Materials and Design 30 (2009) 37313737

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Comparative study of mechanical and tribological properties of alumina

coatings formed on aluminium in various conditions
W. Bensalah a,*, K. Elleuch b, M. Feki a, M. DePetris-Wery c, H.F. Ayedi a
a

Unit de recherche de Chimie Industrielle et Matriaux (URCIM), ENIS, Dpartement de Genie Des Materiaux, B.P.W. 1173-3038, Sfax, Tunisia
Laboratoire des Systmes Electromcaniques (LASEM), ENIS, B.P.W. 1173-3038, Sfax, Tunisia
c
IUT Mesures Physiques dOrsay Universit Paris XI, Plateau du Moulon, 91400 Orsay, France
b

a r t i c l e

i n f o

Article history:
Received 16 December 2008
Accepted 10 February 2009
Available online 15 February 2009
Keywords:
C. Alumina coating
E. Vickers microhardness
I. Abrasion
I. Failure

a b s t r a c t
Inuence of oxalic acid addition to sulphuric acid bath on the mechanical properties of the oxide layers
formed on aluminium has been examined. For this purpose two Doehlert experimental designs with
three variables (temperature, current density, sulphuric acid concentration) and four variables (oxalic
acid concentration, temperature, current density, sulphuric acid concentration) were realized. Four
responses were studied namely: growth rate (Ve), Vickers microhardness (D), weight loss after abrasion
(Wa) and deection at failure (Df) of the anodic oxide layer. A comparative study based on surface
responses was achieved. Compared with sulphuric acid bath, it was found that the addition of oxalic acid
permits high growth rates, high abrasion resistance and high microhardness but less ductile layers. The
observed mechanical properties of the oxide layers can be related to their morphology revealed by SEM
observations and their chemical composition determined by GDOES.
2009 Elsevier Ltd. All rights reserved.

1. Introduction
As weight-saving materials, aluminium and aluminium alloys
are becoming increasingly important for both technical and economical considerations [1,2]. However, poor friction property and
wear resistance restricted their applications in the industrial elds
requiring sliding contact. In order to improve mechanical properties of aluminium, anodizing has been commonly used [1,2].
Anodizing, a surface treatment which originated in the 1930s, is
an electrochemical process, consists on converting aluminium into
its oxide by appropriate selection of the electrolyte and the anodizing conditions, such as current density, voltage and temperature
[3,4]. By adjusting the conditions used in the anodizing process,
oxide layers can be produced with almost any desired properties,
from thin lms used in decorative applications to the extremely
hard, corrosion resistant oxides used in engineering applications
[59]. In the last few decades, the effect of anodizing conditions
and the composition of single acid electrolytes, i.e. solution of sulphuric acid, chromic acid, phosphoric acid or oxalic acid, on the
properties of the anodic layer such as corrosion resistance, microhardness and abrasion resistance were investigated [58]. To improve the properties of the anodic layer and/or to nd an
alternative of chromic acid anodizing process, mixed acid electro-

* Corresponding author. Tel.: +216 74 274 088; fax: +216 74 275 595.
E-mail address: walbensalah@yahoo.fr (W. Bensalah).
0261-3069/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.matdes.2009.02.005

lytes such as oxalic acidchromic acid, nitric acidsulphuric acid

and boric acidsulphuric acid were implemented [911].
In previous works [12,13], we have optimized some of mechanical properties of the anodic oxide layer elaborated on aluminium
in sulphuric acid and oxalic acidsulphuric acid baths using two
Doehlert experimental designs. The electrolyte composition, temperature and current density were retained as variables to conduct
each study.
The objective of this paper is to investigate the effect of oxalic
acid addition to a sulphuric acid bath, on the thickness and the
mechanical properties of the elaborated oxide layers, namely:
Vickers microhardness (D), weight loss after abrasion (Wa) and
deection at failure (Df). Comparisons were made using the previously established models obtained from Doehlert experimental design applied to each of the anodizing process [12,13]. Moreover,
the morphology and the composition of the anodic oxide layer
were examined by scanning electron microscopy (SEM), optical
microscopy and glow-discharge optical emission spectroscopy
(GDOES).
2. Experimental
2.1. Materials and procedures
Parrallelipedic AA1050 samples 100  25  3 mm3 were used
as the substrate for anodic conversion treatment. Prior to anodizing, samples were mechanically polished to P1000 grade paper

