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Chapter 10

CORROSION BEHAVIOUR OF ALUMINIUM


IN MARINE ENVIRONMENTS

1. Characteristics of marine environments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147


1.1 Sea water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
1.2 Sea atmosphere . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
2. Corrosion behaviour of aluminium under control of the natural film of oxide . . . . . . . . . 148
3. Influence of the pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
4. Influence of alloying elements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
5. Forms of aluminium corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.1 Uniform corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.2 Pitting corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
5.3 Transcrystalline corrosion and intercrystalline corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
5.4 Exfoliation corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
5.5 Waterline corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
5.6 Crevice corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
6. Bimetallic corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
6.1 The galvanic cell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
6.2 Conditions of bimetallic corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.3 Concept of potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
6.4 Practical aspects of bimetallic corrosion of aluminium in marine environments . . . . . . . . . . . . . . . . . . . 155
6.5 Submerged mixed contacts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
6.6 Emerged mixed contacts in open air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
6.7 Influence of the type of metal in contact with aluminium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
7. Aluminium tarnishing and blackening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
8. Role and prevention of marine fouling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157
9. Effects of welding and design arrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
9.1 Effect of welding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
9.2 Effect of design arrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
10. Sensitivity to corrosion of aluminium alloys in marine applications . . . . . . . . . . . . . . . . 159
10.1 Choice of alloys for marine applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
10.2 Sensitivity of 5000 series alloys to intercrystalline corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
11. Corrosion tests . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
11.1 Exfoliation corrosion testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
11.2 Test for intercrystalline corrosion of the 5000 alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
11.3 Test for intercrystalline corrosion of the 6000 alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 163
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145
145
10. CORROSION BEHAVIOUR OF
T HE MARINE ENVIRONMENT
highly aggressive towards
most materials, as amply demons-
is Based on our very long experience
of aluminium’s corrosion behaviour
in marine atmospheres and in sea
perhaps to prevent disappoint-
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
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146
146
ALUMINIUM IN MARINE ENVIRONMENTS
1. CHARACTERISTICS
southern hemisphere have a virtu-
ally uniform total salinity, 32 to 37
g.l-1, including 30 g.l-1 of sodium
course the polluting elements
modify the corrosivity of sea water
vis à vis aluminium (2).
OF MARINE ENVI- chloride or “salt”.
RONMENTS The salinity of enclosed or isolated
seas can be very different from 1.2 Sea atmosphere
A distinction must be made that of the great oceans, and may
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 Sea water
Persian Gulf 57 g.l-1 [2]. wind. The effect of sea air depends
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 8 rosion tests show that alu-
ppm (1) oxygen, minium’s 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 18 °C) 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 30 °C) (2) The diluted sea water in river
(temperature, pressure) or biologi- show that there is no significant estuaries is usually more aggressive to
materials, including aluminium, than
cal (flora and fauna), on the resist- difference between the two sites water off shore. This paradox can be
ance to corrosion of metals can be despite their difference in salinity explained in various ways: the
neither truly isolated nor sepa- (ratio of 1:2) [3]. precipitations of calcium and magnesium
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
The great oceans – the Atlantic, minium may change when the slower. Domestic or industrial wastes
modify physical-chemical balances and
the Indian and the Pacific – which water in a port is polluted by urban may themselves contain corrosive
connect with one another in the or industrial waste, provided of agents.

LIVING QUARTER
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147
147
2. CORROSION BEHA-
3. INFLUENCE
4. INFLUENCE
VIOUR 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
aluminium’s 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) -2 -1

1
mg.dm .h
0
-1 Alkaline
dissolution
-2 in AlO2-
Acid
dissolution
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-3
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
148 the oxide layer very slightly.
Figure 123
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS

