Transactions of the IMF

The International Journal of Surface Engineering and Coatings

ISSN: 0020-2967 (Print) 1745-9192 (Online) Journal homepage: http://www.tandfonline.com/loi/ytim20

Sulphuric acid anodising of EN AC-46500 cast

aluminium alloy

B Gastón-García, E García-Lecina, M Díaz-Fuentes, J A Díez & C Müller

To cite this article: B Gastón-García, E García-Lecina, M Díaz-Fuentes, J A Díez & C Müller (2011)
Sulphuric acid anodising of EN AC-46500 cast aluminium alloy, Transactions of the IMF, 89:6,
312-319

To link to this article: http://dx.doi.org/10.1179/174591911X13167804921037

Published online: 12 Nov 2013.

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 Sulphuric acid anodising of EN AC-46500 cast
aluminium alloy
B. Gastón-Garcı́a1, E. Garcı́a-Lecina*1, M. Dı́az-Fuentes1, J. A. Dı́ez1 and
C. Müller2
In this study, the anodising behaviour of commercial EN AC-46500 cast aluminium alloy in
sulphuric acid electrolyte was investigated in order to determine the optimal experimental
conditions. The results showed that the high content and variety of alloying elements disrupted
the classical porous morphology and changed the typical V–t curves of the high purity aluminium
anodising. The effects of electrolyte concentration, bath temperature, current density and
anodising time on the characteristics of the anodic layers obtained were studied, and it was
observed that the increase in any of these parameters produced a decrease in the mechanical
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properties of the layers. The best results were obtained by anodising at 5 vol.-%H2SO4, at
5?0 A dm22 during 30 min at 0uC. The application of a polishing pretreatment improved the film
appearance and did not modify the mechanical properties of the film, but considerably
decreased the film thickness.
Keywords: Aluminium, Anodising, Intermetallic particles, EN AC-46500

Introduction in the case of high purity aluminium, the anodising

Aluminium has been widely used in industry for
decades. Its low density, high strength to weight ratio
and its corrosion resistance make aluminium and its
alloys the material of choice for many applications in
the aircraft, aerospace, automotive, architectural and
packaging industry, among others. Aluminium alloys
can be divided into two main categories, namely casting
alloys and wrought alloys. Although y85% of alumi-
nium is used for wrought products as foils, extrusions
and rolled plates, the industrial interest in cast alumi-
nium alloys is gradually increasing due to its low cost
and excellent fluidity, which allow the low cost produc-
tion of complex components with high size. However,
their poor tribological properties and low corrosion
resistance notably reduce their application.
In general, tribological and corrosion properties of
aluminium and its alloys can be improved by anodising.
This electrochemical technique increases the thickness of
the natural oxide layer, converting the surface of the
aluminium alloy into a ceramic coating (Al2O3) with
improved hardness, wear and corrosion resistance.1,2 The
characteristics of the anodic alumina oxide layer (AAOL)
formed depend not only on the anodising conditions, i.e.
composition of electrolyte, current density, voltage,
temperature, etc.,3–6 but also on the chemical composi-
tion and metallurgical history of the alloy. Thus, although
1
Surface Finishing Department, CIDETEC-ik4, Pu Miramón 196, E-20009
San Sebastián, Spain
2
ELECTRODEP, Departament de Quı́mica Fı́sica, Facultat de Quı́mica,
Universitat de Barcelona, C/Martı́ i Franquès 1, E- 08028 Barcelona, Spain
*Corresponding author, email egarcia@cidetec.es
process is easily performed and aesthetic, functional and
high ordered porous AAOL can be obtained,7–9 com-
mercial aluminium alloys contain intermetallic particles,
elements in solid solution and, in some cases, impurities
that negatively influence the general anodising response.10
The final result is AAOL with cracks, voids and regions of
different compositions which determine the aesthetic,
physical and mechanical characteristics of the anodic
oxide film formed.11–16
In this sense, it is known that it is difficult to obtain
appropriate AAOL on cast aluminium alloys, mainly
owing to low composition homogeneity, high porosity
and presence of large concentration of alloying
elements such as silicon and copper which are in the
form of intermetallic compounds and are added to the
matrix in order to increase the fluidity of the molten
metal and the resistance of the material.17–20 Thus,
although comparative studies of the anodising beha-
viour of some cast alloys with Al and AlSi type alloys
are well documented,21–25 a systematic study is still
necessary in order to overcome the anodising limita-
tions, determine the optimal anodising conditions and
obtain good quality anodising films on different cast
alloys of industrial interest. That is the case of EN AC-
46500 die cast aluminium alloy, one of the most
popular die cast alloys used in the production of com-
ponents with complicated shapes that require strength
including air brake castings, gear cases and air cooled
heads. This alloy contains relatively large concentra-
tions of alloying elements that exceed the solid
solubility in aluminium, forming second phase particles
during solidification. In the present paper, the effect of
different experimental parameters on anodising of

