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Corrosion Science 43 (2001) 20932109

Eect of heat treatment on liform corrosion of

aluminium alloy AA3005
A. Afseth a,c,*, J.H. Nordlien b, G.M. Scamans c, K. Nisancioglu a

Department of Materials Technology and Electrochemistry, NTNU, N-7491 Trondheim, Norway

Department of Corrosion and Surface Technology, SINTEF, N-7465 Trondheim, Norway
Alcan International Limited, Banbury Laboratory, Southam Road, Banbury OX16 7SP, UK
Received 14 July 2000; accepted 4 January 2001

The eect of heat treatment on the liform corrosion (FFC) susceptibility of rolled aluminium alloy AA3005 at temperatures in the range 150500C is investigated. A drastic loss of
corrosion resistance takes place as a result of annealing at temperatures in excess of 350C.
TEM investigations revealed a highly deformed near-surface region, approximately 1 lm
thick, on the as-received material. The presence of this surface layer is caused by shear deformation of the surface region during rolling. The enhanced deformation undergone by the
surface layer promotes secondary intermetallic precipitation in this region during subsequent
heat treatment. The resulting microstructure, where the near-surface region contains a higher
density of ne intermetallic particles and lower solid solution levels of the more noble alloying
elements than the underlying bulk, results in preferential attack of this layer during corrosion
processes and is identied as the main cause of the observed loss of FFC resistance. 2001
Elsevier Science Ltd. All rights reserved.
Keywords: Aluminium; Filiform corrosion; Deformed surface layers,Thermo-mechanical processing

1. Introduction
Recent work has brought to attention the detrimental eect of high temperature heat treatment on the liform corrosion (FFC) resistance of several wrought
Corresponding author. Present address: Alcan International Limited, Banbury Laboratory, Southam
Road, Banbury OX16 7SP, UK. Tel.: +44-1295-452888.
E-mail address: (A. Afseth).

0010-938X/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
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A. Afseth et al. / Corrosion Science 43 (2001) 20932109

aluminium alloy systems [14]. In particular it was shown that a highly corrosionresistant, hard temper 3005 alloy becomes very susceptible to FFC after annealing for
2 h at 440C. The loss of corrosion resistance was attributed to changes in the
electrochemical properties of a thin layer of metal in the surface of the heat treated
material [14]. The mechanism of these changes brought about by annealing was not
established, but some signicant observations were made. The changes in the properties of the surface oxide as a result of annealing were not considered to cause the
increased FFC susceptibility. Furthermore, the near-surface of the rolled alloy sheet
was shown to exhibit a highly deformed, micrograined layer. It was necessary to
chemically remove, e.g., by etching, a surface layer, which had at least the same
thickness as the micrograined layer to obtain a surface resistant to FFC on the annealed material.
Localised corrosion of multiphase aluminium alloys with signicant levels of alloying/impurity elements is generally accepted to be controlled by microgalvanic
coupling phenomena between the aluminium rich matrix and intermetallic particles
[5,6]. Previous work relating electrochemical and corrosion properties to the substrate microstructure has highlighted the importance of intermetallic particle composition, distribution and levels of alloying elements in solid solution [58]. For 3000
series alloys, the eect of manganese in solid solution on the general electrochemical
and corrosion properties of the bare substrate is well known [6,911].
The aim of the present work has been to identify the factors responsible for the
drastic loss of FFC resistance of alloy AA3005 due to heat treatment. In particular
attention was given to the characterisation of microstructural changes in the bulk
and in the near-surface region as well as changes in the surface oxide as a function of
annealing temperature. An attempt is made to correlate these microstructural observations with measured corrosion properties. The electrochemical properties of the
surfaces under consideration are further elucidated in a related paper to obtain a
more complete understanding of the FFC mechanism on this material.
2. Experimental
2.1. Materials/materials characterisation
The material used was a commercial, DC-cast AA3005 alloy supplied as 0.67 mm
rolled sheet in extra hard (H19) temper. The chemical composition of the alloy, as
determined by spectrographic analysis, is reported in Table 1.
Panels of the material, 10  12:5 cm2 in size, were degreased in acetone prior to
annealing for 2 h at selected temperatures in an air circulation furnace, followed by
Table 1
Chemical composition of the alloy used in this study


