5. FORMS OF ALUMI-
5.2 Pitting corrosion
during sheet metal working, fold-
ing or welding operations provide
ideal pockets where pits can
NIUM CORROSION This very localised form of corro- develop during the first few weeks
sion is common to many metals of immersion in sea water.
This section only deals with the (figure 124) and is characterised by
forms of corrosion that might be the formation of cavities in the What is important for the user is to
found in marine environments on material. The diameter and depth know the rate at which the pits
wrought alloys of the 1000, 3000, of the cavities vary depending on a deepen once they are initiated.
5000 and 6000 series, and on the number of parameters inherent in Unlike other metals, e.g. zinc,
silicon casting alloys (40000) or either the metal itself (type of whose corrosion products are sol-
magnesium casting alloys (50000). alloy, manufacturing process etc.) uble, alumina Al(OH)3 is insoluble
or its environment, e.g. concentra- in water so that, once formed, it
These are: tion of mineral salts. adheres to the surface of the
■ uniform corrosion, metal inside the pit cavities. In this
■ pitting corrosion, Aluminium is sensitive to pitting way, hydrated alumina consider-
■ transcrystalline corrosion, corrosion in environments where ably inhibits exchanges between
■ intercrystalline corrosion, the pH is close to neutral, which the metal and sea water or atmos-
■ exfoliation corrosion, essentially means all natural pheric moisture.
■ waterline corrosion, environments such as surface
■ crevice corrosion, water, sea water and atmos- The rate of pitting corrosion in alu-
■ bimetallic corrosion. pheric moisture. minium and its alloys therefore
decreases very rapidly in most
Unlike in other common metals, media including sea water, and
5.1 Uniform corrosion
this type of corrosion is worthy of measurements of pit depths taken
our attention because the corro- at regular intervals have shown
This type of corrosion is accompa- sion pits of aluminium are always that the rate of pitting “v” is a fac-
nied by a regular, uniform covered by very large white blis- tor of time “t” by equations of the
decrease in thickness over the ters of gelatinous hydrated alu- type v = Kt1/3.
whole surface area of the metal. mina Al(OH)3. The blister is always
The rate of dissolution can vary much larger than the underlying Many decades of experience with
from a few microns per year in a cavity. the use of unprotected aluminium
non-aggressive environment to in coastal construction (roofs, wall
several microns per hour depend- Pitting corrosion occurs at sites panels) and in shipbuilding corrob-
ing on the type of acid or base in where the natural film of oxide is orate the results obtained in the
solution in the water. imperfect due to thinning, local laboratory, from natural exposure
rupture or gaps caused by various or at corrosion testing stations
In marine environments, whether factors associated with manufac- over long periods of time: the
immersion in sea water or expo- turing conditions, additives and so depth of pits hardly changes once
sure to sea air, uniform corrosion forth. Experience shows that they have formed during the initial
is minuscule, of the order of one areas which are ground or scored months of service.
micron per year, and is not meas-
urable. PITTING CORROSION OF ALUMINIUM
We can therefore say that the
service life of aluminium alloy Cl- H2
equipment properly designed and

3/2 H2
6 OH- 3/2 O2

built for use in a marine environ- 3 H+


ment will not be limited by this


type of corrosion. 3H2O AI(OH)3 Cu


Al3+

Oxide

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Al3Fe

3e- 3 e-
149
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 Transcrystalline
micrographic examination is
that aluminium equipment can be 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 (fig- Corrosion inside the metal, at especially elongation, and can
ure 125) as it does to immersion in grain level, can spread in two ways even cause component failure.
sea water (figure 126). In both (figure 127):
cases the pits are rarely deeper ■ in all directions: corrosion Intercrystalline corrosion spreads
than one millimetre even after sev- affects all metallurgical consti- from pits. There is no correlation
eral 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
βAl3Mg2 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.
400 ➤ maximum Intercrystalline corrosion can
occur when three conditions
200 ➤
mean come together:
■ presence of a corrosive aqueous
0
5 10 15 20 medium,
■ difference in potential of at least
Length of exposure (years) 100 mV between the intermetal-
Pechiney, Centre de Recherche de Voreppe lics and the solid solution,
Figure 125 ■ continuous precipitation of inter-
metallics in the grain boundaries.
IMMERSION IN SEA WATER
Given the 400 mV difference in
Maximum depth of pits potential between the βAl3Mg2
800 (microns)
phase and the grain, aluminium-
600 magnesium alloys are sensitive to
this form of corrosion under well
400 defined and well known condi-
tions, as reviewed in Section 10.2.
200 They depend on the conditions of
working and the conditions of
0 service.
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1 5
Length of immersion (years) It is normal to quantify the inten-
Pechiney, Centre de Recherche de Voreppe
sity of intercrystalline corrosion by
150
150 the number of grain layers that are
Figure 126
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS

TRANSCRYSTALLINE AND waterline of barges and boats with


INTERCRYSTALLINE CORROSION unpainted hulls is not particularly
corroded by this medium. The
same applies to foundation piles
and the floats of landing-stages
etc. in marinas.
In flowing water this effect is very
weak as the meniscus is continu-
ally being renewed.
In stagnant water, the area either
side of the air/water boundary line
must be painted to avoid the risks
of waterline corrosion.

Transcrystalline Corrosion Intercrystalline Corrosion

Figure 127
WATERLINE
CORROSION
affected by it, and it is accepted and the elongated texture of grains). Aluminium
that intercrystalline corrosion is In the aluminium-magnesium
superficial and harmless when it alloys (5083, 5383, 5086 etc.), the
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. - 800 mV Air

