Materials and Corrosion 2009, 60, No. 6
200805097 415
The effect of heat treatment on the corrosion
behaviour of 319 aluminium alloy
The effect of various heat treatments on the corrosion behaviour
of 319 T1 cast aluminium alloy was investigated. From this alloy,
specimens were heat treated in T5, T6 and two steps solution heat
treatment T6 conditions and afterwards were subjected to electro-
chemical corrosion in a 0.1 M NaCl solution (pH 12). From the
1 Introduction
Aluminium alloys due to their light weight, physical and
mechanical properties, corrosion resistance and low cost
have been widely used in various technological and industrial
applications. However, in order to obtain the best possible
properties, the use of heat treatment after the casting
procedure is frequently essential. Some recent reports
concerning the heat treatments and technological properties
of 319 cast aluminium alloy (wt%: 89.5%Al-6.5%Si-4%Cu)
and other relative aluminium alloys are given below:
Sokolowski et al. [1] studied the effect of high temperature
solution treatment on the 319 aluminium alloy mechanical
properties. In particular they performed a two steps solution
treatment [2 h at 495 8C (first step), 4 h at 515 8C (second
step), quenching in water and ageing at 250 8C for 3 h] and
studied how this heat treatment affected the mechanical
properties of this alloy. They observed that 319 cast alloy
with two steps solution treatment, in comparison to T5 and
T6 treatments, had improved mechanical properties (hard-
ness > 98 HBN, yield point > 169 MPa).
Panagopoulos et al. [2] investigated the effect of laser
surface treatment on the corrosion behaviour of commer-
cially pure aluminium in a 0.5 M NaCl solution (pH 6), by
means of potentiodynamic corrosion. The laser used was a
pulsed KrF Excimer laser (l 248 nm, J 300 mj/pulse).
These investigators observed that the laser-treated specimen
had increased corrosion resistance as the corrosion potential
shifted to nobler values. This phenomenon was mainly
attributed to the formation of a passive anticorrosive film. On
the other hand, no passivity regions were observed for the as-
received specimens, whose corrosion rate remained approxi-
mately stable throughout the potentiodynamic experiments.
Afseth et al. [3] studied the effect of high temperature
annealing on the electrochemical behaviour of AA3005
wrought aluminium alloy in a sodium chloride solution.
These investigators observed that high temperature anneal-
ing resulted in microstructural changes of the surface layer of
AA3005 wrought aluminium alloy. In particular high

C. N. Panagopoulos, E. P. Georgiou, K. I. Giannakopoulos
Laboratory of Physical Metallurgy, National Technical Univer-
sity of Athens, Zografos, 15780, Athens (Greece)
E-mail: chpanag@metal.ntua.gr
www.wiley-vch.de/home/wuk 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/maco.
C. N. Panagopoulos*, E. P. Georgiou and
K. I. Giannakopoulos
above treatments, T5 heat treatment did not improve the corrosion
resistance of the as-received alloy in contrast to T6 heat treatment
which improved the corrosion resistance of the same alloy. How-
ever, two steps solutionizing T6 treatment showed the best cor-
rosion resistance of the aluminium alloy.
temperature annealing brought about secondary precipitation
of (Mn, Fe)3SiAl12 intermetallic phase and the formation of a
thin Al2O3 oxide film. These changes were found to improve
the anticorrosive behaviour of this alloy, since its suscept-
ibility to filiform corrosion was reduced considerably.
In this research investigation, 319 cast aluminium alloy
was heat treated in T5, T6 and two steps solution treatment
conditions. The effect of the above heat treatments on the
corrosion behaviour of the aluminium alloy in a 0.1 M NaCl
solution (pH 12) was examined. The above solution was
used since the aluminium alloy shows interesting corrosive
behaviour in strong alkaline solutions. It is well known that
aluminium and aluminium alloys are susceptible to corro-
sion, when immersed in alkaline solutions. However, such
solutions are frequently used for various industrial and
domestic purposes [4]. It is more particularly the case in the
food industry, where cleaning is carried out daily, with
solutions having a pH > 10.
