [J]. Corrosion, 1995, 51(1): 71−78. 94−103.
[11] GHALI E. Corrosion resistance of aluminum and magnesium alloys: [24] HSU C H, MANSFELD F. Technical note: Concerning the
Understanding, performance, and testing [M]. New Jersey: John conversion of the constant phase element parameter Y0 into a
Wiley & Sons, 2010: 180. capacitance [J]. Corrosion, 2001, 57(9): 747−748.
[12] VENUGOPAL A, PANDA R, MANWATKAR S, SREEKUMAR K, [25] SUAY J J, GIMENEZ E, RODRIGUEZ T, HABBIB K, SAURA J J.
KRISHNA L R, SUNDARARAJAN G. Effect of micro arc oxidation Characterization of anodized and sealed aluminum by EIS [J].
treatment on localized corrosion behaviour of AA7075 aluminum Corrosion Science, 2003, 45(3): 611−624.
alloy in 3.5% NaCl solution [J]. Transactions of Nonferrous Metals
Society of China, 2012, 22(3): 700−710.

2024-T3 铝合金在硫酸−硼酸−磷酸中的阳极氧化和腐蚀行为
M. SAEEDIKHANI, M. JAVIDI, A. YAZDANI
Department of Materials science and Engineering, School of Engineering,
Shiraz University, Shiraz 7134851154, Iran

摘 要：在含有 10%硫酸、5%硼酸和 2%磷酸的混合电解液中，对 2024-T3 铝合金进行阳极氧化处理，以提高其

耐腐蚀性能。使用电化学阻抗频谱分析研究阳极氧化处理后合金的腐蚀行为。利用塔菲尔图和盐水喷雾技术进行
对比发现，与只用磷酸或硫酸和硼酸的电解液相比，使用含有 10%硫酸、5%硼酸和 2%磷酸的混合电解液阳极氧
化处理后的 2024-T3 铝合金，具有更好的耐腐蚀性和持久性。该电解液可以替代普遍用于阳极氧化铝合金的铬酸
盐浴。
关键词：阳极氧化；2024-T3 铝合金；混合电解液；EIS
(Edited by Jing-hua FANG)