Selective tests that can be used to


detect the sensitivity of aluminium 5.5 Waterline corrosion - 980 mV Water
alloys to intercrystalline corrosion
are given in Section 11. This form of corrosion affects
semi-submerged metal structures,
especially steel, in which the sub- Figure 128
5.4 Exfoliation corrosion
merged zone close to the air/water
boundary can suffer preferential
Exfoliation corrosion is a form of corrosion that is sometimes
corrosion that spreads along severe (6).
planes parallel to the direction of
rolling (or extrusion). Between In aluminium, this corrosion is due
these planes are very thin sheets to the difference in the concentra-
of sound metal. The build-up of tion of chlorides caused by evapo-
corrosion products causes the cor- ration in the thinnest part of the
roded zone to swell, peeling away film of water wetting the metal
leaves of metal like the layers of (figure 128). The result is a differ-
an onion, hence the name “exfolia- ence in dissolution potential which
tion corrosion”. can be significant between the
bottom and top of the meniscus (5) Cf. Section 11.
The sensitivity of aluminium alloys which is anodic and therefore cor- (6) In steel, this form of corrosion,
known as “corrosion by differential
to this very characteristic form of roded [4]. aeration”, is due to the difference in the
Alcan Marine

corrosion (figure 136, p. 162) concentration of oxygen between the


depends on the production condi- Aluminium and its alloys are layer of water that is in direct contact
with air – which is therefore richer in
tions (the rolling or extrusion largely immune from this form of oxygen – and the layer beneath.
process, rates of work hardening corrosion in sea water, so the Corrosion occurs below the waterline. 151
151
5.6 Crevice corrosion
6. BIMETALLIC CORRO-
6.1 The galvanic cell
Crevice corrosion, also known as SION 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 ■ the one that is consumed – cal-
of alumina is very often found common metals of the type found led the anode – undergoes an oxi-
between the two sheets. in shipbuilding (or other applica- dation reaction:
When joining components how- tions). M → Mn + + ne-
ever it is essential to avoid leaving or
recesses that might provide a Such an assessment is a neces- Al → Al3 + + 3e-
foothold for corrosion in the long sary exercise, as it is neither pos- when it is aluminium,
term. Intermittent welds on struc- sible nor even desirable for com- ■ the other – the cathode – under-
tures that are permanently or even mercial and technical reasons to goes a reduction reaction, usually
only occasionally immersed construct ships and equipment to the H+ ions present in the
should therefore be avoided. that are made entirely of alu- water (8):
minium. On pleasure craft for H+ + e- → H2
example, transmission shafts,
screws, valves and pipes are The amount of hydrogen that is
almost never made from alu- given off bears no direct relation-
minium. ship to the mass of metal that is
dissolved at the anode. Under
It is therefore the task of the standard conditions – 25 °C at a
designer and operator to ensure pressure of 1013 mbar – it is 33.6
that contact between aluminium litres for 27 grams of aluminium.
and other metals in marine envi-
ronments cannot cause bimetallic The reactions at the anode and the
CREVICE corrosion. This is a straightforward cathode occur simultaneously and
CORROSION matter provided they follow a are balanced in electrical charges
number of elementary rules based “e-”. The complete reaction for the
on fundamental principles, in par- bimetallic corrosion of aluminium
ticular the concepts of the galvanic is as follows:
cell and the potential scale, and of
course on experience.

H+
Cl- H+
➤ e-
Al3+ (7) So called because the first current
➤ Al3+ Al3+ generator invented by Alessandro Volta
Al3+ Al Al3+
3+
H+ H+ H+ in 1800 was a “pile“of zinc and copper
Al3+ discs insulated from one another by felt
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e-

and immersed in a diluted solution of
sulphuric acid.
(8) The H+ ions are produced either by
the dissociation of the water itself or by
152
152 an acid dissolved in the water.
Figure 129
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS

PRINCIPLE OF A GALVANIC CELL INSULATION OF ALUMINIUM


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 métal
(Steel…)
Zn → Zn2 + 2e-

Dilute acid solution


Figure 130 Figure 131

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 Conditions of
One simple way of avoiding exchange of ions (10).
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 shipbuilding, it has been superseded by
Alcan Marine

fresh water (or rainwater) whose When hybrid joints made from cathodic protection for immersed
structures (cf. Chapter 11).
resistance attains several thou- plates of steel and aluminium alloy (10) It goes without saying that this
sand W.cm-1, depending on the that are bolted together without initial corrosion cannot be expected to
source of the water. any insulation are taken apart after provide reliable long term protection. 153
153
DISSOLUTION POTENTIAL OF ALUMINIUM ALLOYS
6.3 Concept of potential
(NACL SOLUTION, H2O2, ASTM G 69)
Alloy Potential mV SCE
This is a thermodynamic phenom-
enon that measures a metal’s ten- 1050A – 750
dency to oxidize. The more elec- 3003 – 740
tronegative the potential, the
more the metal tends to oxidize. 5052 – 760
5056 – 780
Potential is measured in millivolts 5083 – 780
(mV) against a reference electrode
and in a defined medium. 5086 – 760
Corrosion specialists usually use 5154 – 770
the saturated calomel electrode
(SCE) as the reference. 5182 – 780
5454 – 770
The result is a classification or 5456 – 780
‘potential scale‘ of metals and
alloys; table 67 shows a part of 6005A – 710
this scale for the common metals 6060 – 710
in natural sea water in motion.
6061 – 710
The rankings on this scale can be 6063 – 740
used to predict which of the two
metals in contact with each other 42000 (A-S7G03) – 820
in an aqueous medium, or more 51300 (A-G5) – 870
specifically in sea water, will be Table 66
attacked:
■ if both metals have electrone-
gative potential, it will be the DISSOLUTION POTENTIALS
more electronegative, MEASURED IN NATURAL SEA WATER IN MOTION AT 25°C
■ if one metal is electropositive it
Alloy Dissolution Potential (mV SCE) (*)
will be the electronegative.
Graphite + 90
In this combination for example: Stainless steel – 100
Zinc Ed = – 1130 mV
Iron Ed = – 610 mV Titanium- – 150
it is the zinc that corrodes (11). Inconel – 170
Experience shows that bimetallic Cupronickel 70-30 – 250
corrosion only occurs when the Cupro-nickel 90-10 – 280
two metals in contact have a dif- Bronze – 360
ference in potential of at least
100 mV. Brass – 360
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