ß 2011 Institute of Metal Finishing

Published by Maney on behalf of the Institute
Received 31 March 2011; accepted 26 July 2011
312 DOI 10.1179/174591911X13167804921037 Transactions of the Institute of Metal Finishing 2011 VOL 89 NO 6
 Gastón-Garcı́a et al.
commercial EN AC-46500 cast aluminium alloy in
sulphuric acid electrolyte is reported. The growth and
morphological characterisation of the oxide layers
obtained are discussed, and microhardness and wear
resistance have been assessed and compared with those
of the substrate. Moreover, the effect of a mechanical
pretreatment on the anodic film obtained has also been
analysed. Results from this work may assist in selecting
the most appropriate experimental conditions for the
development of high quality anodic oxide layers on this
cast alloy that would made possible the implementation
of aluminium in areas where it was not considered
possible hitherto.
Experimental
Flat shaped industrial pieces of cast aluminium alloy EN
AC-46500 provided by an aluminium die cast manu-
facturer were used in the present work [chemical
composition (wt-%): Al, 83?55; Si, 11?01; Cu, 2?28; Zn,
1?22; Fe, 0?887; Mg, 0?511; Mn, 0?200; Pb, 0?0959; Ni,
0?0736; Ti, 0?0468; Cr, 0?0322; Sn, 0?0256; other,0?07].
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An active area of 13?5 cm2 was considered for the
experiments and the rest of the sample was protected
with commercial resin. Before anodising, samples were
submitted to a pretreatment process in order to prepare
the surface for the anodising process: soaking in an
alkaline cleaner at 45–50uC for 10 min, and desmutting
in an acid solution at room temperature for 10 min.
Samples were thoroughly rinsed in deionised water after
each step. In some cases, aluminium samples were
submitted to a mechanical pretreatment before the
anodising process.
The anodising process was performed in a sulphuric
acid electrolyte at 5 and 15 vol.-% concentrations. A two
electrode thermostated cell of 10 L with a cylindrical
stainless steel cathode and agitation by air was used.
Aluminium samples were anodised under galvanostatic
conditions, varying the current density between 1?0 and
8?0 A dm22. The current was applied by a direct current
power supply (SM300-5; Delta Elektronika, Zierikzee,
The Netherlands) and the evolution of the voltage
during anodising was measured and transferred to
a computer by a multimeter (HP34401A; Agilent
Technologies, Santa Clara, CA, USA). The temperature
of the electrolyte was maintained constant by a
cryostatic bath (F12-MC; Julabo, Seelbach, Germany)
at three different values, i.e. 25, 0 and 20uC. Anodising
time was varied from 30 up to 120 min. Finally, samples
were thoroughly rinsed in deionised water and air dried.
Microstructural and morphological characterisations
of the substrate and the oxide layers were performed
by optical microscopy (OM; EPIPHOT 200; Nikon,
New York, USA) and scanning electron microscopy
(SEM; JSM 5500 LV; JEOL, Tokyo, Japan). To avoid
charging, the samples were covered with a thin gold
layer, applied by a sputter coater (SCD 005; Bal-Tec,
Pfäffikon, Switzerland). Energy dispersive X-ray spec-
troscopy (EDS; INCA ENERGY SERIE 200; Oxford
Instruments, Oxfordshire, UK) was used for qualitative
elemental chemical analysis. The thickness of the anodic
oxide layers was determined by OM analysis of the oxide
cross-sections. The data represent the average and
standard deviation of 30 readings for each sample.
Hardness of different layers was measured by a
microhardness tester (FISCHERSCOPE HM2000;
Transactions of the Institute of Metal Finishing
Sulphuric acid anodising of EN AC-46500 cast aluminium alloy
Fischer, Hünenberg, Switzerland) in cross-sections of
the samples, using a final load of 15 mN and a load
application time of 10 s. This load was selected to avoid
the influence of the substrate or the resin in the
microhardness measurements of the layers obtained in
different anodising conditions. Vickers hardness was
obtained by averaging 10 measurements on each sample.
Wear tests were performed using a ball on disc tribometer
(THT; CSM Instruments, Peseux, Switzerland) at room
temperature. A 100Cr6 steel ball with a diameter of 6 mm
was used as the counterface material. The wear tests were
conducted under a normal load of 5 N, with a rotation
diameter of 6 mm, at a sliding distance of 465 m and a
sliding speed of 4 cm s21. After testing, a section profile of
the wear tracks on the oxide layer was performed by a
contact profilometer (TALYSURF INTRA 50MM; Taylor
Hobson, Leicester, UK). From this information, maximum
depth penetration and wear section area were determined.
The volumetric wear factor of the different oxide layers K
was calculated using the following equation
K~2p rA=Nd (1)
where r is the rotation radius (mm), A is the wear section
area (mm2), N is the normal load applied and d is the sliding
distance (m).
Results and discussion
Microstructure of cast alloy
The microstructure of the EN AC-46500 aluminium
alloy was characterised by OM and SEM–EDS. In the
optical micrograph in Fig. 1a, intermetallic particles and
microvoids originating during the casting process can be
distinguished from the aluminium alloy matrix. From a
morphological point of view, the intermetallic particles
observed in this alloy could be classified into two main
groups: particles with polyhedrical shape with sizes in
the range of 10–25 mm, and particles with an acicular
geometry having sizes up to 25 mm. The EDS analyses
carried out in both types of particles showed that the
polyhedrical shape particles were composed of Al–Fe–
Si–Mn–Cr; whereas, the particles with acicular shape
contained Al and Cu (inset, Fig. 1a). A detailed obser-
vation by SEM–EDS of the matrix of this aluminium
alloy (Fig. 1b) also revealed the presence of granular a-
Al phase surrounded by Si phase platelets formed in the
interdendritic regions as part of the Al–Si binary
eutectics.26
Voltage–time evolution during formation of
anodic oxide layer on cast alloy
In order to study the effect of different experimental
parameters on the film growth, voltage–time (V–t)
responses were recorded during anodising experiments
(Fig. 2).
Figure 2a shows the V–t transients for anodising
processes at different current densities in a 15 vol.-
%H2SO4 electrolyte. In general, it was observed that
there was an increase in the potential with time during
the first minute of the experiment until attaining a
relatively constant value. The final voltage increased
with current density from 55 V at 1?0 A dm22 to almost
80 V at 5?0 A dm22. In the case of 8?0 A dm22, a slight
decrease in the final voltage was observed, probably
related to low quality films produced by heating effects
2011 VOL 89 NO 6 313
 Gastón-Garcı́a et al. Sulphuric acid anodising of EN AC-46500 cast aluminium alloy