2 Experimental procedures
The material used in this study was a 319 T1 cast
aluminium alloy ingot of hemispherical shape, which was
produced by die-casting procedures. Its wt% chemical
composition was 88.5% Al, 6.5% Si, 3.7% Cu, 1% Fe, 0.2%
Mn, 0.2% Ni and 0.1% Cr (wt%). From this material, alloy
specimens of 4 cm
2 cm
1 cm dimensions were made.
These specimens, before the heat treating procedures,
were polished with SiC papers having increasing finishes and
3 mm diamond paste. Afterwards the polished alloy
specimens were submitted to the following heat treatments:
T5, T6 and two steps solution treatment, in an automatic
furnace with Ar atmosphere. These treatments consisted of
the following steps:
T5: no solutionizing, no quenching, 8 h at 205 8C (ageing).
T6: solution treatment for 12 h at 515 8C, quenching into
water and ageing for 3 h at 155 8C.
Two steps solution T6 heat treatment: first step at 495 8C
for 2 h followed by a second step at 515 8C for 4 h, quenching
into water and ageing at 250 8C for 3 h.
The as-received and heat treated alloy specimens were
immersed in a Kellers solution (2 ml HF 3 ml HCl 5 ml
HNO3 190 ml H2O) for 2 min at 25 8C, in order to reveal
416 Panagopoulos, Georgiou and Giannakopoulos
their surface microstructure. Then, they were observed in a
Jeol 6100 scanning electron microscope (SEM), which was
connected with a Noran TS 5500 electron dispersive X-ray
analyzer (EDAX).
The roughness of each specimen was measured with the
aid of a Marr Perthen Profilometer. The roughness tests were
considered essential so as to ensure that the exposed surface
of the 319 cast aluminium specimens in the corrosive
medium was similar. Finally, from each specimen a 1 cm2
surface was selected for the potentiodynamic corrosion
experiments. The remaining surface of the specimens was
isolated with epoxy, in order to avoid direct contact with the
corrosive solution, apart from a small area which was
connected with the Potentiostat.
The potentiodynamic corrosion experiments were per-
formed with the aid of an EG&G potentiostatgalvanostat
instrument in a 0.1 M NaCl solution (pH 12). The pH of the
corrosion solution was adjusted by using quantities of
concentrated NaOH. A standard calomel electrode was used
as a reference electrode and a graphite electrode as a cathode.
The scan rate that was selected was 0.2 mV/sec and all
experiments were conducted without de-aeration. For the
study of the corrosion products a Siemens D 5000 X-ray
diffractometer with Cu Ka radiation (l  1.54 A), Cu filter
and a graphite monochromator were also used.
The values given for different parameters are the mean
value of five independent experiments.
3 Results and discussion
A typical structure of as-cast 319 T1 aluminium alloy
obtained from the SEM microscope is given in Fig. 1a. In this
Fig. 1. Microstructure of 319 aluminium alloy in: (a) as-cast T1 condition, (b) T5 heat treatment condition, (c) T6 heat treatment condition
and (d) in two steps T6 solution heat treatment
Materials and Corrosion 2009, 60, No. 6
figure, regions rich in silicon can be observed, which had a
dark colour and the shape of needles, the aluminium alloy
matrix and two different phases, one with light grey colour
and one with white colour. With the simultaneous use of the
EDAX spectrometer it was found that the light grey regions
were rich in iron and their chemical composition was in wt%
69.3% Al, 19.4% Fe, 8.6% Si and 2.7% Mn, while the white
regions were CuAl2 precipitates.
The difference between the heat treated and the as-cast
319 T1 aluminium alloys lies in the change of the form of the
CuAl2 precipitates. The CuAl2 precipitates in T5 treated
specimens did not possess a definite shape and were mainly
observed near the iron-rich regions, Fig. 1b.
After the T6 heat treatment, the aluminium alloy appeared
to have formed CuAl2 precipitates that had a cylindrical
shape and were spread throughout the surface of the alloy,
Fig. 1c.