A. Afseth et al. / Corrosion Science 43 (2001) 20932109


air cooling. The total weight change as a result of annealing was determined. The
weight of the oxide formed was determined by lm stripping in a chromicphosphoric acid bath according to ASTM B137.
Thermoelectric power (TEP) measurements [12] were carried out on the dierent
substrate conditions to monitor changes in manganese solid solution levels in the
bulk of the material as a function of annealing temperature.
The composition of bulk intermetallic particles larger than 1 lm was determined
by semi-quantitative electron microprobe analysis (EMPA) of selected cross-sectional samples polished through 1 lm diamond paste. This analysis was performed
by scanning at least 10 selected areas of 200  200 lm2 near the centre of the sheet
The bulk and the near-surface structure of selected specimens were investigated
using SEM (JEOL JSM 820) and TEM (JEOL FX2000), both equipped with X-ray
EDS analytical capabilities. Bulk SEM samples were prepared by polishing crosssections through 1 lm diamond paste, while the surface and near-surface regions
were investigated on taper sectioned samples prepared by ultramicrotomy. Electron
transparent cross-sectional foils of near-surface material for TEM investigation were
prepared by using a ReichertJung Ultracut ultramicrotome and a diamond knife
2.2. Corrosion testing
FFC susceptibility was assessed by an accelerated laboratory test. Replicate
panels corresponding to each annealing condition were acetone degreased, followed
by wire-bar coating with a heat curing polyurethane coating. 1 An approximate dry
lm thickness of 15 lm was obtained. A 10 cm long scribe was made in the coating
45 to the rolling direction using a steel tipped scribing tool. The uncoated side and
the edges of the panels were protected with a transparent tape to avoid corrosion
other than from the applied scribe. Corrosion was initiated by immersing the scribed
panels in concentrated aluminium chloride 600 g=l AlCl3 for 2 h [2]. The samples
were then taken out, excess aluminium chloride solution on the panels was carefully
removed and the panels were placed in a constant humidity cabinet maintained at
40C and 82% R.H for 1000 h, the latter in accordance with DIN EN 3665.

3. Results
3.1. Filiform corrosion
Fig. 1 shows macrographs of corrosion tested panels after 1000 h of exposure
in the constant humidity chamber. The length of laments from the scribe and
the extent of underlm corrosion in general increased with increasing annealing

Coates Coating PCA 2209-002, Mjndalen, Norway.


A. Afseth et al. / Corrosion Science 43 (2001) 20932109

Fig. 1. Macrographs showing FFC morphology after 1000 h of exposure in constant humidity chamber.
(a) As-received sample and samples annealed 2 h at (b) 200C, (c) 300C, (d) 350C, (e) 400C and (f)

temperature. It can also be observed that a signicant change in the corrosion

morphology took place for samples annealed at temperatures in excess of 350C.
While the as-received sample exhibited well dened, individual lamental corrosion
attacks with a signicant lifting of the organic coating, the corrosion morphology of
the high temperature annealed samples was that of a uniform, broad front attack
from the scribe accompanied by very little lifting of the coating. The severe corrosion
attacks seen in Fig. 1(f) for the sample annealed at 500C was caused by coalescence
of laments and severe underlm corrosion near the scribe.
Fig. 2 shows the measured lament lengths as a function of annealing temperature. The reported lament length was determined as the average of the three longest
laments, measured perpendicular to the scribe on each of the replicate panels tested
for each annealing condition. The susceptibility to FFC increased gradually with
increasing annealing temperature up to 350C, followed by a drastic increase at
375C. Increasing the annealing temperature above 375C did not cause signicant
further increase in the corrosion susceptibility.
3.2. Corrosion morphology
The lament corrosion morphologies for 1000 h corrosion tested samples of the
as-received substrate, representative of highly corrosion-resistant surfaces, and material annealed at 450C for 2 h, representative of surfaces with poor corrosion resistance, were investigated in SEM after removing the organic coating and corrosion
products. Fig. 3 shows SEM micrographs acquired from dierent positions within a