1 Images (OM and SEM) of cross-sectional EN AC-46500 cast aluminium alloy. a Low magnification image of sample
microstructure. Inset shows EDS spectrum of intermetallic particles: (1) Al–Fe–Si–Mn–Cr particles; (2) Al–Cu particles
(small Au peaks are due to metallic gold that was sputter coated on aluminium alloy). b Detail of areas with different
morphologies in aluminium alloy matrix. Inset shows EDS spectrum from two marked zones

(Joule effect) generated under high current anodising steady state was accompanied by voltage fluctuations
conditions. In all the cases studied, the final voltage (55– indicative of cracking and reanodising processes pro-
80 V) was considerably higher than that obtained for voked by high level of stresses in the layer.28,29 When
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pure aluminium anodising (20–25 V), as a consequence
of a higher resistivity of the oxide or the substrate/
oxide interface probably due to the presence of oxygen
gas filled voids which hinder the ions transport
processes.21,27 Moreover, in most of the cases, the
analysing the curves at the initial stage of anodic
oxidation (i.e. first 2 min), three different regions (I, II
and III) were detected before the onset of steady state
voltage (region IV) (Fig. 2b). Thus, at the beginning of
the anodising process and regardless of the current

a, b effect of current density: 15 vol.-%H2SO4 electrolyte at 0uC and 1?0, 3?0, 5?0 and 8?0 A dm22 (marked with letters a,
b, c and d respectively); c effect of electrolyte concentration: 15 and 5 vol.-%H2SO4 electrolytes (marked with letters a
and b respectively) at 0uC and 5?0 A dm22; d effect of temperature and anodising time: 15 vol.-%H2SO4 electrolyte at 20,
0 and 25uC (marked with letters a, b and c respectively), at 5?0 A dm22 for 120 min
2 Voltage–time curves registered during galvanostatic anodising of EN AC-46500 cast aluminium alloy under different
conditions

