CHAPTER

Aluminium casting alloys

G.9
Chapter outline
9.1 Main aluminium casting alloys......................................................................................................526
9.2 Applications of aluminium casting alloys and corrosion resistance .................................................527
9.3 Corrosion resistance of aluminium casting alloys........................................................................... 528
9.4 Parameters governing corrosion resistance of aluminium casting alloys..........................................529
9.4.1 Metal source: primary or recycled metal .....................................................................529
9.4.2 Casting mode ...........................................................................................................529
9.4.2.1 Remark .............................................................................................................. 530
9.4.3 Metal quality............................................................................................................530
9.4.4 Modification of AleSi alloys ......................................................................................531
9.4.5 Influence of copper...................................................................................................531
9.4.5.1 Aluminiumesilicon alloys without copper ............................................................. 531
9.4.5.2 Aluminiumesiliconecopper................................................................................. 532
9.4.5.3 Aluminiumesiliconemagnesium.......................................................................... 532
9.4.6 Influence of iron.......................................................................................................532
9.4.7 Influence of other elements .......................................................................................533
9.5 Stress corrosion cracking resistance............................................................................................. 533
9.6 Filiform corrosion resistance.........................................................................................................534
References ..........................................................................................................................................535

From the very beginning of the ‘chemical’ production of aluminium in 1856, Saint-Clair Deville [1]
and Woehler [2] found that silicon is soluble in aluminium and that it is therefore possible to produce
an aluminiumesilicon alloy [3]. Between 1856 and 1886, a significant portion of the 2,000 kg of
average annual production of ‘chemical’ aluminium with the Saint-Clair Deville process was used by
silversmiths to make statuettes, art objects and jewellery (Fig. G.9.1). To harden the aluminium, sil-
icon, in particular, or copper, was added.
The industrial development of the aluminium foundry began in the early 1920s, once the
aluminiumesilicon binary diagram, the parameters of the aluminiumesilicon eutectic1 and the sodium
modification, patented by A. Pacz in 1921, were well understood. A 12 to 13 wt.% silicon alloy was
marketed under the brand name of ‘Alpax’2.

1
Silicon content 11.7 wt.%, 577
C.
2
In Germany this alloy was called ‘Silumin’.
Corrosion of Aluminium. https://doi.org/10.1016/B978-0-08-099925-8.00038-7
Copyright © 2020 Elsevier Ltd. All rights reserved.
525
526 Chapter G.9 Aluminium casting alloys

FIGURE G.9.1
Aluminium and gold bracelet, circa 1850, attributed to the French silversmith Honoré Séverin Bourdoncle
(1823e93). Paris, Les Arts Décoratifs, Musée des Arts Décoratifs.
Photo credit: ©Paris, Les Arts Décoratifs.

The rise of the automobile, from the 1920s onwards [4], led to the development of cast aluminium
alloys for engine parts: crankcases, cylinder heads, etc. [5]. The first studies of the corrosion resistance
of aluminium casting alloys began immediately [6].

9.1 Main aluminium casting alloys

The main aluminium casting alloys are listed in Table G.9.1 with their closest AA designations to the
EN 1706 standard compositions [7].3 Among aluminiumecopper alloys, AlCu4MgTi (204.0, 21000)
is the most common alloy. It is a structurally hardened alloy. It has poor corrosion resistance and
should not be exposed to bad weather or any other aggressive environment without protection.
Aluminiumesilicon (without copper) alloys with compositions close to that of the eutectic:
➢ AlSi12a (413.0, 44200) with Cu < 0.05 wt.% Cu;
➢ AlSi12b (413.0, 44100), with Cu < 0.15 wt.% Cu.
These alloys are widely used for fittings in the building industry, and in household appliances, since
they have good corrosion resistance.
Aluminiumesiliconecopper alloys, where the silicon content varies from 7 to 9 wt.% and that of
copper from 2 to 4 wt.%, such as AlSi6Cu (319.0, 45000), AlSi7Cu0.5Mg (45500), AlSiCu3 (333.0,
46200), AlSi9Cu3(Fe) (333.0, 46000), AlSi12CuNiMg (336.0, 48000), have high strength at room and
elevated temperatures [8]. They are widely used in the automotive industry: pistons, cylinder heads,

3
The correspondence between the EN 1706 and AA designations is established by comparing standardized compositions,
which may differ somewhat from one system to another.
 9.2 Applications of aluminium casting alloys and corrosion resistance 527

Table G.9.1 Extract of standardized compositions (wt.%)

