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C O R R O S I O N B E H AV I O U R O F A L U M I N I U M
IN MARINE ENVIRONMENTS
2. Corrosion behaviour of aluminium under control of the natural film of oxide . . . . . . . . . 148
145
10. CORROSION BEHAVIOUR OF
MARINE ENVIRONMENT is Based on our very long experience perhaps to prevent disappoint-
T HE
highly aggressive towards
most materials, as amply demons-
of aluminiums corrosion behaviour
in marine atmospheres and in sea
ments and avoid unnecessary
protection.
trated by the dilapidated state of water [1], we can now assert that
old ships and wrecks (whether the service life of aluminium in Even though, around the middle
made from wood or steel) that can marine environments will be excep- of the 20th century, metallurgists
be seen lying abandoned around tionally long and can be measured and corrosion specialists per-
our coasts. in decades!!! We can truly claim fected alloys that are intrinsi-
that aluminium is the metal of the cally resistant to corrosion in
There are few metals capable of sea of the modern age. marine environments the alu-
withstanding this hostile environ- minium-magnesium alloys that
ment unprotected. Bronze is one Although this evidence is now belong to the 5000 series cases
of these metals, and in museums widely accepted, the issue of the of corrosion still occur now and
around the Mediterranean we may resistance of aluminium to corro- then. An examination of these
admire statues recovered from the sion in marine applications is cases shows that very often the
ancient wrecks which they once important enough to merit a cause of the corrosion lies in the
adorned and which have lain sub- digression of some length and design of the structure and in
merged in the sea for centuries, detail to review a number of service conditions to which alu-
even millennia. basic principles and in doing so minium is not suited.
TRICAT 50
Alcan Marine
146
ALUMINIUM IN MARINE ENVIRONMENTS
in the southern hemisphere have course the polluting elements
1. a virtually uniform total salinity, modify the corrosivity of sea water
CHARACTERISTICS 32 to 37 g.l-1, including 30 g.l-1 of vis vis aluminium (2).
OF MARINE sodium chloride or salt.
ENVIRONMENTS The salinity of enclosed or isolated
seas can be very different from 1.2
A distinction must be made that of the great oceans, and may Sea atmosphere
between sea water and sea vary seasonally down the year. The The aggressive nature of sea air is
atmosphere. Baltic for example has a total salin- aggravated by moisture and sea
ity of 8 g.l-1, the Black Sea 22 g.l-1, spray consisting of very fine dro-
the Mediterranean 41 g.l-1 and the plets of sea water borne on the
1.1 Persian Gulf 57 g.l-1 [2]. wind. The effect of sea air depends
Sea water on the direction and strength of
The sea is a liquid medium that The hostility of sea water to met- the prevailing winds, and is greatly
contains the following substances als and other materials is due to its diminished at a distance of a few
in equilibrium: abundance of chlorides Cl-. kilometres inland.
dissolved mineral salts, some
30 to 35 g per litre, Experience and the results of cor-
dissolved gases, including 5 to rosion tests show that alu-
8 ppm (1) oxygen, miniums resistance to corrosion is
living organisms, the same whatever the sea or
decomposing organic matter, ocean. Comparative tests carried
mineral matter in suspension. out on the same alloys submerged
in the North Sea (16 to 17 g.l-1 chlo-
This mix forms a very complex rides, annual temperature variation
medium in which the influence of 0 to 18C) and the Arabian Gulf
each individual factor, whether (26 to 34 g.l-1 chlorides, annual (1) ppm = parts per million or mg.l-1.
chemical (composition), physical temperature variation 17 to 30C) (2) The diluted sea water in river
estuaries is usually more aggressive
(temperature, pressure) or biologi- show that there is no significant
to materials, including aluminium,
cal (flora and fauna), on the resist- difference between the two sites than water off shore. This paradox
ance to corrosion of metals can be despite their difference in salinity can be explained in various ways: the
precipitations of calcium and magnesium
neither truly isolated nor sepa- (ratio of 1:2) [3].
carbonate which deposit a more or less
rately quantified. protective film on the metal do not occur
The corrosion behaviour of alu- in diluted sea water. Biological activity
is slower. Domestic or industrial wastes
The great oceans the Atlantic, minium may change when the
modify physical-chemical balances
the Indian and the Pacific water in a port is polluted by urban and may themselves contain corrosive
which connect with one another or industrial waste, provided of agents.