(11) This accounts for the effectiveness


Aluminium – 750
of coating steel with zinc, and hence the Zinc – 1 130
use of galvanised steel in many
applications where it must be protected Magnésium – 1 600
154
154 from corrosion.
(*) mV SCE = millivolts, saturated calomel electrode. Table 67
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS

In a marine environment therefore ■ a submerged structure (quick


there is no risk of bimetallic corro- works) 6.6 Emerged mixed
sion between these alloys. This is ■ an emerged structure (dead
also true of casting alloys, and is works) – the type of metal must contacts in open air
the reason why stiffeners in 6000 also be considered in this case. Many decades of experience with
alloys are frequently used welded aluminium applications in marine
to plate in 5000. Note: Anodising affords no protec- environments, both on board ships
tion from bimetallic corrosion. and in on-shore coastal installa-
tions, show that contacts with
6.4 mild steel, whether bare or coated
Practical aspects of
bimetallic corrosion
6.5 Submerged mixed
(galvanised, cadmium plated), and
stainless steel cause no significant
of aluminium in contacts bimetallic corrosion of aluminium
marine environments As we have already shown, when and its alloys (15) in the 1000,
Bimetallic corrosion is a very contacts are submerged, bimetallic 3000, 5000 and 6000 series (16).
localised phenomenon and very corrosion of aluminium is unavoid-
often confined to the contact able when in contact with most
zone. In theory, the current den- common metals (13). The intensity
sity that determines the rate of of this corrosion will depend on the
dissolution of the anodic metal is a type of metal, on the composition
function of the relationship: of the environment and on the
cathodic surface length of time if the contact area is
anodic surface submerged occasionally rather
than continuously.
Experience shows that this area
relationship is of no great rele- The aluminium structure must be
vance, as bimetallic corrosion protected, and there are a number
occurs primarily in or near the con- of ways of achieving this:
tact zone, and so the anode area ■ Insulation, by inserting plastic
must be judged to be more or less seals between the two metals.
equal to the cathode area. Taking pipework as an example, a
gasket of sufficient thickness is fit-
Expressed in practical terms, a ted between the aluminium flan-
small component such as a screw ges of the pipe and the flange of a
or probe made from copper or stainless steel or brass valve.
copper alloy and attached to a ■ Painting: the surface of the
large aluminium alloy structure cathode, i.e. of the other metal,
without any insulation – and per- must first be masked. Painting the
manently submerged – will cause aluminium only is far less effec-
severe bimetallic corrosion at the tive.
point of attachment. ■ Cathodic protection is the most
(12) Except cadmium, zinc and
practical solution (14) and the one magnesium. There will be no bimetallic
Aluminium’s position on the scale used most often to neutralise the corrosion of aluminium in contact with
of potential (table 67) means that galvanic couples between a ship’s fasteners made from galvanised or
cadmium-plated steel. Instead, as long
in virtually every instance in which aluminium hull and the propulsion as there is zinc or cadmium on the steel,
it is joined to another common system (shaft and screw) and these metals will dissolve to protect it.
metal (12), it will be the anode of other items attached to the hull (13) This will also apply to mixed
the resulting battery and so likely (intake strainers, various accesso- contacts in the bilges of a ship if water
stagnates there.
to suffer bimetallic corrosion if the ries). (14) Cf. Chapter 11.
conditions are right. (15) For a number of reasons: a layer of
Note. A steel tool such as a span- corrosion products (rust, alumina) forms
To fully appreciate the risks of the ner left behind in the bilge of a on the contact faces, inhibiting
Alcan Marine

bimetallic corrosion of aluminium vessel can cause bimetallic corro- electrochemical reactions as we have
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
155
As a result, such contacts are now Once the resin has set, place
6.7