A. Afseth et al. / Corrosion Science 43 (2001) 20932109


Fig. 2. Filament length as a function of annealing temperature after 1000 h of corrosion testing.

corrosion lament on the as-received substrate sample. The low magnication image
in the corner of Fig. 3(a) indicate the shape of the corrosion lament and the
positions where micrographs were acquired. The very tip of the lament head is
shown in Fig. 3(a), where the unexposed surface can be seen in the lower region of
the image. The majority of the surface area within the lament head was unaected
by corrosion and attacks were in the form of small, individual, crystallographic pits
with large, uncorroded areas in between. Further back in the lament, as shown in
Figs. 3(b) and (c), the crystallographic pitting was found to be enhanced around
larger, constituent intermetallic particles, while there were still uncorroded areas
visible. Similar corrosion morphologies have been reported by Leth-Olsen [1], and
are generally referred to as successive pitting corrosion.
SEM micrographs of the heat treated sample are given in Fig. 4. The lament
head is shown in Fig. 4(a), where the uncorroded surface can be seen on the left hand
side of the image. The mode of corrosion can be seen to dier signicantly from that
observed for the as-received sample with only a very supercial type of attack and no
localised corrosion pits. Throughout the corrosion aected area it was found that the
surface was uniformly and supercially etched. A surface layer of metal had been
dissolved and a high density of small intermetallic particles was left exposed in the
surface as seen in the right hand side of Fig. 4(a) and in more detail in Fig. 4(b).
Unlike the as-received sample, where extensive pitting was observed around larger
intermetallic particles exposed in the surface within the lament, no pitting attacks
near constituent intermetallics were seen for the annealed sample as shown in Fig.


A. Afseth et al. / Corrosion Science 43 (2001) 20932109

Fig. 3. Corrosion morphology of alloy 3005 in as-received condition after 1000 h corrosion testing. The
small, low magnication image shows positions where micrographs were acquired: (a) Area in the tip of
the lament head. The uncorroded surface can be seen in the lower end of the image, corrosion attacks are
in the form of individual pits. (b) Area in the body of the lament, extensive crystallographic pitting can be
seen as well as an area unaected by corrosion. (c) Enhanced pitting corrosion near constituent intermetallic particles.

3.3. Weight loss measurements

The weight change measured during annealing and the weight of the surface oxide
as measured according to ASTM B137 are plotted against annealing temperature in
Fig. 5. Annealing at the temperatures lower than 350o C caused an insignicant
weight change or a slight weight loss attributed to evaporation of rolling lubricants
not removed by the acetone degreasing practise. In this temperature range, only a
slight increase was observed in the amount of surface oxide formed. Above 350C a
signicant increase in the specimen and oxide weight was observed as a result of
increased surface oxidation.

A. Afseth et al. / Corrosion Science 43 (2001) 20932109


Fig. 4. Corrosion morphology of alloy 3005 annealed 2 h at 450C after 1000 h corrosion testing. The
small, low magnication image shows position where micrographs were acquired: (a) Area in tip of lament head. The uncorroded surface can be seen on the left hand side of the image, the corrosion front is
approximately in the centre of the image, (b) Area in the body of the lament. A high density of secondary
precipitates are exposed on a uniformly corroded area of the surface. (c) Slightly enhanced corrosion near
a larger, constituent intermetallic particle exposed in the surface.

3.4. Thermoelectric power measurements

The TEP relative to high purity aluminium measured for the dierent annealing
temperatures is given in Fig. 6. The main contribution to the observed changes in the
TEP of the present alloy comes from the changes in the level of manganese in solid
solution [1316]. Large negative TEP values correspond to high levels of manganese
in solid solution. The data in Fig. 6 indicate that precipitation of manganese bearing


A. Afseth et al. / Corrosion Science 43 (2001) 20932109

Fig. 5. Weight change during annealing and weight of oxide lm as a function of annealing temperature
for samples heat treated 2 h.