LIVING QUARTER
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147
2. 3. 4.
CORROSION INFLUENCE INFLUENCE
BEHAVIOUR OF THE PH OF ALLOYING
OF ALUMINIUM ELEMENTS
UNDER CONTROL The rate of dissolution of the oxide
OF THE NATURAL film is determined by the pH of the Some alloying elements of alu-
FILM OF OXIDE environment (figure 123). It is very minium alloys actually reinforce
fast in acid and alkaline media and the protective character of the nat-
Aluminium owes its excellent cor- slow in media that are close to pH- ural oxide film, while others
rosion resistance to the presence neutrality (pH 5 to 9). The oxide weaken it. The former include
on the metal of a permanent film film is therefore very stable in sea magnesium, whose oxide (magne-
of natural oxide that consists of water whose pH is 8 8.2. sia) combines with the alumina to
alumina (Al2O3) and makes the enhance the protective properties
metal passive to the environ- Contrary to widespread belief, the of the natural oxide film, account-
ment. pH is not the only criterion that ing for the remarkable corrosion
must be taken into account when performance of magnesium alloys
Although it is extremely thin, predicting the behaviour of alu- in the 5000 series: 5754, 5083,
between 5 and 10 nanometers (3), minium in an aqueous environ- 5383, 5086 etc.
the oxide film forms a protective ment the nature of the acids or
barrier between the metal and the bases also plays an essential part. Copper on the other hand is one of
surrounding environment as soon This is very important when the elements that weaken the pro-
as the metal comes into contact selecting a cleaning or pickling tection provided by the oxide film,
with an oxidizing medium such as product for aluminium. which is why the use of copper
atmospheric oxygen or water. The aluminium alloys in the 2000
film forms within about one thou- Thus while hydrogen acids such as series and those belonging to the
sandth of a second and can even hydrochloric and sulphuric are very 7000 series with added copper is
form under oxygen pressures as aggressive towards aluminium not advisable in marine applica-
low as 1 millibar. (the more so in a strong solution), tions unless special protection is
concentrated nitric acid has no provided.
The physical-chemical stability of effect on aluminium (4) and can be
the oxide film is therefore key to used in concentrations stronger
aluminiums resistance to corro- than 50% to pickle aluminium and
sion, and depends on the charac- its alloys. Organic acids only have
teristics of the environment, such a very moderate action on alu-
GANGWAY
as its pH, and on the composition minium.
of the alloy itself.
This is equally true in alkaline envi-
ronments caustic soda and
potassium attack aluminium
fiercely, whereas the effect of con-
SOLUBILITY OF ALUMINA centrated ammonia is much less
severe. The same applies to
pH of sea water organic bases.
Log (V)
mg.dm-2.h-1
1
-1 Alkaline
dissolution
-2 in AlO2-
Acid
Alcan Marine
-3 dissolution
in Al3+
(3) 1 nanometer = one thousand
0 2 4 6 8 11 12 14 millionth of a metre (10-9 m).
(4) Its oxidizing function even reinforces
148 the oxide layer very slightly.
Figure 123
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS
type of corrosion. Oxide
3+
Al
Alcan Marine
Al3Fe
3 e- 3 e-
149
Figure 124
This slowdown in the rate of pit- It is invisible to the naked eye, and
ting corrosion explains the fact 5.3 micrographic examination is
that aluminium equipment can be Transcrystalline needed to detect it, usually with a
used for decades in certain natural corrosion and magnification of 50. When it pene-
environments (country air, sea air, intercrystalline trates deep into the metal it
sea water) without any protection. corrosion affects its mechanical properties,
This applies as much to sea air Corrosion inside the metal, at especially elongation, and can
(figure 125) as it does to immer- grain level, can spread in two ways even cause component failure.