hardly ever protected on ships (17) 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
marine environment it is advisable bimetallic corrosion of the alu-
where possible to provide insula- minium and the entrainment of
(16) In some cases copper alloys in the tion between the two metals to lead salts generated by that corro-
2000 and 7000 series are sensitised to avoid local deterioration in the sion in the presence of moisture.
corrosion on contact with steel.
(17) For safety reasons (cf. Chapter 9),
appearance of the aluminium. Lead salts will cause pitting corro-
all metal masses on board a ship or on a sion in those areas of the hull
structure intended to house electrical Verdigris however (the corrosion where they are entrained by mois-
installations must be equipotentially product of copper and its alloys) ture.
bonded. Even if contacts are insulated
for reasons of corrosion or convenience, is aggressive towards aluminium
an electrical connection by means of a and its alloys and is reduced to If the lead ballast is fastened to
cable or braided wire must still be tiny particles of copper when in the hull directly, it must be care-
provided at one point.
(18) Cf. Chapter 9.
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.
ATTACHMENT OF LEAD Lead Mercury
OR IRON BALLAST Lead is often used as ballast for Aluminium in contact with mer-
pleasure craft. The combination of cury suffers very severe corrosion
aluminium and lead reacts very which takes the form of flaky
strongly in sea water, and it is white ‘blooms’ that spread widely
therefore essential to prevent where the quantity of mercury is
water entering the keel if this is significant or finely divided. The
Aluminium ballasted with lead shot or pig effect of mercury is all the more
hull ➤
Insulating
➤ washers lead. The following procedure is insidious as it tends to occur at
Insulating
➤ usually used to prevent the risk of low points where fine droplets of
gaskets and bimetallic corrosion which can be mercury accumulate.
sleeves very severe (19):
■ Carefully degrease the inside of

(19) All the careful precautions taken to


the keel space that is accessible

Galvanised insulate the lead from the walls of the


Alcan Marine

Ballast (lead from the bottom of the boat, keel will be wasted if the keel weldments
steel bolts placed prior 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
156 keel, keel in the medium term.
Figure 132
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS

It is therefore most inadvisable to


carry mercury instruments such as
barometers or thermometers on
7. ALUMINIUM TARNIS-
As with other metals, antifouling
paints can be used on aluminium
to prevent the growth of marine
board a ship when spillage or HING AND BLACKE- encrustations (20).
breakage might cause severe cor- NING
rosion of the hull. However there is one very impor-
Aluminium in a humid atmosphere tant restriction: antifouling paints
Graphite or in contact with sea water or based on salts of copper, mercury
Although graphite is not a metal fresh water tarnishes to a degree or lead cause severe corrosion (21)
(but a metalloid), contact with it in that depends on the medium. This and should be avoided. This
a wet environment causes bimetal- phenomenon, known as blacken- bimetallic corrosion is due to the
lic corrosion that is more or less ing, is not a type of corrosion but reduction of copper, mercury and
intense depending on the porosity merely an alteration of the visual lead salts in contact with the alu-
of the graphite. It is therefore inad- properties of the film of natural minium surface and can do
visable to use graphite based lubri- oxide. It does not produce any irreparable damage to the hull of a
cants on aluminium boats. subsequent sensitivity to corro- vessel.
sion.
There is as yet insufficient experi-
ence with the use of carbon fibre In a marine environment, blacken-
equipment on board aluminium ing can be prevented on certain
ships to be able to draw conclusions items by anodising or polishing
about contact between aluminium them. Anodising is by far the more
and carbon fibre composites. lasting method, and is used on
Laboratory tests with immersion boat masts.
in synthetic sea water show that (20) Cf. Chapter 11.
aluminium suffers a mild and very (21) The use of antifouling paints based
on minerals salts is actually banned.
superficial attack when in contact
with carbon fibre parts. 8. ROLE AND PREVEN-
Note: When in port, craft should TION OF MARINE
be moored/anchored using ropes FOULING
made from hemp or synthetic
fibres as this creates an ‘open cir- Unlike salts of copper (or mer-
cuit’ between the aluminium craft cury), aluminium salts are not toxic
and the metal anchor or bollards to living organisms and they can WELDMENT ON A GANGWAY
on the quayside. therefore easily attach themselves
to aluminium surfaces where they
will grow unchecked unless dis-
lodged.
Such marine encrustations include
barnacles, corals, algae, sponges
etc., but cause no appreciable cor-
rosion to the underlying metal
apart from a very superficial attack
to a depth of a few hundredths of
a millimetre. Shells leave a virtually
indelible impression on the metal.
Alcan Marine