3732

W. Bensalah et al. / Materials and Design 30 (2009) 37313737

followed by (i) chemical polishing in a 15:85 (v/v) mixture of concentrated HNO3 and H3PO4 at 85 C for 2 min, (ii) etching in 1 M
NaOH solution at room temperature for 1 min and (iii) chemical
pickling in 30% (v/v) HNO3 solution at room temperature for 30 s.
Water rinsing was used after each step. Afterwards, samples were
anodized in vigorously stirred acid solutions (sulphuric acid and
oxalicsulphuric acid bath) maintained within 0.1 C of the set
temperature for 90 min then washed in deionised water and dried.
The used cathodes were also aluminium sheets. Sulphuric, nitric
and phosphoric acids are analytical grade chemicals.

2.3. Methodology and design of experiments

The Doehlert experimental design [14] was performed to study
the effect of the anodizing conditions on the performance of the retained baths and on the aluminium oxide layer properties. As currently used in experimental design, natural variables Uj were
transformed into coded variables Xj according to the following
relation [1517]:

Xj

U j  U j 0
DU j

2.2. Testing methods

In order to characterize the anodic oxide layer, four tests were
conducted. The oxide layer thickness was measured using ELCOMETER 355 Top Thickness Gauge. The Vickers microhardness was
carried out using DELTALAB HVS-1000 tester (200 g load for 15 s).
Abrasion tests were conducted using a pin-on-disc machine.
Anodized samples with dimensions of 20  20  3 mm3 were
brought into contact with 320 grit SiC paper, xed on a rotating
disc with a constant speed of 20 rpm. The applied normal load
was 5 N and the test duration was 1 min.
Deection at failure of the anodic oxide lms on aluminium was
measured by performing three point exure tests on parrallelipedic samples 100  25  3 mm3 at room temperature. A universal
machine [Lloyd instruments LR 50KN] was used for this purpose.
Loading speed was xed at 2 mm min1 and the calibrated distance was 50 mm.
The morphology of the oxide layer was studied from the top
side of the layer using a Scanning Electron Microscope SEM (Jeol
JSM-6400F and Philips XL30).
The morphology of worn oxide layer surfaces was studied using
a LEICA optical microscope.
The distribution of species in the anodic oxide layer was determined by depth proling using a Jobin Yvon GD Proler instrument
equipped with a 4 mm diameter anode and operating at pressure
of 800 Pa and a power of 600 W in an argon atmosphere. The relevant wave-lengths (nm) were as follows: Al, 396.15; O, 130.22, S,
181.73 and C, 156.14. The sputtering layer was 6 lm thick.

where Uj(0) is the value of Uj at the centre of the study domain and
DUj is the variation step. Doehlert design requires N = k2 + k + N0
experiments, where k is the number of the factors and N0 the number of centre runs. Experiments at the centre are required to conduct statistical tests. For example, Doehlert experimental design
in coded variables corresponding to 4 variables is given in Table
1. The delimited zones correspond to the three and four variables
experimental designs. Experiment 1 is the central run for each of
the experimental design. Replicates at the central level of the variables (experiments 2225) were conducted in order to estimate the
pure error variance.
A full quadratic model, including interaction terms, was assumed to describe the relationship between each response Yi and
experimental variables Xj:

Y^ b0

k
X
j1

bj X j

k
k
X
X

bjh X j X h

j1 hj1

k
X

bjj X 2j

j1

where b0 is the constant of the model, bj the rst degree coefcients,

bjh the cross-products coefcients and bjj the quadratic coefcients.
It is to mention that NEMROD W software [18] was used for
data calculation and treatment.

3. Results and discussion

3.1. Variables, study domains and model expressions

Table 1
Doehlert experimental design in coded variables (k = 4 and N0 = 4).