314 Transactions of the Institute of Metal Finishing 2011 VOL 89 NO 6

 Gastón-Garcı́a et al.
a at 3?0 A dm22 (homogeneous surface); b at 8?0 A dm22 (powdery surface)
3 Images (SEM) of top view of anodic alumina layers formed on EN AC-46500 aluminium alloy after anodising in 5
vol.-%H2SO4 electrolyte at 25uC for 120 min
density, there was a slope change y7 V (transition I–II)
associated with the presence of an air formed film on the
surface of the alloy.27 The time period during which this
transition potential was stable decreased with the
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increase in current density. Subsequently, the curve
was characterised by a linear increase in voltage with
time limited by another slope change (transition II–III),
which may be related to pore nucleation. The rate of
voltage increase with time was enhanced by increasing
the anodising current density. Moreover, while the exact
transition II–III potential depended on the experimental
current density, it occurred at voltages similar to those
of pure aluminium (25–35 V). Beyond that point,
instead of observing a voltage decline to the steady
stage value (general behaviour of pure aluminium), an
increase in voltage with time at a progressively reducing
rate until achieving a steady stage voltage was observed
(region III).
As it has been described, anodising of EN AC-46500
results in a different V–t response from that observed for
pure aluminium anodising, probably due to secondary
processes that take place during the formation of the
alumina film, such as anodic oxidation of intermetallic
particles, oxygen evolution, cracking and reanodising
processes.21
Moreover, the analysis of different experimental
conditions showed that the voltage profiles also pre-
sented different features as a function of the electrolyte
concentration (Fig. 2c) and temperature (Fig. 2d). Thus,
it was observed that the transition voltages correspond-
ing to the transitions from II to III regions of the V–t
curves increased with the decreases in electrolyte
concentration and temperature. Moreover, the final
voltage decreased with the increases in electrolyte
concentration and temperature.
Morphology, microstructure and thickness of
anodic oxide layers
In an effort to correlate the differences among the
voltage response with the properties of the films, the
morphology, structure and thickness of the AAOL were
analysed.
Morphology and structure
The surface appearance of the EN AC-46500 anodised
samples varied according to the anodising conditions.
Under suitable experimental conditions (e.g. 5 vol.-%H2SO4,
25uC, 3?0 A dm22 and 120 min), the anodised film showed
Transactions of the Institute of Metal Finishing
Sulphuric acid anodising of EN AC-46500 cast aluminium alloy
an homogeneously aesthetic dark grey colour and only
few, very thin cracks were visible on its surface (Fig. 3a).
However, when higher current densities, temperatures and
anodising times were applied, the anodic oxide layers showed
a brown pale tonality that in some cases was rough and
powdery and could be easily detached from the substrate. The
surface of these samples showed the presence of numerous
wide cracks (Fig. 3b), linked to the deterioration of the layer
properties by thermally enhanced (field assisted and chemical)
severe oxide dissolution. These results are in agreement with
V–t transients recorded (Fig. 2a), where it was observed that
the final voltage corresponding to 8?0 A dm22 was slightly
lower than that corresponding to 5?0 A dm22.
The SEM observation of the cross-sections of the
anodic oxide layers revealed an undulating aluminium/
oxide interface (Fig. 4a) under all experimental condi-
tions, attributed to the different oxidation reactivities of
the aluminium matrix in comparison with the inter-
metallic particles.11–16,23 In addition, the anodic layers
presented considerable porosity and cracks. Most of
them were likely to have come from acicular particles
dissolution (principally formed by Cu and Al) taking
place during the anodising process, because no such
precipitates were found within the anodic layer. This
result is consistent with the considerations of other
authors who declared that particles with similar
chemical composition (Cu2Al) tended to be anodic
relative to the aluminium matrix.14,30 Apart from this,
previous studies showed that oxidation of copper was
also associated with the generation of oxygen within the
anodic film and the proliferation of oxygen bubbles
with high pressure.31–34 These bubbles may grow and
coalesce and the contained gas may be released by the
rupture of the oxide film. Moreover, the stress
generated during the growth of the anodic oxide films
may also contribute to the cracking of the film.35 The
consequence of such processes is the development of
anodic layers of bad quality.
On the other hand, polyhedrical particles (Al–Fe–Si–
Mn–Cr) did not prevent or hinder the growth of the
anodic film but seemed to remain partly oxidised after
anodic oxidation. In this sense, the highlighted area in
Fig. 4a shows the evolution of one of these intermetallic
particles subjected to the anodising process. The
composition of both regions of the particle was
determined by EDS (Fig. 4b). The analysis of the upper
part (1) showed the presence of oxygen and sulphur
2011 VOL 89 NO 6 315
 Gastón-Garcı́a et al. Sulphuric acid anodising of EN AC-46500 cast aluminium alloy