The structure of the 319 alloy specimens with two steps
solutionizing T6 treatment bore great resemblance to those
which were T6 treated. However, the two steps solutionizing
process seems to result in a larger size of CuAl2 precipitates,
Fig. 1d.
By conducting potentiodynamic corrosion experiments in
the NaCl solution for the T1, T5, T6 and two steps solution
T6 treated specimens the potentiodynamic graphs in Fig. 2
were obtained.
As it can be observed, all specimens had exhibited
passivity areas during the anodic polarization periods.
For the as-cast 319 T1 aluminium alloy the anodic branch
of the polarization curve started at 1350 mV versus SCE
(open circuit potential), Fig. 2. When the anodic potential
reached a value close to 1150 mV versus SCE, the
polarization curve turned to passive region, which extended
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Materials and Corrosion 2009, 60, No. 6
Fig. 2. Potentiodynamic graph of 319 T1 as-cast, T5, T6 and two
steps solution T6 treated aluminium alloy in 0.1 M NaCl solution
(pH 12)
up to 500 mV versus SCE. During the passivity period it is
believed that that the grown alumina layer dissolves
uniformly (taking into account the pH of the solution).
However, after this electrochemical process pitting occurs
with repassivation up to the breakdown potential. Stable
growth of pits occurs at potentials higher than the breakdown
potential. Pitting was mainly brought about by the presence
of chloride ions in the solution.
According to McCafferty [5], the chloride ions of the
corrosive media are absorbed on the protective film of the
aluminium surface. Then, they penetrate the protective film
and interact with the underlying surface of bulk aluminium,
and dissolve local regions of aluminium, forming pits. In
addition, another mechanism has also been proposed for the
formation of pits on the aluminium surface. This mechanism
assumes that the chloride ions penetrate the protective film,
interact with other ions, forms atoms and molecules within
pockets, at the interface of aluminium alloy-oxide film.
These molecules acquire high pressure, which is able to
break the protective oxide film and escape to the solution [6].
For the next step of the pitting process, both mechanisms
assume repassivation of the pits by the concentrating electric
current, due to localized high electric field.
At 500 mV versus SCE, a breakdown potential was
observed. During this potential, the protective layer of 319
T1 cast aluminium alloy specimen was partially destroyed by
pitting and the polarization current acquired higher values.
After the heat treating treatments, significant changes,
concerning the corrosion behaviour of 319 T1 cast
aluminium alloy, were observed. The passitivity area of
the T5 treated aluminium alloy had been formed at 1200
mV versus SCE (Fig. 2) and extended up to 600 mV versus
SCE. The specimens which were treated in T6 conditions,
had formed a steady-state passive region from 1200 to
600 mV versus SCE and the two steps solution T6 treated
specimens from 1200 to 700 mV versus SCE, Fig. 2.
By comparing the potentiodynamic curves for the as-
received and heat treated aluminium specimens, it could be
said that all specimens exhibited passivity areas. In addition,
pitting and repassivation phenomena were evident in the
anodic branch of the potentiodynamic curves. However,
significant changes were observed in the passivity area, as
the breakdown potential was observed to decrease with heat
treatment procedure.
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Heat treatment and corrosion of 319 Al alloy 417
Table 1. Corrosion currents and potentials obtained from the
potentiodynamic curves (Fig. 2)
Alloy Corrosion Corrosion potential
current (mA) (V) versus SCE
319 T1 190 S1.31
319 T5 260 S1.38
319 T6 105 S1.29
319 with two steps 95 S1.30
solution T6 treatment
From the above curves, the corrosion current of each
specimen was obtained and presented in Table 1. By
comparing the corrosion currents, it is observed that the 319
cast aluminium alloys which had T6 and two steps
solutionizing T6 treatments had the smallest corrosion
current and therefore better anticorrosive resistance, in
comparison to the as-received and T5 treated 319 T1 cast
aluminium alloy specimens. Between the first two speci-
mens, the alloy with the two solutionizing steps had the most
increased anticorrosive resistance.