In order to compare the performances of sulphuric acid and

oxalic acidsulphuric acid anodizing processes, a Doehlert experimental design was applied for each of them. Four responses were
retained:
1 (lm min1),
growth rate of the anodic oxide layer, Ve, noted Y
2
Vickers microhardness of the anodic oxide layer, D, noted Y
(HV),
3
weight loss by abrasion of the anodic oxide layer, Wa, noted Y
(mg),
4 (mm).
deection at failure of the anodic oxide layer Fr, noted Y

Table 2
Study domains.
Variables

Centre Uj(0)

Variation step DUj

Sulphuric acid anodizing process

5
U1 (C)
7
U2 (A dm2)
1
U3 (g L )
3

Number of levels

14
2
160

11
1
40

Oxalic sulphuric acid anodizing process

U1 (g L1)
5
7
U2 (C)
7
U3 (A dm2)
3
U4 (g L1)

10
16.5
2
160

8
13.5
1
40

W. Bensalah et al. / Materials and Design 30 (2009) 37313737

3733

Three variables Uj were selected for the sulphuric acid anodizing process: (i) U1: the anodizing temperature, T (C), (ii) U2: the
current density, J (A dm2) and iii) U3: the sulphuric acid concentration, Csul (g L1). The study domain (number of levels, centre
and variation step) is given in Table 2. The obtained models were
validated using ANOVA analysis. Their expressions were the following [12]:

Y^ 1 0:527  0:064X 1 0:279X 2 0:013X 21  0:004X 22

0:022X 23  0:006X 1 X 2 0:014X 1 X 3 0:001X 2 X 3
Y^ 2 478:2  135:6X 1 41:8X 2 12:2X 3  190:3X 21  248:9X 22
22:9X 23  75:1X 1 X 2 258:6X 1 X 3  192:9X 2 X 3
Y^ 3 25:35 15:98X 1 0:43X 2 2:94X 3 8:05X 21  0:35X 22
 3:55X 23 3:46X 1 X 2 1:71X 1 X 3  3:46X 2 X 3
Y^ 4 6:32  0:86X 1 1:55X 2 0:41X 3 0:42X 21  0:31X 22
 0:17X 23 0:12X 1 X 2 0:27X 1 X 3  0:08X 2 X 3
Four variables Uj were retained for the oxalicsulphuric acid anodizing process: (i) U1: the oxalic acid concentration, Cox (g L1), (ii)
U2: the anodizing temperature, T (C), (iii) U3: the current density,
J (A dm2) and (iv) U4: the sulphuric acid concentration, Csul
(g L1). The corresponding study domain is given in Table 2. The
expressions of the validated models were the following [13]:

Fig. 1. Growth rate of the anodic oxide layer versus T, J: (a) Csul = 160 g L1 and
Cox = 10 g L1; (b) Csul = 160 g L1 and Cox = 0 g L1.

Fig. 3. Vickers microhardness of the anodic oxide layer formed in oxalicsulphuric

acid bath versus T, J: (a) Csul = 160 g L1 and Cox = 6 g L1; (b) Csul = 160 g L1 and
Cox = 10 g L1; (c) Csul = 160 g L1 and Cox = 15 g L1.

Fig. 4. Vickers microhardness of the anodic oxide layer versus T, J: (a)

Csul = 160 g L1 and Cox = 10 g L1; (b) Csul = 160 g L1 and Cox = 0 g L1.

Fig. 2. SEM of the anodic oxide layer obtained under: (a) T = 15 C, J = 2 A dm2 and Csul = 160 g L1; (b) Cox = 10 g L1, T = 15 C, J = 2 A dm2 and Csul = 160 g L1.