157
157
EFFECT OF DESIGN
ARRANGEMENTS
BAD GOOD BAD GOOD

Moisture

Moisture Watertight seal ➤


Watertight seal

Exterior
Exterior

Watertight seal

Area easy to clean


Area difficult to Good paint
clean adhesion



Alcan Marine

Poor paint adhesion Discontinuous weld Continuous weld

158
158
Figure 133
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS

9. EFFECTS
It is therefore essential to assist
the drainage of water and conden-
sation on divisions and partitions
10. SENSITIVITY TO
OF WELDING subject to temperature variations, CORROSION OF
AND DESIGN and to provide as much ventilation ALUMINIUM ALLOYS
ARRANGEMENTS as possible for spaces that are IN MARINE APPLI-
more or less accessible (ballast CATIONS
Design layouts can significantly tanks, holds etc.).
influence the corrosion perform- These areas, as well as watertight Many decades of experience with
ance of aluminium alloy structures buoyancy chambers, must be reg- marine applications of aluminium
in service. ularly inspected and may require have shown that its resistance to
more frequent maintenance than corrosion is remarkable.
the rest of the structure.
9.1 Effect of welding
Nevertheless:
Finally, anything that encourages ■ some series of alloys are not
Experience shows that the corro- the permanent presence of mois- suited to this type of application,
sion behaviour of welded struc- ture, such as certain types of lin- ■ production processes must be
tures made from alloys belonging ing, must be carefully avoided. For designed to avoid accidentally sen-
to the 1000, 3000, 5000 and 6000 example, expanded foam (or insu- sitising 5000 series alloys to struc-
series is similar to that of non- lation blankets made from rock- tural corrosion (intercrystalline cor-
welded surfaces. In other words, wool or similar materials) placed rosion, exfoliation corrosion or
weld seams and heat affected against an aluminium division for stress corrosion).
zones will not be the site of pref- thermal insulation must be posi-
erential corrosion provided weld- tioned so that it cannot trap con- Finally, service conditions must also
ing is done according with the rel- densation or attract moisture. be controlled to ensure that certain
evant codes of practice and with limits of temperature and time are
the right filler alloys (22). Floor coverings should also be not exceeded. The H116 temper has
adhesive bonded to prevent the the advantage of undergoing
The same applies to adhesive ingress of moisture between the mandatory inspection for sensitivity
bonding which does not affect the covering and the aluminium to exfoliation corrosion.
corrosion behaviour of compo- “floor”.
nents joined by this process.
Note: Stray electrical currents can 10.1 Choice of alloys for
be a determining factor leading to
9.2 Effect of design
corrosion of the hull surface in marine applications
contact with sea water. As is While the 5000 and 6000 series
arrangements stated in Chapter 10 (23), the hull alloys will be preferred for their
Despite the excellent resistance to (and any other metal structure on resistance to corrosion, their weld-
corrosion of the alloys used in the boat) must never act as a ability and their level of mechanical
shipbuilding (and in marine appli- return conductor for the current, characteristics, other wrought
cations), instances of corrosion whether this is d.c. or a.c. alloys belonging to the 1000 and
are occasionally seen in service. 3000 series are suitable for use in
non-structural applications for dec-
An examination of these cases oration, interior fittings etc.
shows that it is most often the
design layout that causes these The use of 2000 and 7000 series
problems. Figure 133 illustrates alloys on the other hand must be
classic cases of design layouts the exception in view of their poor
that are detrimental to good corro- resistance to corrosion, and they
sion performance. require special protection when
used in a marine environment.
Experience shows that areas where
Alcan Marine

water stagnates or where dust (or The 2000 and 7000 series copper
soot) can accumulate can suffer alloys cannot be welded with the
very severe corrosion in the form of (22) Cf. Chapter 6. classical arc processes. The 7000
deep pits and even perforations. (23) Chapter 9. series alloys without copper, e.g. 159
159
7020 or 7108, are easy to weld The precipitation of the β phase on
however, and present a high level 10.2 Sensitivity of 5000
the grain boundaries has a ten-
of mechanical characteristics after dency to be continuous, and will
welding, an attractive attribute that series alloys be the more rapid and more
could be an advantage for sheet to intercrystalline dense:
metal working in general and ship- corrosion ■ the higher the level of magne-
building in particular. It has been well known since the sium,
early 1950s that aluminium-mag- ■ the higher the service tempera-
Even so, the heat affected zone is nesium alloys can have a tendency ture, and
highly sensitive to exfoliation cor- to intercrystalline corrosion, the ■ the greater the degree of strain
rosion in all environments, so more so the higher the level of hardening.
much so that the development of magnesium, which is why indus-
these alloys has had to be aban- trial alloys do not normally contain As figure 135 shows, the tempera-
doned except in very specific more than 5.5 % magnesium. ture range between 125 and 225 °C
applications out normal fields. is one of high sensitisation, and
This sensitivity is due to the sensitisation can start at even lower
In the absence of any significant changes in the distribution of the temperatures for the alloys with the
progress in the control of sensitiv- magnesium in the metal in the most magnesium, over 5%.
ity to exfoliation corrosion, it is not solid state. The solubility of mag-
possible with our present level of nesium in aluminium is very high As we have already seen, these
knowledge (24) of the metallurgy at high temperatures – 15 % at intermetallics are anodic relative
of these alloys to use them in 450 °C – but is no more than 1 % to the mass of the grain, their
naval construction without special at ambient. potential is –1150 mV SCE, a dif-
protection [5]. ference of some 400 mV from the
When the temperature falls below solid solution, which is consider-
The casting alloys commonly used 450 °C, the magnesium precipi- able. There is therefore a risk of
in marine applications are the tates in the form of intermetallics intercrystalline corrosion if their
42100 (A-S7G03), the 42200 (A- Al3Mg2 (or Al8Mg5), commonly precipitation is continuous on the
S7G06) and the 51100 (A-G3). referred to as “β phase”. But when grain boundaries and if the envi-
certain conditions occur these ronment is corrosive.
precipitates can collect on the
grain boundaries, and the metal is
then “sensitised”. A micrograph
examination soon reveals whether
the alloy is sensitised or not (fig-
ure 134).