Alloy Si Cu Mg Mn

EN 1706 AA

Chemical
symbol Numerical
(a)
AlCu4MgTi 4.2 0.15
21100 204.0 0.20 5.0 0.35 0.10
AlCu4MnMg 4.0 0.15 0.20
21200 206.0 0.10 5.0 0.50 0.50
AlSi7Mg03 6.5 0.25
42100 A356.0 7.5 0.05 0.45 0.10
AlSi7Mg06 6.5 0.45
42200 357.0 7.5 0.05 0.70 0.10
AlSi10Mg 43000 9.0 0.20
360.0 11.0 0.05 0.45 0.45
AlSi10MnMg 9.0 0,10 0.40
43500 365.0 11.5 0.05 0.60 0.80
AlSi12(b) 10.5
44100 B413.0 13.5 0.05 0.45 0.10
AlSi9Cu3(Fe) 8.0 2.0 0.15
46000 333.0 11.0 4.0 0.55 0.55
AlSi8Cu3 7.5 2.0 0.05 0.15
46200 333 9.5 3.5 0.55 0.65
AlSi7Cu3Mg 6,5 3.0 0.30 0.20
46300 320.0 8.0 4.0 0.60 0.65
AlMg3 2.5
51100 514.0 0.55 0.05 3.5
a
Ti 0.15 to 0.30.
Note: when only one value for the composition is given, this corresponds to the maximum concentration of the element.

heat exchangers, wheels, transmission housings, etc. Due to their copper content, these alloys do not
have sufficient corrosion resistance for use outside automotive (or industrial vehicle) applications.
Aluminiumesiliconemagnesium alloys including AlSi7Mg0.3 (A356.0, 42100), AlSi7Mg0.6
(357.0, 42200) and AlSi10Mg(a) (360.0, 43000) or AlSi10Mg(b) (360.0, 43100) are structural alloys.
They have many automotive, aeronautical and mechanical applications. They have excellent cast-
ability, good weldability and good resistance to corrosion. This is also true for 357.0 [9].
Aluminiumemagnesium alloys, including AlMg3 (514.0, 51000), have excellent corrosion
resistance and good anodizing properties. This alloy is used for the manufacture of decorative parts in
furniture and fittings.

9.2 Applications of aluminium casting alloys and corrosion resistance

The requirements in terms of corrosion resistance differ significantly depending on the sector of
application of aluminium casting alloys.
528 Chapter G.9 Aluminium casting alloys

In practice, it is necessary to distinguish the following areas:

➢ Automotive ‘under the hood’, i.e., parts used in the structure of engines, gearbox housings, etc. In
most cases, alloys from the aluminiumesiliconecopper alloys mentioned above are used. The very
long experience of these automotive applications with aluminiumesiliconecopper alloys shows
that the risks of corrosion have been controlled. The use of engine coolant is specially
conditioned with corrosion inhibitors to prevent corrosion of aluminium casting alloys (and
other steel, copper, etc. components);
➢ Other automotive parts such as suspension parts, AlSi7Mg0.3 wheels (A356.0, 42100), AlSi7Mg0.6
brake parts (357.0, 42200), ductile thin die-cast structural parts in AlSi10MnMg alloys (365.0,
43500) and AlMg5Si2Mn (512.0, 51500) are made of copper-free aluminiumesilicon alloys for
their good corrosion resistance (and their level of mechanical properties);
➢ Mechanical and aeronautic structural parts subject to stress. They are mainly manufactured with
aluminiumesiliconemagnesium alloys AlSi7Mg0.6 (357.0, 42200). The requirements mainly
concern pitting corrosion resistance and stress corrosion resistance;
➢ Various equipment that can be exposed outdoors: road signs, lighting, fittings, etc., either
aluminiumesilicon including AlSi12 (313.0, 44000), aluminiumesiliconemagnesium AlSi7Mg0.3
(A356.0, 42100) or aluminiumemagnesium including AlMg3 (514.0, 51100) is used mainly for
decorative furniture hardware and also fittings [10]. These parts are often the visible part of
equipment where appearance is important. As they are often exposed outdoors to various
atmospheres including the marine environment, they must have good resistance to pitting
corrosion, filiform corrosion and of course other forms of corrosion: stress corrosion, exfoliation
corrosion.
Based on the assumption that the multi-decadal experience has made it possible to choose the
appropriate aluminium casting alloys (including the way parts are produced) for automotive appli-
cations, the following comments mainly concern mechanical applications and various equipment. In
practice, the question of corrosion resistance arises when there is exposure to bad weather or contact
with water. The case of central heating radiators is an example.