3734

W. Bensalah et al. / Materials and Design 30 (2009) 37313737

Y^ 1 0:546 0:002X 1  0:044X 2 0:303X 3  0:008X 4

0:006X 1 X 3  0:039X 2 X 3  0:021X 1 X 4  0:001X 2 X 4
0:001X 3 X 4 0:009X 21  0:011X 22 0:007X 23  0:052X 24
Y^ 2 458:4 19:2X 1  130:8X 2  14:7X 3  7:7X 4 72:7X 1 X 2
 11:6X 1 X 3  16:2X 2 X 3  25:5X 1 X 4 35X 2 X 4
103:5X 3 X 4 14:6X 21  120:1X 22  30:7X 23  25:2X 24
Y^ 3 21:4  3:2X 1 1:847X 2 0:939X 3 1:739X 4  9:238X 1 X 2
2:654X 1 X 3 8:131X 2 X 3 2:056X 1 X 4  1:004X 2 X 4
1:42X 3 X 4 1:1X 21 1:1X 22 5:39X 23  8:349X 24
Y^ 4 3:6 0:270X 1 0:191X 2 1:347X 3 0:032X 4 0:173X 1 X 2
 0:551X 1 X 3  0:271X 2 X 3  0:427X 1 X 4  0:283X 2 X 4
0:052X 3 X 4 0:55X 21  0:217X 22 0:367X 23  0:34X 24
Fig. 5. Weight loss by abrasion of the anodic oxide layer formed in oxalicsulphuric
acid bath versus T, J: (a) Csul = 160 g L1 and Cox = 6 g L1; (b) Csul = 160 g L1 and
Cox = 10 g L1; (c) Csul = 160 g L1 and Cox = 15 g L1.

3.2. Comparison of the anodizing processes

The established models for the retained anodizing processes
will be used to undertake comparisons via response surfaces.

Fig. 6. Weight loss by abrasion of the anodic oxide layer versus T, J: (a)
Csul = 160 g L1 and Cox = 10 g L1; (b)Csul = 160 g L1 and Cox = 0 g L1.

3.2.1. Growth rate of the anodic oxide layer

The effect of oxalic acid addition to sulphuric acid bath on the
growth rate can provide rapid information on the anodic layer
structure modications. Hence these modications can be related
to and help to understand possible effect on the mechanical properties of the oxide layer.
Fig. 1 shows surface responses of growth rates corresponding to
sulphuric acid (Fig. 1b) and oxalic/sulphuric acid (Fig. 1b) anodizing processes. As can be seen, (i) oxalic acid addition enlarges the
temperature domain and (ii) favours the growth rate of the anodic
oxide layer. For both anodizing processes, high values of the
growth rate are obtained with high current densities and low electrolyte temperatures. In fact, the addition of oxalic acid (weak acid)
to sulphuric acid (strong acid) decreases the aggressiveness of the
electrolyte towards the oxide and favours, thus, the oxide layer
growth [10]. On the other hand, the increase of current density

Fig. 7. Optical microscopy of worn surfaces: (a) non treated aluminium; anodic oxide layers, (b) Cox = 0 g L1,(c) Cox = 6 g L1, (d) Cox = 15 g L1 for T = 16.5 C, J = 2 A dm2 and
Csul = 160 g L1.

W. Bensalah et al. / Materials and Design 30 (2009) 37313737

make the dissolution of the oxide in the bottom of pores more pronounced and lead to higher growth rates [9].
SEM photographs, on top surface, of anodic layers formed in sulphuric acid and oxalic acidsulphuric acid baths are shown in
Fig. 2.
Both anodic layers present a porous structure. In Fig. 2a the
structure is more open with higher pore diameters (black spots)
and lower wall thicknesses. It could be noted that at some locations the oxide walls between neighboring pores had completely
been dissolved, inducing a merging of the involved pore mouths.
Fig. 2b shows oxide nuclei (white dots) [19] and small pores separated by thick pore walls. From these observations, the anodic layer
formed with the addition of oxalic acid appears more compact.
Therefore, the organic acid addition forms thicker and less porous
anodic oxide layers.
3.2.2. Vickers microhardness of the anodic oxide layer
Three oxalic acid concentrations, i.e. 6 g L1, 10 g L1 and
15 g L1, were selected to investigate the effect of current density
and electrolyte temperature on the microhardness evolution
(Fig. 3). Surface responses indicate that the amount of added oxalic
acid changes signicantly the microhardness of the oxide layer.
High concentrations of the added acid lead to high Vickers microhardness of the layer for temperatures superior than 10 C.
On the other hand, the trend indicates that increasing the current density in the selected range does not change signicantly
the microhardness of the formed oxide layers. It is to mention that
a tendency to decrease at the highest current densities seems to
occur.
As observed, increasing oxalic acid concentration leads to a little increase in layer thickness which can also generates an increase
of sulfate anions composition along the deeper pore walls [20]. All
these facts seem to enhance the anodic oxide layer microhardness.
In addition, higher driving force accelerates the reactions at the
substrate/oxide which can causes cracks in this region. These
cracks are considered most likely ascribed to the internal stress
generated by the growth of the oxide [21]. At the oxide/electrolyte
interface many defects can also occur (open porosities, local burning, roughening, etc.) [2224]. All these defects are expected to decrease the microhardness of anodic oxide layers.
Fig. 4 shows surface responses of Vickers microhardness obtained by sulphuric acid and oxalic/sulphuric acid anodizing pro-