Fig. 6. Relative TEP of alloy AA3005 vs. super purity Al as a function of annealing temperature.

intermetallic phases took place at annealing temperatures P 250C. The sample

annealed at 300C had more manganese precipitated than the samples annealed at
temperatures in the range 325400C. A maximum amount of precipitated manganese was measured for the sample annealed at 450C. A similar temperature dependence of the precipitation kinetics of manganese bearing intermetallic particles
has been reported for cold worked AA3004 [17]. The reduced precipitation in the

A. Afseth et al. / Corrosion Science 43 (2001) 20932109


temperature range 325400C was attributed to the onset of recrystallisation restricting the precipitation process. For the sample annealed at 500C the solid
solution level of manganese was higher than that of the as-received material indicating redissolution of secondary precipitates.
3.5. Electron microprobe analysis and SEM observations
Intermetallic particles larger than approximately 1 lm were analysed by EMPA
on polished cross-sections of the as-received material and material annealed for 2 h
at 450C. Annealing had no signicant eect on the composition of the larger,
constituent intermetallic particles in the bulk of the samples. In both conditions
investigated, approximately 60% of the particles were (Fe,Mn)Al6 phase, and the
remainder were a-(Fe,Mn)3 SiAl12 phase, with an iron to manganese ratio in the
range 0.80.9 for both phases. In addition to the larger, constituent intermetallic
particles, the material investigated contained a high density of nely dispersed,
secondary precipitates with sizes in the range from a few ten nanometers to a few
hundred nanometers. These secondary precipitates were too small to be analysed by
EMPA. The size distributions of particles in the range 0.10.7 lm were measured
using images analysis of series of SEM backscatter images. As shown in Fig. 7, heat
treatment at 450C resulted in a signicant increase in the number density of the
smallest particles measured, with diameters in the range 0.10.2 lm. This result is in
accordance with the TEP measurements which also indicated signicant secondary
precipitation during heat treatment at this temperature. It should be noted that the
substrates investigated also contained precipitates smaller than 0.1 lm, but that these
were not detected by the technique used.
The surfaces and near-surface regions of the same two tempers were investigated
also by SEM using taper sectioned specimens shown in Fig. 8. The surfaces of the

Fig. 7. Size distribution of intermetallic particles in the size range 0.10.7 lm measured in bulk of samples
of alloy 3005 in as-received and annealed (2 h at 450C) conditions.


A. Afseth et al. / Corrosion Science 43 (2001) 20932109

Fig. 8. SEM backscatter images showing the near-surface regions of taper sectioned (a) as-received material and (b) sample annealed at 450C for 2 h. The sample surfaces are on the left edge of the images. The
lm bars correspond to approximate depth from the surface.

samples are on the left side of the images. SEM backscatter electron images reveal
larger, constituent intermetallic particles and a high density of ne, secondary precipitates. The larger intermetallic particles were generally smeared over by a layer of
aluminium metal close to the surface. In addition to the intermetallic particles it
is possible to observe the grain structure of the near-surface regions on the two
samples. The as-received sample had a highly deformed near-surface structure with
very small grains, while the sample annealed at 450C had a fully recrystallised
structure with grain sizes generally exceeding 50 lm.
Low energy EDS measurements of the surfaces showed a signicant magnesium
enrichment in the surface oxide of the annealed sample. In addition, the thickness
and composition of the oxide on the annealed sample was found to vary with
position. Fig. 9 shows EDS measurements acquired at an accelerating voltage of 3
keV for samples seen in Fig. 8. These measurements are useful for obtaining a
qualitative indication of the composition and relative thickness of the various surface
oxides. Fig. 9(a) shows a spectra acquired from an area on a freshly microtomed
section of the as-received sample, the low oxygen to aluminium ratio indicates a thin,
air-formed oxide lm. The higher oxygen signal for the as-received surface (Fig. 9(b))
indicates a thicker surface oxide than that on the microtomed section. No signicant
magnesium enrichment was detected. Fig. 9(c) shows the spectra acquired from an
area in the surface of the annealed sample, the oxygen signal was signicantly higher
than for the as-received surface and there was also a signicant amount of magnesium detected. Fig. 9(d) shows the spectra acquired from a point on the annealed
sample surface which appeared darker than the surroundings in the SEM backscatter
mode. The higher oxygen and magnesium signals indicate an area of a thicker and
more magnesium enriched oxide.