9.3 Corrosion resistance of aluminium casting alloys

In aluminiumesilicon alloys, the main phases are the solid solution, primary silicon and secondary
precipitates such as AlFeSi, AlFeSiMg, AlFeSiMn and Mg2Si. Silicon has an open circuit potential
(OCP) of e0.260 mV SCE and is cathodic compared to a solid solution. Nevertheless, the risk of a
galvanic couple is low because of the polarization of Si particles [11].
The b-AlFeSi phase is nobler than the matrix. In aqueous media, the metal is susceptible to
localized corrosion, but the addition of manganese reduces the cathodic effect of iron and therefore the
risk of galvanic corrosion [12].
Mg2Si has an OCP of 1,200 mV SCE and is anodic with respect to the matrix. There is therefore
the possibility of localized corrosion of Mg2Si particles with formation of SiO2 and MgO oxides.
These oxides cover the particles and slow down further corrosion [13].
 9.4 Parameters governing corrosion resistance of aluminium casting alloys 529

Experience shows that copper-free aluminium casting alloys generally have better pitting corrosion
resistance than wrought alloys processed by rolling or extrusion. This would be due to the fact that the
oxide film of the ‘foundry skin’ is more resistant than that of wrought semi-finished products.
Further, it is often found that the machined parts of a casting are more susceptible to pitting
corrosion than the rest of the unmachined surface. On the machined surfaces, the original casting skin,
formed at high temperature during the solidification of the liquid metal, has been replaced by an oxide
film formed at room temperature during machining.
In general, copper-free siliconealuminium casting alloys with or without magnesium have very
good resistance to atmospheric corrosion. The depth of pitting on these alloys does not exceed 200 mm
after 10 years of exposure in a marine or industrial atmosphere [14,15].

9.4 Parameters governing corrosion resistance of aluminium casting

alloys
The corrosion resistance of aluminium casting alloys depends on several parameters:
➢ Metal source e primary or recycled metal;
➢ Casting mode;
➢ Metal quality;
➢ Modification route used for aluminiumesilicon alloys;
➢ Copper content;
➢ Iron content.

9.4.1 Metal source: primary or recycled metal

One of the advantages of aluminium is its ability to be recycled. The majority of automotive parts
made of aluminiumecopper alloys are made from ‘secondary’ recycled metal. All other things being
equal, the composition of impurities such as Fe, Cu, Zn, Pb, Sn, etc. is always higher in recycled metal
than in primary metal. Higher levels of impurities result in a weakening of the corrosion resistance of
recycled aluminium casting alloys, the adhesion of decorative or protective coatings, and their service
life. Hence recycled metal may be insufficient for applications exposed to the weather.

9.4.2 Casting mode

Conventional casting processes such as sand, shell and pressure casting do not make any significant
difference to corrosion resistance.
New ‘semi-solid metal’ casting processes have been developed since 1980 [16]. They are used to
manufacture near net shape products. There are two such processes:
➢ Thixocasting from a billet of solid metal with a globular microstructure reheated into the semi-
solid range followed by a forming process such as high-pressure die casting;
➢ Rheocasting, the semi-solid metal slurry is prepared directly from the liquid [17].4

4
Thixocasting and rheocasting processes were very common in the 1990s but are almost no longer used.
530 Chapter G.9 Aluminium casting alloys

80

Corrosin current density (PA.cm–2)

70 Gravity cast

60
Rheocast
50
40
30
Thixoform(600°C)
20
Thixoform(590°C)
10
0
0 1 2 3 4 5
Ac/Aa

FIGURE G.9.2
Local galvanic corrosion current density between silicon particles and the eutectic aluminium phase in
gravity-cast, rheocast and thixoformed A356 alloy.
From Tahamtan and Fadavi Boostani [20].

Surface potential maps by scanning Kelvin probe force microscopy reveal that on the AlSi7Mg0.3
(A356.0, 42100) alloy, cast by rheocasting, intermetallics and silicon particles have a smaller potential
difference compared to the matrix than on the same alloy gravity cast [18]. According to Arrabal [19],
this is due to the globular form of the a-phase precipitates and the refinement of iron- and silicon-
bearing intermetallic particles, promoted by the rheocasting process. The refined morphology of sil-
icon particles in this rheocast alloy facilitates the formation of a homogeneous passive film and the
rapid repassivation of the metal.
According to Tahamtan [20] and Yu [21], the thixoforming process improves pitting corrosion
resistance and stress corrosion of aluminiumesiliconemagnesium alloys. This is because there is a
reduced area ratio between noble silicon particles and the less noble eutectic phase (Fig. G.9.2).