4 a SEM image of cross-sectional anodic alumina layer formed on EN AC-46500 aluminium alloy after anodising in
15 vol.-%H2SO4 electrolyte at 0uC and 5?0 A dm22 for 30 min. Highlighted area corresponds to partially anodised Al–
Fe–Si–Mn–Cr particle. b EDS spectrum from different regions marked in a (small Au peak is due to metallic gold that
was sputter coated on anodic alumina layer to reduce electrical charging during SEM measurements)

coming from the sulphuric acid electrolyte used for the Thickness
anodising process.3 Moreover, the constituent elements The way in which the anodising parameters affect the
of the polyhedrical particles were also detected (Al, Fe,
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thickness of the anodic films is shown in Fig. 5. In this

Si, Mn and Cr). The differences in the peak intensities
of the oxidised part (1) when compared with that of the
residual particle (2) suggests a Si enrichment and an
impoverishment of the rest of the alloying elements.
Similar results have been obtained for other aluminium
alloys.12,16,23
As was previously mentioned, two regions were
determined in the aluminium matrix, one more silicon
enriched than the other. After the anodising process, the
difference between the morphologies of both regions was
more accentuated, as can be observed in Fig. 4a. The
EDS analysis showed that the rougher areas (3)
presented higher silicon content than the smoother ones
(4). According to previous results,23,36 the presence
of these silicon particles may cause changes in the
distribution of the current in favour of less resistive
adjacent aluminium matrix. Consequently, the oxide
grows around the particle which remains trapped in the
anodic layer. Anodic oxidation of silicon particles seems
also to occur, although only partially and at a reduced
rate compared with the adjacent aluminium matrix.
sense, as expected, for the same temperature and
anodising time, the mean thickness of the oxide layers
increased with current density (Fig. 5a), as the effect of
increasing the current density is to speed up the rate of
growth. On the other hand, no differences were observed
among the average thickness values of anodic films
obtained from the two different electrolyte concentra-
tions studied. This would indicate that the efficiency of
the anodising process, from the electrochemical point of
view, was similar in both electrolytes.
The progress of thickness with time and temperature
effect is shown in Fig. 5b. The results showed that the
thickness of the layer increased with anodising time,
although this rise was enhanced when operating
temperature was lower. In fact, at a current density of
5?0 A dm22 and an anodising time of 120 min, it was
possible to obtain films with thicknesses superior to
100 mm at 25 or 0uC, while no more than 60 mm were
obtained at 20uC. The results indicate that there is a
balance between oxide film formation and its redissolu-
tion in the sulphuric acid electrolyte, and that this

a effect of electrolyte concentration and current density (at 0uC for 30 min); b effect of temperature and anodising time
(in 15 vol.-%H2SO4 electrolyte at 5?0 A dm22)
5 Thickness of anodic alumina layers formed on EN AC-46500 aluminium alloy after anodising under different conditions

316 Transactions of the Institute of Metal Finishing 2011 VOL 89 NO 6

 Gastón-Garcı́a et al. Sulphuric acid anodising of EN AC-46500 cast aluminium alloy

a effect of electrolyte concentration and current density (at 0uC for 30 min); b effect of temperature and anodising time
(in 15 vol.-%H2SO4 electrolyte at 5?0 A dm22)
6 Vickers microhardness of anodic alumina layers formed on EN AC-46500 aluminium alloy after anodising under differ-
ent conditions

controls the upper limit of thickness which can be vol.-%H2SO4 (Fig. 7), and, because of this, presented
produced under any particular operating conditions.37 higher microhardness values. The data also showed a
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small reduction in mean microhardness values as the