The corrosion potential versus SCE of each specimen was
also obtained, Table 1. By comparing the corrosion potentials
in Table 1, it could be observed that the as-cast specimens
and those treated in T6 and two steps solutionizing T6
conditions had similar corrosion potentials. However, T5
heat treated aluminium specimen had a more negative
potential, which means that it had slightly increased
tendency to be corroded in comparison with the specimens
having the other treatments. From this observation, the
corrosion potentials of the specimens were in accordance
with the obtained corrosion current densities.
In Fig. 3, a typical XRD diagram obtained from the
corrosive surface of 319 aluminium alloy specimen, with two
steps solution treatment, is presented. Hydrated aluminium
oxides were only identified on the surface film.
As no significant changes were observed in the rich in
silicon phases among the heat treated 319 cast aluminium
alloys, the increase in the corrosion resistance was believed
to have been caused by the increase in the amount of CuAl2
precipitates in the heat treated specimens.
Specifically, the as-cast and T5 treated 319 aluminium
alloys had a lower corrosion resistance, as the diffusion of
copper in the aluminium matrix was also lower, due to the
absence of solutionizing. In contrast, the specimens that were
heat treated in T6 and two steps solution treatment conditions
Fig. 3. XRD diagram of corroded 319 aluminium alloy with two
steps solution T6 heat treatment
418 Panagopoulos, Georgiou and Giannakopoulos
had a higher diffusion of copper in the aluminium matrix and
thus formed more CuAl2 precipitates during the ageing
process. The increase in the amount of CuAl2 precipitates
during the heat treatment process, as it was found earlier, is
believed to be responsible for the improved anticorrosive
behaviour of the alloy. The CuAl2 precipitates support the
block of the halide ions in the surface layers of the alloy and
thus hinder the corrosion process. It is also believed that the
corrosion susceptibility of the aluminium alloy is strongly
affected by the amount of dilute copper content in the
aluminium matrix. Liu et al. [7] observed that the increase in
copper concentration in the aluminium matrix led to
increased corrosion rates of aluminiumcopper alloys.
4 Conclusions
The study of the corrosion behaviour of 319 T1 cast
aluminium alloy after T5, T6 and two stage solution T6
treatment in a 0.1 M NaCl solution (pH 12) leads to the
following conclusions:
i. All the aluminium alloy specimens with the different
heat treatment procedures exhibited passivity areas in the
anodic branch of the potentiodynamic corrosion experi-
ments.
Materials and Corrosion 2009, 60, No. 6
ii. Solutionizing showed the highest corrosion resistance of
the aluminium alloy.
iii. Two steps solution T6 treatment is preferable to the
single step of T6 treatment which were used in this study,
since the alloy appears to have better corrosion
resistance.
5 References
[1] J. H. Sokolowski, M. B. Djurdjevic, C. A. Kierkus, D. O.
Northwood, Mater. Proc. Technol. 2001, 109, 174.
[2] C. N. Panagopoulos, D. Dimopoulos, A. Michaelides, 9th
International Symposium on Gas Flow and Chemical Lasers,
Crete, Greece, September 1992, pp. 687691.
[3] A. Afseth, J. H. Nordlien, G. M. Scamans, K. Nisancioglu,
Corros. Sci. 2002, 44, 145.
[4] G. Daufin, J. P. Labbe, J. Pagetti, Corros. Sci. 1977, 17, 901.
[5] E. McCafferty, Corros. Sci. 1995, 37, 481.
[6] C. B. Bargeron, R. C. Benson, J. Electrochem. Soc. 1980, 127,
2528.
[7] Y. Liu, M. A. Arenas, S. J. Garcia-Vergara, T. Hashimoto, P.
Skeldon, G. E. Thompson, H. Habazaki, P. Bailey, T. C. Q.
Noakes, Corros. Sci. 2008, 50, 1475.
(Received: June 6, 2008) W5097
(Accepted: August 1, 2008)
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