9.4.2.1 Remark
According to Goulart [22], it does not appear that the corrosion resistance of aluminiumesilicon alloys
is systematically improved by a fine structure. Further, the coarser dendritic structures tend to improve
corrosion resistance of the hypoeutectic Ale9 wt.% Si alloy and that this is associated with the
morphology of the interdendritic eutectic mixture.

9.4.3 Metal quality

The pitting corrosion resistance of aluminium casting alloys depends on the quality of the metal, in
particular the presence of porosity. On aluminiumesilicon alloys immersed in natural seawater for
69 days, Bjorgum observed that in porous specimens the depth of pitting corrosion varies from 0.1 to
1 mm while, without porosity, the pitting depth reaches less than 50 mm [23]. Porosities are micro-
cavities in which humidity can stagnate, thus constituting favourable conditions for corrosion.
 9.4 Parameters governing corrosion resistance of aluminium casting alloys 531

FIGURE G.9.3
Weight loss in 4% acid sulphuric aqueous solution versus modification with 80 ppm Na and 290 ppm Sr.
From Liao et al. [24].

9.4.4 Modification of AleSi alloys

The results of Liao’s laboratory tests [24] show that there is a clear difference in corrosion sensitivity
between sodium and strontium modifications, which is more favourable to the latter (Fig. G.9.3). The
explanation for this significant difference lies in the orientation of the a-Al dendrites parallel to the
direction of heat flow with strontium, whereas they are, on the contrary, disoriented with sodium
modification. With strontium, the attack in acid solution spreads in the form of finer pits, whereas they
are larger, and in particular, branched, on the sodium-modified alloy.

9.4.5 Influence of copper

As with wrought aluminium alloys, copper in solid solution has no influence on the corrosion resis-
tance of aluminiumesilicon casting alloys [25].

9.4.5.1 Aluminiumesilicon alloys without copper

On these alloys, the addition of copper causes the precipitation of the q-phase Al2Cu at grain
boundaries, which increases with copper content. A continuous network on grain boundaries can occur
[26]. As shown in Fig. G.9.4, the addition of copper in an aluminiume12 wt.% silicon alloy reduces
the evolution of hydrogen during etching in an acid solution (0.1 M HCl þ 0.1 M H2SO4) compared to
the copper-free alloy. According to Zor [27], this is due to the fact that the addition of copper induces a
tendency towards intergranular corrosion to the detriment of generalized corrosion on this type of
alloy.
532 Chapter G.9 Aluminium casting alloys

Al–Si
Al–Si + 1% Cu
Al–Si + 5% Cu

t (hours)

FIGURE G.9.4
Evolution of hydrogen by the corrosion of an Ale12Si alloy as a function of copper content.
From Zor et al. [27].

The compilation of long-term exposure results under natural atmosphere or accelerated salt spray
tests shows that the upper copper concentration limit, tolerable for corrosion resistance, is about 1
wt.% [28e30].
The addition of copper has no significant impact because the corrosion remains very superficial and
does not spread in the form of intergranular corrosion. The addition of up to 1.4 wt.% copper and up to
0.80 wt.% zinc has no influence on the corrosion resistance in water of an aluminiume12 wt.% silicon
recycled metal alloy for the manufacture of central heating radiators.

9.4.5.2 Aluminiumesiliconecopper
The sensitivity to stress corrosion cracking on these alloys disappears with overaging at 210
C, and the
corrosion then becomes transgranular [31].

9.4.5.3 Aluminiumesiliconemagnesium
According to Richard [32], up to 0.20 wt.% copper has no influence on the corrosion resistance of
AlSi7Mg0.3 alloys (A356.0, 42100). At a copper content of 0.50 wt.%, AlSi7Mg0.6 alloys (357.0,
42200) are highly sensitive to stress corrosion in the underaged T64 temper but less so in the T6 temper
or in the overaged T7 temper. According to Meynet [33], the limit can be increased to 0.45 wt.% on
AlSi9Mg alloys (365.0, 43300).