Mechanical properties of anodic oxide layers:
microhardness and wear resistance
Microhardness and wear resistance are intimately
associated with the rate of growth and the solvent
action of the electrolyte, which not only determine the
thickness of the coating but also its porosity, its
mechanical properties and its chemical composition.
Microhardness
Vickers microhardness values measured in the middle of
the cross-sectional anodic films and their corresponding
standard deviations are shown in Fig. 6. The results
showed that under the anodising conditions studied,
the microhardness values of the anodic oxide layers
obtained were superior to that of the aluminium
substrate (140¡10 HV0?0015).
However, some differences were observed as a func-
tion of the operating conditions. Thus, a slight decrease
in mean microhardness values with the increase in
the electrolyte concentration was observed (Fig. 6a).
This effect could be explained as a result of the differences
in the quality of the layers. Thus, anodic films obtained
at 5 vol.-%H2SO4 were more compact and with less
cracks, pores and defects than those obtained at 15
current density increased, especially at 8?0 A dm22, in
agreement with morphology results previously described
(Fig. 3b).
On the other hand, the effect of electrolyte tempera-
ture and anodising time on the microhardness of the
anodic layers obtained was also studied (Fig. 6b).
Similar results were obtained on anodising at 25 and
0uC, with higher microhardness values than those
obtained at 20uC. This behaviour is in agreement with
the literature38 where it is described that anodising
processes performed at temperatures near 0uC are
characterised by thicker oxide layers with lower porosity
and better microhardness values than those formed in
processes carried out at 18–22uC. The results also
showed that microhardness decreases when long anodis-
ing times were applied. Thus, there is a critical time for
each anodising condition and, exceeding it, the anodic
film growth can be slowed down or stopped and
chemical attack from the electrolyte may damage its
integrity.
In all the cases, the rather high relative standard
deviations of the hardness measurements reflect the
compositional and structural heterogeneity and non-
uniformity of the anodic oxide films.

a 5 vol.-%; b 15 vol.-%
7 Images (SEM) of cross-sectional anodic alumina layers formed on EN AC-46500 aluminium alloy after anodising in sul-
phuric acid electrolytes of different concentrations at 0uC and 5?0 A dm22 for 30 min

Transactions of the Institute of Metal Finishing 2011 VOL 89 NO 6 317

 Gastón-Garcı́a et al. Sulphuric acid anodising of EN AC-46500 cast aluminium alloy

9 Images (SEM) of top view of anodic alumina layer

a without mechanical pretreatment; b with previous
mechanical polishing
8 Voltage–time curves registered during galvanostatic ano-
dising of EN AC-46500 cast aluminium alloy in 5 vol.-
%H2SO4 electrolyte at 0uC and 5?0 A dm22 for 30 min
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formed on mechanical polished EN AC-46500 alumi-
nium alloy after anodising in 5 vol.-%H2SO4 electrolyte
at 0uC and 5?0 A dm22 for 30 min
Polished samples were submitted to the chemical
pretreatment and the anodising process. V–t transients
obtained during anodising of these surfaces (Fig. 8) showed