Fig. 8. Deection at failure of the anodic oxide layer formed in oxalicsulphuric

acid bath versus T, J: (a) Csul = 160 g L1 and Cox = 6 g L1; (b) Csul = 160 g L1 and
Cox = 10 g L1; (c) Csul = 160 g L1 and Cox = 15 g L1.

3735

cesses. As can be seen, oxalic acid addition enlarges the

temperature domain and enhances signicantly the response overall the working domain. For both of the anodizing processes, only,
at low electrolyte temperatures, oxides with high microhardness
were formed.
3.2.3. Weight loss by abrasion of the anodic oxide layer
As proceeded with the Vickers microhardness, the same oxalic
acid concentrations were selected to investigate the inuence of
current density and temperature on the weight loss by abrasion
of the elaborated anodic oxide layers (Fig. 5). The tendencies indicate that the amount of added oxalic acid has a strong positive effect on the abrasion behavior. In fact, with high oxalic acid
concentrations low weight losses were recorded.
On the other hand, high abrasion resistance of the oxide layer is
obtained at low temperatures and current densities. From Fig. 5
two domains can be distinguished. For temperatures superior than
10 C, high oxalic acid concentrations are required to ensure high
abrasion resistance. At temperatures inferior than 10 C, only low
oxalic acid concentrations are sufcient to produce abrasion resistant layers.
Fig. 6 shows that oxalic acid addition to the sulphuric acid bath
enhances the abrasion resistance of the anodic oxide layers for
temperatures up to 10 C. The variation of the current density, in
the working domain, does not change signicantly the response.
The morphology of the worn surface is strongly dependent on
the anodizing conditions. The change in morphology may be observed in Fig. 7. Four samples are shown after abrasive wear tests.
As can be seen, non treated aluminium has experienced severe
abrasive wear. Distinct parallel and continuous grooves with high
quantity of plastic deformation were occurred (Fig. 7a). With the
addition of oxalic acid, grooves were reduced to ne scratches
(Fig. 7bd) and plastic deformations were observed. Surface cracks
were sometimes noticed (Fig. 7b). From Fig. 7bd, there is no drastic change in morphology of the worn surfaces was perceived with
increasing addition of oxalic acid. The main wear mechanism for
the treated specimens was dominant by abrasive wear. Apparently,
the above characteristics of worn surfaces can be related to the surface microhardness of different specimens.
3.2.4. Deection at failure of the anodic oxide layer
The obtained anodic oxide on aluminium is hard and usually
accompanied by the risk of brittle failure, especially under surface-concentrated loads from static or cyclic contacts. In this paragraph, the inuence of oxalic acid added to sulphuric acid bath on

Fig. 9. Deection at failure of the anodic oxide layer versus T, J: (a) Csul = 160 g L1
and Cox = 10 g L1; (b) Csul = 160 g L1 and Cox = 0 g L1.

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W. Bensalah et al. / Materials and Design 30 (2009) 37313737

deformation and fracture of these lms will be discussed. The effect of current density and electrolyte temperature on the deection at failure of anodic layers was examined through three
oxalic acid concentrations: 6 g L1, 10 g L1 and 15 g L1. The tendencies (Fig. 8) indicate that the amount of added oxalic acid has
a negative effect on the deection at failure. In fact, with high oxalic acid concentrations more brittle oxide layers were formed.
According to Fig. 9, oxalic acid addition leads to less ductile anodic oxide layers and this throughout the study domain.