A. Afseth et al. / Corrosion Science 43 (2001) 20932109


Fig. 9. EDS spectra of alloy 3005 samples acquired in SEM at 3 keV for (a) freshly microtomed surface,
(b) as rolled surface, (c) surface of sample annealed for 2 h at 450C and (d) point analysis from region
with thicker oxide on annealed sample.

3.6. TEM observations

The near-surface microstructure of the as-received substrate and a sample annealed for 2 h at 450C was investigated on cross-sectional foils prepared by
ultramicrotomy. In the near-surface region of the as-cold-rolled material, shown in
Fig. 10(A), a layer with a very ne grain structure can be observed. The thickness of
this heavily deformed layer varied considerably along the surface investigated. On
the average, the thickness was about 1 lm, and it consisted of elongated aluminium
grains of 100400 nm in thickness. In the outermost part of the layer, even smaller
grains, <50 nm, together with mixed in oxide phases was observed. Annealing
caused general recrystallisation of the substrate. The heat treatment also caused
signicant surface oxidation. Fig. 10(B) shows the annealed specimen revealing a
fully recrystallised near-surface region with the thermally formed surface oxide. In
places where the micrograined surface layer contained incorporated oxide phases,
the ne grain structure was retained after heat treatment. Such an area is shown in
Fig. 11 together with EDS spectra from point analyses of phases labelled on the
micrograph. The metallic grain, A, contained only aluminium. The intermetallic
particle, B, contained Al, Si, Mn and some Fe indicating that it was a secondary
precipitated a-(Fe,Mn)3 SiAl12 particle. The surface oxide, C, was strongly enriched


A. Afseth et al. / Corrosion Science 43 (2001) 20932109

Fig. 10. TEM micrographs showing near-surface microstructure of (A) as-received sample and (B) sample
annealed at 450C for 2 h. Specimens cut parallel to rolling direction (RD).

Fig. 11. TEM micrograph and EDS point analysis from near-surface region of sample annealed for 2 h at

in magnesium. The incorporated oxide particle, D, also contained a signicant

amount of magnesium but less so than the surface oxide.

4. Discussion
In accordance with previous ndings [14], the present results indicate that high
temperature heat treatment of a cold-rolled, hard temper 3005 alloy result in a
drastic loss of FFC resistance. The increase in FFC was accompanied by a change in
the corrosion morphology from that of a successive pitting type of attack seen on the

A. Afseth et al. / Corrosion Science 43 (2001) 20932109


as-received substrate, to a highly supercial surface etching for the high temperature
annealed material. During annealing at elevated temperatures, there is general recrystallisation of the cold-rolled microstructure, secondary precipitation of manganese bearing intermetallic phases and signicant surface oxidation whereby a highly
magnesium enriched thermal oxide is formed.
Previous work in this laboratory has shown that changes in the properties of the
surface oxide by itself cannot explain the increased susceptibility to FFC for heat
treated materials [1,2]. Furthermore it was demonstrated that a signicant amount of
metal has to be removed from the surface, e.g. by etching, in order to restore a good
corrosion resistance for high temperature heat treated material. On the basis of these
results it was suggested that unidentied microstructural changes in a surface layer of
the metal occurred as a result of annealing, leading to increased FFC susceptibility.
This suggested active layer on the surfaces of annealed substrates exhibited also
signicantly dierent electrochemical properties from that of the bulk material. In
this work, we showed that a basic microstructural change resulting from annealing
is the precipitation of nely dispersed, secondary phases which are mainly of type
a-(Fe,Mn)3 SiAl12 . TEM investigations further conrmed previous ndings [1,4] that
the near-surface region of the as-received, hard temper material contains a heavily
deformed, micrograined surface layer. Heat treatment at 450C caused general recrystallisation of the alloy except for parts of the highly deformed surface layer,
where the very ne grain structure was retained due to pinning of grain boundaries
by incorporated oxide phases.
The presence of the heavily deformed, micrograined layer in the surface of rolled
aluminium sheet materials is attributed to enhanced shear deformation of the surface
region in the rolling process. A schematic illustration of the surface shear stress
through the roll gap is shown in Fig. 12. As the aluminium sheet enters the roll gap at
a lower speed than the linear peripheral velocity of the rotating rolls, friction between the sheet and the rolls causes the surface to be subjected to a high shear stress
in the rolling direction. As the sheet is reduced in thickness its speed increases in the
roll gap. After passing the neutral plane, where the speed of the sheet equals that of
the rolls as indicated in the gure, the sheet moves faster than the rolls. The shear
stress is thus reversed such that the surface layer is smeared in the direction opposite
to the rolling direction [18,19]. The very ne grain sizes observed indicate that the
amount of plastic deformation the surface undergoes is signicantly higher than that
experienced by the bulk of the material. Due to the enhanced plastic deformation,
work hardening renders the micrograined surface layers more brittle than the underlying bulk. As a result of repeated rolling passes the surface layers break-up and
become smeared over by softer, underlying metal, or they fold over and reweld to the
surface, thereby encapsulating the incorporated oxide phases. This suggested
mechanism for the formation of the micrograined layers would in principle apply
equally to hot and cold rolling processes. However, it is suggested that the highly
deformed surface region is created mainly during the high reduction passes in the hot
rolling steps of processing of the sheet material. The high magnesium content of the
observed incorporated oxide phases indicate that these were formed at elevated