sion in sea water (figure 126). In (figure 127):
both cases the pits are rarely in all directions: corrosion Intercrystalline corrosion spreads
deeper than one millimetre even affects all metallurgical consti- from pits. There is no correlation
after several years. tuents indiscriminately, it is not between the depth to which inter-
selective. This is transgranular or crystalline corrosion penetrates
transcrystalline corrosion, so cal- and the diameter of the corrosion
led because it spreads inside the pits. In other words, intercrystalline
grains, corrosion can spread in depth from
along preferential paths: corro- very small superficial pits.
sion spreads along the grain boun-
daries. Unlike transgranular corro- Intercrystalline corrosion is caused
sion, this type of corrosion consu- by the difference in electrochemi-
mes very little metal. cal potential that can exist
between the actual grain and the
grain boundary zone where inter-
metallic compounds, such as the
Al3Mg2 phase for magnesium
SEA SHORE EXPOSURE
alloys, can precipitate. The dissolu-
tion potential of this intermetallic
800 Depth of pits is very electronegative: -1150 mV
(microns) SCE (saturated calomel electrode)
600 compared with the grain: -750 mV.
the number of grain layers that are process, rates of work hardening
affected by it, and it is accepted and the elongated texture of grains).
that intercrystalline corrosion is In the aluminium-magnesium
superficial and harmless when it alloys (5083, 5383, 5086 etc.), the - 800 mV Air
does not spread beyond 3 or 4 lay- H116 temper, examined with the
ers, as is observed in the alloys of ASSET test (5), is immune to this
the 6000 series. type of corrosion.
- 980 mV Water
The sensitivity of aluminium alloys which is anodic and therefore cor- aeration, is due to the difference in the
to this very characteristic form of roded [4]. concentration of oxygen between the
layer of water that is in direct contact
corrosion (figure 136, p. 162)
with air which is therefore richer in
depends on the production condi- Aluminium and its alloys are oxygen and the layer beneath.
tions (the rolling or extrusion largely immune from this form of Corrosion occurs below the waterline. 151
5.6
Crevice corrosion
6. 6.1
The galvanic cell
BIMETALLIC
Crevice corrosion, also known as CORROSION When two dissimilar metals or
deposit attack, occurs in tiny alloys such as copper and zinc are
recesses beneath deposits where For a long time, the often exagger- placed in direct contact (or are
water penetrates but is not ated fear of bimetallic corrosion electrically connected) in a wet
refreshed (figure 129). impeded growth in the use of alu- and electrically conductive envi-
minium, both in naval construction ronment, e.g. a sulphuric acid
The spread of crevice corrosion in and in coastal equipment. solution, one of the two metals, in
aluminium is usually minimal, due this case zinc, will dissolve while
no doubt to the precipitation of Today, after many years of experi- the other, copper, retains its
alumina a product of corrosion ence with the use of aluminium in integrity and appearance.
which quickly seals off access to marine environments, we can
the crevices. When a bolted or riv- properly assess and quantify the This is a battery (7) (or galvanic cell)
eted joint that has been immersed risks of bimetallic corrosion of alu- consisting of two electrodes, each
for a very long time in sea water is minium in mixed assemblies of which is a metal (figure 130):
dismantled, a continuous deposit between aluminium and other
of alumina is very often found common metals of the type found the one that is consumed cal-
between the two sheets. in shipbuilding (or other applica- led the anode undergoes an oxi-
tions). dation reaction:
When joining components how- M Mn+ + ne-
ever it is essential to avoid leaving Such an assessment is a neces- or
recesses that might provide a sary exercise, as it is neither pos- Al Al3+ + 3e-
foothold for corrosion in the long sible nor even desirable for com- when it is aluminium,
term. Intermittent welds on struc- mercial and technical reasons to the other the cathode
tures that are permanently or even construct ships and equipment undergoes a reduction reaction,
only occasionally immersed that are made entirely of alu- usually to the H+ ions present in
should therefore be avoided. minium. On pleasure craft for the water (8):
example, transmission shafts, H+ + e- H2
screws, valves and pipes are
almost never made from alu- The amount of hydrogen that is
minium. given off bears no direct relation-
ship to the mass of metal that is
It is therefore the task of the dissolved at the anode. Under
designer and operator to ensure standard conditions 25C at a
that contact between aluminium pressure of 1013 mbar it is 33.6
and other metals in marine envi- litres for 27 grams of aluminium.