When the anodized aluminium is subjected to exural test, the

oxide layer undergoes elastic deformation while the metal substrate undergoes elasticplastic deformation. As the continuity between the anodic oxide layer and the substrate must be
maintained at their interface before failure, this gives rise to interfacial shear stress when the hard oxide layer, which shows little
deformation, inhibits deformation of the substrate. As a result of
the interfacial shear stress, force is transferred from aluminium
to the oxide layer thus inducing the tensile stress in the coating.

Fig. 10. Back side optical micrographs of anodized samples elaborated under: (a) T = 15 C, J = 2 A dm2 and Csul = 160 g L1; (b) Cox = 10 g L1, T = 15 C, J = 2 A dm2 and
Csul = 160 g L1.

1000

Al
O*1000
Al
S*40

Intensity (arb.unit )

800
600

o
400

200
0

100

200

300

400

Abrasion time (s)

1000

Al

Intensity (arbit. unit)

Intensity (arbit. unit)

800

600

o
400

(1)
S

200

C
0

100

80

O*1000
C*10
Al
S*40

200
300
400
Abrasion time(s)

500

600

C*40

60

40

(2)
20

0
0

200

400
600
Abrasion time (s)

800

Fig. 11. GDOES prole of anodized surface obtained under: (a) T = 14 C, J = 2 A dm2, Csul = 160 g L1; (b) Cox = 10 g L1, T = 14 C, J = 2 A dm2, Csul = 160 g L1: (b-1)
distribution of Al, O, C and S; (b-2) distribution of C.

W. Bensalah et al. / Materials and Design 30 (2009) 37313737

As the substrate deformation increases, this tensile stress will

accumulate and eventually reach the fracture strength of the coating. Parallel long cracks were, then, observed on the surface of the
oxide layer in a direction perpendicular to the tensile loading axis
(Fig. 10). According to all the obtained results (not shown here), the
patterns of the fractured oxide layers were independent to the bath
composition. In fact, it was reported that the deection at failure
and the average crack spacing between normal fracture lines were
signicantly affected by the thickness of the anodic oxide layer
[25].
3.3. Chemical analysis of the anodic oxide layer
In order to inspect possible incorporation of sulfate and oxalate
anions in porous oxide layer, chemical analysis of the oxide layer
was conducted using GDOES. Fig. 11 shows a depth prole of the
oxide layer elaborated in sulphuric acid bath (Fig. 11a) and sulphuric acidoxalic acid bath (Fig. 11b and c). The distribution of aluminium, oxygen and sulphur were revealed clearly through the
oxide layer elaborated in sulphuric acid bath. With the addition
of oxalic acid to sulphuric bath, the GDOES of the oxide layer shows
the presence of carbon. The presence of sulphur and carbon can be
and C2 O2
anions
explained by the inward migration of SO2
4
4
through the pores of the layer [26,27]. A relatively narrow peak located at the inner interface metal/oxide suggests an accumulation
of SO2
4 ions (inner interface).
4. Conclusion
A comparative study of the sulphuric acid and oxalic acidsulphuric acid anodizing processes was conducted using response
surfaces. A three variables (temperature, current density, sulphuric
acid concentration) and four variables (oxalic acid concentration,
temperature, current density, sulphuric acid concentration) Doehlert experimental designs were applied for each process. Four responses were retained namely: growth rate (Ve), Vickers
microhardness (D), weight loss after abrasion (Wa) and deection
at failure (Df). It was found that the addition of oxalic acid to sulphuric acid bath permits (i) high growth rates and more compact
layers, (ii) high abrasion resistance and microhardness and (iii) less
ductile layers.
From the obtained results, abrasion resistance and microhardness were likely to be highly correlated and the mechanical properties of oxide layers appear to be related with their morphology
revealed by SEM observations and their chemical composition
determined by GDOES.

3737

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