A. Afseth et al. / Corrosion Science 43 (2001) 20932109

Fig. 12. Schematic illustration of surface shear stress distribution in the roll gap.

The presence of highly deformed, micrograined surface layers as a generic feature

of rolled aluminium sheet has recently been reported by Fishkis and co-workers [19]
along with a suggested mechanism for their formation which support the present
ndings. Analogies between the subsurface structure formed during rolling and well
characterised subsurface structures formed during other high shear deformation
processes, such as sliding wear of aluminium alloys [2023], were pointed out.
Recently, Forsyth [24,25] reported corrosion properties of such highly deformed
subsurface layers formed by surface shear deformation through sliding wear or
machining of dierent aluminium alloys. The deformed surface layers on precipitation hardened AlZnMg alloys became susceptible to preferential, supercial
corrosion attack. Corrosion did not take place if the material was solution heat
treated before deformation. A precipitation heat treated AlCuMgSi did not develop a similar sensitivity to preferential surface corrosion as a result of subsequent
deformation. The exact mechanism causing the preferential corrosion of deformed
surface layers on these substrates was not identied, but redistribution of intermetallic particles in the deformed layers was suggested as the main contributing
factor, also in support of the present results.
Interestingly, the eect of very large plastic deformation on the microstructure
and intermetallic particle distribution in aluminium alloys has recently been reported
for bulk deformed samples produced by equal channel angular extrusion or repeated
torsion straining [2629]. Very high strains resulted in aluminiumiron binary alloys
characterised by a micrograined structure with grain sizes comparable to those observed in the deformed surface layers in the present work. Furthermore, the solid
solubility of iron was increased by orders of magnitude beyond the equilibrium
values as a result of breaking up and redissolution of large, constituent FeAl3 intermetallic particles [28,29]. Large deformation and supersaturation of high levels of