ronments cannot cause bimetallic
CREVICE corrosion. This is a straightforward The reactions at the anode and the
CORROSION matter provided they follow a cathode occur simultaneously and
number of elementary rules based are balanced in electrical charges
on fundamental principles, in par- e-. The complete reaction for the
ticular the concepts of the galvanic bimetallic corrosion of aluminium
cell and the potential scale, and of is as follows:
course on experience. 3
Al + 3H2O Al(OH)3 + H
2 2
H+
e-
Cl-
H+
Al3+ (7) So called because the first current
3+
Al Al3+ generator invented by Alessandro Volta
Al3+ in 1800 was a pileof zinc and copper
H+ H+ H+ Al3+ Al3+
Alcan Marine
Electrical connection
e- e-
Anode Cathode
zinc copper
Electrons flow
Aluminium
Sleeve
and Gasket ( PVC,
insulating elastomer)
washers
2H+ + 2e- H2
Ion connection Bolt Other mtal
(Steel)
Zn Zn2+ + 2e-
Hydrogen is given off (at the cath- Electrical continuity between years of immersion in sea water, a
ode) and aluminium (the anode) the two metals, either through very dense alumina poultice is
dissolves, forming alumina Al direct contact or made by means therefore found in the contact
(OH)3. of a fastener such as clamp area. The extent of the corrosion
screws. will be limited because the alu-
mina has significantly slowed the
6.2 One simple way of avoiding exchange of ions (10).
Conditions of bimetallic corrosion therefore is to
bimetallic corrosion insulate the two metals from one Dissimilar metals. This raises
These simplified equations show another as carefully as possible, the concept of potential which we
that for bimetallic corrosion to take and this is easily done with a high shall now discuss.
place, 3 conditions must come ohmic resistance, i.e. an insulating
together simultaneously: material (figure 131) such as neo-
- presence of an electrolyte, prene (9).
- electrical continuity,
- dissimilar metals. As with any battery (or galvanic
cell), anything that retards or
Presence of an electrolyte: the inhibits the electrochemical reac-
contact area between the metals tions on the electrodes reduces its
must be wetted by fresh water or output this is referred to as
sea water. The more conductive polarisation. Applied to the case
the medium, the stronger the of bimetallic corrosion, the accu-
bimetallic corrosion, and it is the- mulation of corrosion products in
refore much more intense in sea the contact zone between the two
water whose resistance is of the metals slows down the process. (9) Once a much-used technique in
order of 10 to 25 W.cm-1 than in
Alcan Marine
Copper 360
The aluminium alloys used in
marine applications have dissolu- Lead 510
tion potentials that are very close Mild steel 610
to one another (table 66).
Cast iron 610
Cadmium 700
Alcan Marine
Aluminium 750
(11) This accounts for the effectiveness
of coating steel with zinc, and hence Zinc 1 130
the use of galvanised steel in many
applications where it must be protected Magnsium 1 600
154 from corrosion.
(*) mV SCE = millivolts, saturated calomel electrode. Table 67
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS
To fully appreciate the risks of the ner left behind in the bilge of a
electrochemical reactions as we have
bimetallic corrosion of aluminium vessel can cause bimetallic corro- seen.
in a mixed joint, we must distin- sion if water is allowed to stagnate (16) In some cases copper alloys in the
guish between: in the same area as the item made 2000 and 7000 series are sensitised to
of steel (or any other metal). corrosion on contact with steel.
155
As a result, such contacts are now Once the resin has set, place
hardly ever protected on ships (17) 6.7 the shot (or pig lead) in position,
or in coastal installations except Influence of the type carefully avoiding contact with the
obviously in cases where rust dis- of metal in contact aluminium edge of the keel,
coloration must be prevented on with aluminium Now pack the spaces around
aluminium structures (in the case The risk of bimetallic corrosion the lead with resin up to a level 20
of contact with steel). Today, may be greater when aluminium is to 25 mm above the ballast,
steel/aluminium transition joints in contact with certain metals and Finally, access to the keel
(18) are used to make welded con- alloys. should be sealed off by suitable
nections between a hull and alu- means to prevent any ingress of
minium alloys. Copper and its alloys moisture into the keel.