MICROGRAPHIC APPEARANCE OF SENSITISED ALLOY 5083


Alcan Marine

5083 Sensitised State 5083 Non-sensitised State


160
160 (24) June 2003.
Figure 134
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 β 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
0,5 Mg-5,59 %
perature, is also a factor when We should remember however

Loss of mass

Mg-5,15 %
evaluating the intensity of sensiti- that the H116 temper will not pre- Mg-4,60 %

sation. This should be obvious, as vent precipitation of the β phase


the rate at which the magnesium on the grain boundaries when the 0
75 100 125 150 175 200 225 250 (°C)
atoms migrate towards the grain service conditions can cause it. After 8 hours immersion in
boundaries obeys the laws of dif- This temper is used very widely in NaCl 3 %, HCI 1 %
fusion in the solid state (the alu- shipbuilding. Figure 135
minium matrix in this case). It is
dependent on temperature
according to the classic equation: (25) It is not because a metal is (26) In the document “AD-Merkblatt W
sensitised by precipitation at the grain 6/1” of May 1982, published by the
boundaries that makes corrosion Vereinigung der technischen
τ = t exp – (Q/RT) inevitable, it depends on the Überwachungsvereine e.V., D 4300
where: environment. Experience has confirmed Essen 1, entitled “Aluminium and
τ = the distance covered this at temperatures well above 65°C, aluminium alloys malleable materials”,
including in heat exchangers operating in the limit is set at 80°C for alloy
t = time sea water. There are road tankers AlMg4.5Mn, equivalent to the 5083, with
T = absolute temperature carrying heavy fuel oil, loaded at 65°C, tolerances of 150°C for periods not
Q is a constant that depends on that have been in service for 20 years or exceeding 8 hours, provided the service
more, with 8 to 10 hours of rotation a pressure is reduced by half and 24 hours
the element. day, i.e. at least 50,000 hours of total if the service pressure is reduced to
time at 65-70°C. But obviously atmospheric.
Too often, the limit at which 5000 sensitisation must be avoided.
alloys with more than 3.5 % mag-
nesium can be used has been set
at 65°C (26). It is in fact the product
of “Time xTemperature” that must
be taken into consideration. On a
5086 for example, it will take
2 years at 65°C or several months MARINA PONTOON AND FLOATS MADE OF 5754
at 100°C to cause continuous pre-
cipitation on the grain boundaries.
The effect of time is cumulative.
The sensitisation of these alloys –
which is always avoidable – can be
due to manufacturing conditions
or service conditions when they
are held at temperature for long
periods.
Much research has been done on
all of these parameters since the
1950s [7]. Sensitisation can be
inhibited by thermal treatments
which cause discontinuous “pearl
necklace” precipitation of the β
phase on the grain boundaries [8].
For many years now, the produc-
tion processes for alloys 5083,
Alcan Marine

5086 and Sealium® – including


the H116 temper – have been spe-
cially adapted for shipbuilding [9] to
avoid the supply of semi-finished 161
11. CORROSION TESTS
sion is measured with the ASSET
test (ASTM G66-99) and suscepti-
NH4Cl - 1 M : 53 g.l-1
NH4NO3 - 0,25 M : 20 g.l-1
bility to intercrystalline corrosion (NH4) 2C4H4O6 - 0,01 M : 1,84 g.l-1
with the ASTM G67 test (NAMLT). H2O2 - at 30 % : 10 ml. l-1
European standard EN 13195-1 (27)
states that alloys 5083, 5383 and Susceptibility to exfoliation corro-
5086 supplied in the H116 temper 11.1 Exfoliation corrosion
sion is assessed against typical
“in the form of sheet, strip and images (figure 136) and result in a
plate must be tested to assess testing grading as shown in table 68.
their resistance to intergranular cor- This is the ASSET test (28) which
rosion and exfoliation corrosion.” is conducted according to ISO
11881 (29) and ASTM G66 (30) on
This test is either the ASSET test samples whose dimensions
(ASTM G66-99) which determines (length and width) are at least 40 x
susceptibility to exfoliation corro- 100 mm. The conditions of this
sion, or any other method agreed test are summarised below:
between supplier and buyer.
After surface preparation by
Section 9 of draft standard ASTM degreasing, alkaline pickling and
B924 04 relates to the 5059, nitric neutralising, the specimens (27) European standard EN 13195-1,
5083, 5086, 5383 and 5456 alloys are immersed for 24 hours at December 2002, “Aluminium and
in the H116 and H321 tempers. 65 °C in the specific reagent of the aluminium alloys – Wrought and cast
Susceptibility to exfoliation corro- 5000 series (31): products for marine applications
(shipbuilding, marine and offshore).
(28) ASSET = Ammonium Salt Solution
Exfoliation Test
(29) ISO 11881, June 2002, Corrosion of
metals and alloys – Exfoliation corrosion
EVALUATION OF RESULTS OF THE ASSET TEST testing of aluminium alloys.
Evaluation Grading (30) Standard test method for visual
assessment of exfoliation corrosion
No significant attack N susceptibility of 5XXX series aluminum
alloys (ASSET test).
Pitting corrosion P (31)
NH4Cl = ammonium chloride,
Generalised corrosion G NH4NO3 = ammonium nitrate,
Exfoliation corrosion EA, EB, EC, ED (NH4)2C4H4O6 = ammonium tartrate,
H2O2 = oxygenated water.
Table 68