9.4.6 Influence of iron

Iron is the most problematic impurity in recycled metal alloys because it forms brittle intermetallics
such as b-Al5FeSi, which are all the more numerous when the iron content is high. In addition, the
 9.5 Stress corrosion cracking resistance 533

Table G.9.2 Influence of elements on corrosion resistance of aluminiume12wt.% silicon alloys

Element Tolerance limit (wt%) Remark

Antimony (Sb) No effect <1.5 wt.%

Boron (B) No significant influence with the Used as grain refiner
amount added
Beryllium (Be) No effect from 0.003% to 0.025 Restrains reaction between molten
wt.% metal and moisture in casting sand
with aluminiumemagnesium alloys
(50000)
Cadmium (Cd) No effect <0.5 wt.%
Lead (Pb) No effect Improves machinability of
heat-treatable alloys
Manganese (Mn) No effect
Nickel (Ni) Noticeable effect even with small
quantities
Phosphorus No effect <0.002 wt.%
Tin (Sn) Noticeable effect even with small
quantities, more than Ni
Titanium (Ti) Beneficial effect Grain refining element
Zinc (Zn) No effect <2 wt.%

increase in iron content has the effect of modifying the solidification temperatures of iron-based in-
termetallics in AlSi7Mg0.3 alloys (A356.0, 42100). This is also true for copper [34].
Corrosion is initiated at the intermetallic iron/silicon particle interface and therefore progresses
through the surface of the eutectic while the primary grains of the a solid solution are only slightly
attacked [35]. A more homogeneous distribution of the second-phase particles in the matrix of 360.0 as
well as refinement and eutectic silicon improves the corrosion resistance of iron-containing alloys [36].
It is generally accepted that up to about 1 wt.% iron has no influence on the corrosion resistance of
aluminiumesilicon alloys [37].

9.4.7 Influence of other elements

From long-term tests in a natural atmosphere and salt spray tests, Cozens [29] studied the influence of
several impurities or voluntary additions on the corrosion resistance of an aluminiume12wt.% silicon
alloy. The results are shown in Table G.9.2.

9.5 Stress corrosion cracking resistance

According to Speidel [38], aluminiumesiliconemagnesium alloys as well as aluminiumemagnesium
alloys have excellent stress corrosion resistance.
534 Chapter G.9 Aluminium casting alloys

Lifetime (hours)
1 000

500

100

50

20

20 120 140 160 180 200

Natural ageing Artificial ageing temperature (°C)

FIGURE G.9.5
Influence of ageing temperature on SCC resistance for an A-U5GT alloy.
From Garat [39].

Aluminiumecopper alloys have many similarities with wrought alloys:

➢ The propagation of stress corrosion cracking is intergranular;
➢ The high content of certain alloying elements such as zinc, magnesium and copper, separately or
together, sensitizes the cast alloys;
➢ Silicon-containing and overaged copper-containing alloys have excellent resistance to corrosion
and stress corrosion;
➢ Residual or sometimes in-service stresses are the main cause of stress corrosion.
The addition of copper sensitizes casting alloys to stress corrosion as shown by Garat [39] for
AlCu4MnMg (206.0, 21200) (Fig. G.9.5) in 80% Rp0.2 stress tests in a 1 M NaCl solution. Corrosion
resistance is minimal in the T7 temper and maximal in the naturally aged T4 and overaged T7 states.

9.6 Filiform corrosion resistance

While many long-term tests have shown that the addition of up to 1 wt.% copper has no significant
impact on the corrosion resistance of aluminiume12 wt.% silicon alloys, nor on their mechanical
properties, the same cannot be said for the resistance of protective and/or decorative coatings. The
current trend is to use recycled alloys, therefore enriched with copper, in particular to manufacture
lighting equipment and for railings. Experience shows that decorative coatings have very poor
adhesion and are quickly removed by the underlying surface corrosion of the metal. In other words, it
 References 535

Table G.9.3 Effect of copper and iron on filiform corrosion performance

Number of filaments Maximum filament Average filament
Iron wt.% Copper wt.% per 10 cm of scribe length (mm) length (mm)

0.10 0.007 9 0.6 0.3

0.10 0.015 10 0.4 0.2
0.20 0.014 37 2.0 0.6
0.15 0.090 65 3.3 1.8

From Courval GJ, Chamberlain B, Pattemore D. Effects of alloy composition and condition on filiform corrosion performance of cast
aluminum wheels. SAE Technical Paper 970021.

seems very difficult to expect good performance of coatings on parts cast with aluminiume12 wt.%
silicon containing copper. It is therefore necessary to use primary metal, without copper, for this type
of application.
According to Courval [40], copper has a very strong influence on the filiform corrosion resistance
of AlSi7Mg0.3 alloys (A356.0, 42100). The critical threshold is 0.10 wt.% when the iron content is
0.15 wt.% (Table G.9.3).

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