Wear resistance that polishing had an effect on the voltage evolution. Thus,
in comparison with non-polished surfaces, no changes on
Wear resistance of anodic layers formed under different
the voltage corresponding to region I were observed, as
experimental conditions was evaluated using a ball on
mechanical treatment does not modify the composition of
disc tribometer (Table 1). The results showed that at
the surface, and because of this, the effect of the air formed
5?0 A dm22 anodising current density, wear resistance
oxide film. However, a slight enhancement of the maximum
was improved with decreasing H2SO4 concentration,
corresponding to the breakdown of the barrier layer
temperature and anodising time. In all the cases, except
(y37 V) (region II) was observed, suggesting a more
at the highest anodising time studied (90 min), the wear
resistive behaviour associated with a higher thickness and/or
resistance was better than that of the substrate, which
compactness of the barrier layer.
indicates that the poor wear characteristics of EN AC-
The pretreatment of the aluminium surface also
46500 cast alloy can be improved by anodising under
influenced the morphology and structure of the resulting
certain experimental conditions.
AAOL. Thus, it can be seen (Fig. 9) that after me-
On the other hand, the results showed that, in
chanical pretreatment, more compact films with some
general, the wear rate of the films changed following the
3D structures were obtained. No cracks were detected
same tendency as the microhardness measurements.
and the roughness of the surface was lower than that of
However, in some cases, samples with similar micro-
non-polished samples (Table 2). However, polishing had
hardness values lead to different wear resistance re-
a negative effect on the efficiency of the process and
sponses. This could be attributed to the fact that the
films with ,50% of the thickness were obtained,
microhardness measurements were performed at micro-
indicating that current losses due to other processes,
scopic scale and therefore only local regions of the
such as oxide dissolution and/or oxygen evolution, were
anodic layer were evaluated. On the contrary, the
higher on the polished surfaces, probably due to changes
determination of wear resistance involves a bigger test
in the structure, thickness and reactivity of the barrier
area and as a result, the wear resistance values are
and porous alumina layer. Moreover, instead of what
mostly dependent on the presence of defects such as
was expected, compactness of the film did not lead to a
porous and cracks.
significant improvement in the film hardness and wear
resistance.
Mechanical pretreatment effect
In order to improve the quality of the anodic oxide
layers obtained, aluminium samples were submitted to a
Conclusions
mechanical polishing to a mirror-like finish before Sulphuric acid anodising of EN AC-46500 cast alloy
the chemical pretreatment. By the application of this was studied in order to determine the optimal experi-
polishing, the surface roughness Ra of the samples was mental conditions. The high content and variety of
reduced from 0?68¡0?02 mm (without polishing) to alloying elements were responsible for disrupting the
0?05¡0?01 mm (after mirror-like finish). classical porous morphology and changing the typical

Table 1 Thickness, microhardness and wear rate of several anodised samples

Operating conditions Thickness/mm Microhardness/HV K/61026 mm3 N21 m21

EN AC-46500 substrate … 140¡10 446¡20

5 vol.-%H2SO4, 0uC, 5.0 A dm22, 30 min 36.7¡3.2 370¡92 9¡2
15 vol.-%H2SO4, 0uC, 5.0 A dm22, 30 min 39.1¡3.3 319¡71 65¡13
15 vol.% H2SO4, 0uC, 5.0 A dm22, 90 min 90.5¡4.5 218¡52 587¡23
15 vol.-%H2SO4, 20uC, 5.0 A dm22, 30 min 30.5¡3.4 227¡44 95¡19

318 Transactions of the Institute of Metal Finishing 2011 VOL 89 NO 6

 Gastón-Garcı́a et al.
Table 2 Thickness, microhardness and roughness of
anodised samples after different pretreatments
(5 vol.-%H2SO4, 0uC, 5?0 A dm22, 30 min)
Pretreatment Thickness/mm Microhardness/HV Roughness/mm
Non-polished 36.7¡3.2 370¡92 1.42¡0.21
Polished 13.4¡1.9 437¡99 1.07¡0.07
voltage–time curves of the high purity aluminium.
During anodic oxidation, intermetallic particles with
different behaviours were found, mainly due to their
different oxidation rates compared with the aluminium
matrix. Some of them (such as Al–Cu particles) were
dissolved leaving hollows in the layer; whereas, others
(such as Al–Fe–Si–Mn–Cr) remained trapped into the
oxide film. The variation in the operating parameters,
such as sulphuric acid concentration, bath temperature,
current density and anodising time had a large influence
on the characteristics of the anodic layers. The increase
in any of these variables produced a decrease in the
mechanical properties of the layers and in some cases
even their complete deterioration. The application of a
Downloaded by [University of Montana] at 22:59 09 February 2016
polishing pretreatment modified the V–t transients
recorded and significantly improved the film appear-
ance, but decreased the process efficiency and did not
lead to an improvement in the film hardness. The best
quality anodic oxide films were obtained by anodising in
a 5 vol.-% sulphuric acid electrolyte, at 5?0 A dm22
during 30 min at 0uC. Under these experimental
conditions, oxide layers with good aesthetical appear-
ance, rather high thickness (y40 mm), elevated hardness
(y2?6 times higher than the base material) and low wear
rate (about two orders of magnitude lower than the base
material) were obtained.
Acknowledgements
This paper was partially supported by contract
MAT-2006-12913 from the MEC and FEDER. The
authors gratefully acknowledge financial support from
ANESDUR, S.L., Spain.
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