While contact between aluminium
alloys and copper and its alloys Lead ballast should never be laid
(brass, bronze) causes no appre- on the bare hull, e.g. on the floor
ciable bimetallic corrosion, when of a hold, but should be sealed in a
emerged structures are in a wet watertight covering to prevent the
(17) For safety reasons (cf. Chapter 9),
marine environment it is advisable bimetallic corrosion of the alu-
all metal masses on board a ship or on a
structure intended to house electrical where possible to provide insula- minium and the entrainment of
installations must be equipotentially tion between the two metals to lead salts generated by that corro-
bonded. Even if contacts are insulated
avoid local deterioration in the sion in the presence of moisture.
for reasons of corrosion or convenience,
an electrical connection by means of a appearance of the aluminium. Lead salts will cause pitting corro-
cable or braided wire must still be sion in those areas of the hull
provided at one point.
Verdigris however (the corrosion where they are entrained by mois-
(18) Cf. Chapter 9.
product of copper and its alloys) ture.
is aggressive towards aluminium
and its alloys and is reduced to If the lead ballast is fastened to
tiny particles of copper when in the hull directly, it must be care-
contact with them. These parti- fully insulated from it, as indicated
cles in turn cause local pitting in figure 132.
corrosion in the aluminium, and it
is therefore preferable to protect Lead-based paints should never be
structures that are beneath an used to protect steel components
accessory that is made of cop- on board an aluminium vessel
per, bronze or brass. The opti- because lead oxides, like copper
mum solution is to paint them to oxides, cause severe corrosion to
prevent verdigris forming in the the aluminium in the presence of
first place. moisture.
Galvanised the keel space that is accessible insulate the lead from the walls of the
Ballast (lead keel will be wasted if the keel weldments
steel bolts placed prior from the bottom of the boat,
or cast iron) are porous! Gradual penetration of sea
to casting ballast Apply a layer of resin 15 to
water through cracks due to poor welding
20 mm thick in the bottom of the will cause irreparable corrosion to the
156 keel, keel in the medium term.
Figure 132
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS
157
EFFECT OF DESIGN
ARRANGEMENTS
Moisture
Watertight seal
Exterior
Exterior
Watertight seal
Alcan Marine
158
Figure 133
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS
Temperature is not the only products that are susceptible to SENSITISATION OF 5000 ALLOYS
parameter that governs the precip- corrosion. These alloys are sys- AND MAGNESIUM CONTENT [6]
itation of the phase, as is often tematically controlled by the selec-
and mistakenly forgotten (25). tive tests described below.
Time, i.e. the period spent at tem- g.dm-2
Loss of mass
0,5 Mg-5,59%
perature, is also a factor when We should remember however Mg-5,15%
evaluating the intensity of sensiti- that the H116 temper will not pre- Mg-4,60%
162
From figure 6 of NF ISO 11881 Standard, June 2002 Figure 136
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS
Bibliography
11.2 11.3 [1] Corrosion de laluminium, C. VARGEL,
502 pages, Dunod, 1999.
Test for Test for
intercrystalline intercrystalline [2] Chemical aspects of physical
oceanography, J. LYMAN, R. B. ABEL,
corrosion corrosion Journal Chemical Education, Vol. 35,
of the 5000 alloys of the 6000 alloys 1958, pp. 113-115.
Two tests can be used to deter- These alloys are not susceptible to [3] Effect of the temperature and salt
content of sea water on the corrosion
mine the susceptibility of 5000 alu- exfoliation corrosion. Any suscep- behavior of aluminium, W. HUPPATZ, H.
minium alloys to intercrystalline tibility to intercrystalline corrosion MEISSNER, Werkstoffe und Korrosion, Vol.
corrosion: can be determined by the test 38, 1987, pp. 709-710.
163
CHEVY TOY
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164