A. Afseth et al. / Corrosion Science 43 (2001) 20932109


iron in solid solution signicantly increased secondary precipitation during subsequent heat treatment [29].
In the present work no dierences were detected in the solid solution content of
alloying elements between the highly deformed micrograined surface layer and the
underlying bulk material. However, due to the limitations of the EDS analytical
technique used, further work is required in this area. The TEP measurements showed
that the bulk of the as-received, hard temper material is supersaturated in manganese
and that precipitation of manganese bearing intermetallic particles happen at temperatures in excess of 250C, with a maximum near 450C. The eect of plastic
deformation on the precipitation kinetics of the manganese bearing phases a-(Fe,
Mn)3 SiAl12 and (Mn,Fe)Al6 has been previously documented [1216,30]. Increasing
amount of deformation reduces the temperature at which precipitation starts, and it
may increase the rate of precipitation at the given temperature by orders of magnitude [14,16].
On the basis of this information, it is apparent that the micrograined layers in the
surface of rolled sheet respond dierently to annealing than the less deformed, underlying bulk material. For a given high temperature heat treatment, the precipitation is expected to be more complete in the near-surface layer than in the bulk
material. Thus after heat treatment, the near-surface material will be more depleted
of alloying elements, particularly manganese, in supersaturated solid solution than
the underlying bulk material. A thin layer of purer, less noble aluminium matrix
is therefore formed in the surface, containing a large density of more noble intermetallic particles.
The particular microstructural dierences shown to exist between the near-surface
layer and the underlying bulk must be the cause of the increased FFC susceptibility
for annealed materials. As a result of the compositional dierences mentioned to
occur in the aluminium grains at the surface, the surface layer is expected to act
sacricial to the underlying bulk material in a corrosion process. The high density of
nely dispersed intermetallic particles in the surface layer provides both a larger area
for cathodic reactions to take place and a high density of potential corrosion initiation points in the surface layer. As a result, the surface layer is rapidly attacked
albeit supercially, causing extensive underlm corrosion, rather than the more localised, pitting type of corrosion seen for the as-received substrate. The directional
nature of the FFC attack is also attributable to the observed microstructural differences. The rolling induced surface deformation is highly directional, and the
heterogeneities in the micrograined layers which provide nucleation sites for subsequent intermetallic particle precipitation are generally aligned in the rolling direction, both as grain/subgrain boundaries or as strung-out clusters of ne second phase
debris. Certain areas of the sheet surface will probably also have undergone more
deformation than other areas due to local dierences in work roll surface condition,
lubrication conditions etc., resulting in bands or zones, aligned in the rolling direction, with dierent degrees of surface deformation. During subsequent high
temperature exposure intermetallic phases nucleate at heterogeneities in the alloy
microstructure, preferentially so in the more heavily deformed areas of the nearsurface region. The resulting microstructure consequently consists of zones aligned


A. Afseth et al. / Corrosion Science 43 (2001) 20932109

in the rolling direction with dierent distribution of intermetallic particles. During

FFC, the corrosion front will preferentially attack the most susceptible material, i.e.
the areas with the most cathodically active intermetallic particles and the lowest
manganese solid solution content. As these areas are aligned in the rolling direction,
the FFC also tends to proceed in the same direction.
The properties of the thermally formed surface oxide during annealing may also
contribute to the impaired corrosion properties. Magnesium oxides are less stable
than alumina in acid environments [31], and the magnesium enriched, partly crystalline oxide formed at elevated temperatures on AlMg alloys has previously been
reported to have reduced passivity compared to the amorphous alumina lm [32,33].
Magnesium enrichment of the oxide is further known to impair the adhesion between the substrate and organic coatings or adhesives [34]. The role of the thermally
formed oxide in the present context of materials and processes is discussed in separate papers [35].

5. Conclusions
(1) High temperature heat treatment causes a drastic loss of FFC resistance of
rolled AA3005 sheet material. There exists a critical temperature around 350C
above which severe corrosion will take place. Increasing the annealing temperature
above this threshold does not signicantly increase the amount of corrosion.
(2) The near-surface region of the as-received, hard temper material consists of a
highly deformed, micrograined structure. The thickness of the deformed layer is nonuniform, but generally in the order of 1 lm with grain sizes in the order of 50200
nm. The presence of the highly deformed surface layer is attributed to enhanced
shear strain of the near-surface region in the rolling process.
(3) During heat treatment at high temperatures, secondary precipitation of intermetallic particles is promoted by the high deformation undergone by the micrograined surface layer. This results in a microstructure where the surface layer is more
depleted of noble alloying elements and contains a higher density of nely dispersed
intermetallic particles than the underlying bulk material. It is believed that in a
corrosion process, this surface layer corrodes preferentially compared to the bulk
material, thus leading to a rapid, supercial etching of the surface and poor FFC

Andries Bosland at Alcan International is acknowledged for performing the
EMPA analysis. Financial support from the European Commission through the Brite
Euram programme, contract BRPR CT95 0083 is acknowledged. Finally, the support
of Alcan International is gratefully acknowledged.

A. Afseth et al. / Corrosion Science 43 (2001) 20932109



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