CLASSIFICATION OF EXFOLIATION CORROSION WITH THE ASSET TEST


Alcan Marine

162
From figure 6 of NF ISO 11881 Standard, June 2002 Figure 136
10. CORROSION BEHAVIOUR OF ALUMINIUM IN MARINE ENVIRONMENTS

Bibliography
11.2 Test for
11.3 Test for
[1] Corrosion de l’aluminium, C. VARGEL,
502 pages, Dunod, 1999.
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.
according to ASTM G110 (36) in [4] “Corrosion de l’aluminium sous
couche mince électrolytique, corrosion à
■ The NAMLT tests (32) according the reagent with 57 g. l-1 de NaCl la ligne d’eau et corrosion au stockage”,
to ASTM G67 (33). et 0,3 % de H2O2. C. FIAUD, G. AZERAD, E. GROSGOGEAT,
Journées “Durabilité de l’aluminium et
de ses alliages dans les industries
The samples are immersed in a 70 électriques”, Cefracor Paris, December
to 72 % solution of nitric acid 1986, pp. 33-37.
HNO3 at 30 °C for 24 hours, and [5] “Experience from the construction
weighed before and after the test. and operation of the Stena HSS”, H.
NORDHAMMAR, STENA REDERI, The Third
International Forum on Aluminium Ships,
According to standard B928-04 (32) NAMLT = Nitric Acid Mass Loss Hauguesund, Norway, May 1998.
(34): Test. [6] “Influence de la teneur en
- the batch is passed when the (33) ASTM G67: Standard test method magnésium sur la résistance à la
for determining the susceptibility to corrosion sous tension des alliages Al-
mass loss is < 15 mg.cm-2, intergranular corrosion of 5XXX series Mg”, A. GUILHAUDIS, Pechiney SREPC
- the batch is rejected when the aluminum alloys by mass loss after Report, September 1959.
mass loss is > 25 mg.cm-2, exposure to nitric acid. [7] “Development of Wrought Aluminium-
- for mass losses between 15 and (34) B 928 - 04: Standard Specification Magnesium Alloy”, E. H. DIX, W. A.
for High Magnesium Aluminum Alloy ANDERSON, M. B. SHUMAKER, Technical
25 mg.cm-2, the form of corrosion Sheet and Plate for Marine Service, Paper, No. 14, Alcoa, 1958.
must be determined by micro- February 2004. [8] “Traitements thermiques de
graph examination after phos- (35) According to the formula τ = t exp stabilisation des alliages aluminium-
phoric attack. The batch is rejected –(Q/RT), 7 days at 100 °C is equivalent magnésium à 5% contre les effets de
to 6 months at 60 °C. chauffage à basse temperature”, A.
if the corrosion proves to be inter- (36) ASTM G110: Standard practice for GUILHAUDIS, Revue de l’Aluminium, 1955,
crystalline. evaluating the intergranular corrosion Nos. 223 and 224.
resistance of heat treatable aluminum [9] “Aluminium-Magnesium alloys 5086 and
■ The INTERACID test according
alloys by immersion in sodium chloride + 5456 H116”, C. L. BROOKS, Naval Engineers
hydrogen peroxide solution. Journal, August 1970, pp. 29-32.
to the protocol published in the
Journal of the European
Communities on 13/09/1974, Nos.
C104/84 to 89.
Here the reagent consists of a NO ALUMINIUM CORROSION
solution made from 30 g.l-1 of NaCl
and 5 g.l-1 of 37 % HCl (d =1.19).
The samples are immersed in the
reagent for 24 hours at 23 °C.
After determining the mass loss
(weighed before and after the
test), the samples are examined
under a microscope with a magni-
fication of x200.
These tests can be conducted on
samples heated to 100 °C for 7
Alcan Marine

days (35).

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CHEVY TOY
Alcan Marine

164