ADVANCED CORROSION

Corrosion Behaviour and Protection of Aluminium

Alloys in Sea Water

GIANNISA MASHANAFIE
1906342534
 INTRODUCTION

ALUMUNIUM ALLOY

Aluminum is considered as an extremely corrosion-resistant material due to a thin, protective,

highly adherent oxide film which it forms on the surface.

ALUMUNIUM ALLOY CATEGORIES

Cast
Wrought Series Contents Series Contents

Alloy 1000 Pure aluminum Alloy xxx.0 Indicated casting

2000 Copper directly cast into finished products xxx.1 Indicated ingot
formed by rolling, forging and extrusion
into useful products 3000 Magnesium xxxx F As fabricated
4000 Silicon xxxx W Solution heat treated
5000 Magnesium xxxx O Annealed (wrought alloys)
6000 Magnesium and silicon xxxx H Strain hardened
7000 Zinc xxxx T Thermally threated
8000 Other elements
9000 Unassigned
1.
CORROSION BEHAVIOUR
OF ALUMINIUM UNDER CONTROL
OF THE NATURAL FILM OF OXIDE
Aluminium owen its excellent
corrosion resistance to the presence
on the metal of a permanent film of
natural oxide that consists of alumina
(Al2O3) and makes the metal
“passive” to the environment.
The physical-chemical stability of the
oxide film is therefore key to
aluminium’s resistance to corrosion.
2.
INFLUENCE OF
THE pH
The rate of dissolution of the
oxidefilm is determined by
the pH of the environment. It
is very fast in acid and
alkaline media and slow in
media that are close to pH
neutrality (pH 5 to 9). The
oxide film is therefore very
stable in sea water whose
pH is 8 – 8.2.
3.
INFLUENCE OF ALLOYING
ELEMENTS
Some alloying elements of alumIinium
alloys actually reinforce the protective
character of the natural oxide film,
while others weaken it.
Magnesium – Magnesia combine with
alumina to enhance properties oxide
film < series 5000 : 5083, 5383, etc>
Copper that weaken the protection
provided by the oxide film in marine
applications unless special protection
is provided < series 2000 & 7000>
 Table.1
Figure.1
Influence of alloying element at casting
The rate of dissolution of the oxide film is aluminium alloy
determined by the pH.
Alloy Cu Mn Mg Si Other Application
SOLUBILITY OF ALUMINA 413.0 - - - 12.0 - Marine equipment

443.0 - - - 5.2 - Marine application

Component exposed to
514.0 - - 4.0 - -
seawater

Table.2

Influence of alloying element at wrought

aluminium alloy

No Al Si Cu Mn Mg Cr Zn Other Application

5052 97.2 - - - 2.5 0.25 - - Marine application

6063 98.9 0.4 - - 0.7 - - - Marine & saltwater application

 CORROSION BEHAVIOUR OF AL ALLOY

The ability of aluminum to resist corrosion depends on the

inherent ability to form protective oxide film. such as
Bayerite [α-Al(OH)3], and Boehmite (γ -AlOOH) on its
surface

the passive region (pH = 4 – 8) where the films of oxide

1 forms lies between the acid range (pH = 2−4) and
alkaline range (pH = 8–16).

2 Aluminum dissolves both in acids and alkaline solutions

due to instability of aluminum oxide and hydroxide films

3 The rate of corrosion is low between pH 5.5 and 8.5

where forms alumina oxide Al2O3.3H2O

Figure.2 The Pourbaix diagram for aluminum and water illustrates the stable phases for the
different potentials and pH. (Reproduced by kind permission of NACE Int., Houston, USA) 6
 Al resistant to Ca(OH)2  Good resitance to urban and Following is a summary of electrochemical
1
marine atmoshperes unless contaminated with copper corrosion:
- for example concrete, NH4OH > 10%, salt solutions and most dry gases
Al3+ + 3OH− →Al(OH)3 (anodic reaction)
Al subject to attack by chloride ions.
2 ½O2 + H2O + 2e → 2OH− (catodic reaction)
Al3+ + 3Cl−→AlCl3 + 3e−
- As the concentration of chloride ions is increased, corrosion is enhance
In case of no oxygen: 2H+ +2e → H2 ↑

Above 70% Al containing, boehmite (γ -AlOOH) replace the Upon dissolution of aluminum cation into
3 bayerite (α-AlOOH)3  layers afford corrosion protection to aqueous solution, it diffuses to another area to
aluminum.
precipitate aluminum hydrate (gelatinuous):
Aluminum is not resistant to corrosion in HCl, HF, HClO 4 and
4 Al3+ + 3OH− → Al(OH)3 (Precipitates)
H3PO4, in NH4OH < 10%, and water containing salts of heavy
metal ions. Al3+ + 3H2O → 3H+ + Al(OH)3 (Precipitates)

7
FORMS OF OF ALUMINIUM ALLOY CORROSION
1.
UNIFORM
PREVENTION
CORROSION
 This attack occurs when pH is either
very high or very low. The protective
aluminum oxide layer dissolves
rapidly under the above conditions.
 In marine environments, whether
immersion in sea water or exposure
to sea air, uniform corrosion is
minuscule, of the order of one
micron per year, and is not
measurable.
2.
CREVICE
CORROSION
 The formation of a crevice is followed by formation of a
differential aeration cell.
Control of pH
by inhibitor  The oxygen inside the crevice becomes depleted after a
length of time and the crevice becomes anodic.
Cathodic Al3+ + 3H2O → 3H+ + Al(OH)3.
protection
 When a bolted or riveted joint that has been immersed for a
very long time in sea water, deposit of alumina is very often
found between the two sheets.
 The spread of crevice corrosion in aluminium is usually
minimal
 Figure.3

Crevice corrosion of aluminum can occur in a

saltwater environment PREVENTION

by sealing or welding.

 reduction-reaction occur around the crevice mouth

and take place slowly inside the crevice.
  
 3.  AlCl3 formed reacts outside the pit with water → precipitate
PITTING
CORROSION Al(OH)3
 precipitate Al(OH)3 look like white chimneys which cover
 The mechanism of pitting corrosion of Al alloy
the pits.
is not very different from steels.
Al → Al3+ + 3e− Figure.4

(anodic reaction in the pit) Pitting corrosion mechanimse of aluminium

O2 + 2H2O + 4e → 4OH− PITTING CORROSION OF ALUMINIUM

(catodic reaction adjacent to the pit)
 Cu2+ + 2e → Cu
as deposit
 (Al3+ + 3H2O + Cl− → H+ + AlOHCl+)
The pit cavity continues to acidity and hydrogen evolves.
 The hydrogen bubbles also pump out AlCl 3 (Al3 +
+

3Cl−→AlCl3 + 3e)
Figure.5 Table.3

Effect of pH and oxygen content on seawater Pit depths for different aluminum alloys for six
pitting of aluminum alloy tubes based on 30- months in Pacific ocean
day tests in environmental side unit tests.
Max. pit Avg. pit
Temp Pits per
Alloy depth depth Remark
(F) sq. inch
(inch) (inch)

3003 110 0 0 0 Excellent

Shallow pitted areas

5052 110 0.08 0.002 1
scattered pits

One minor pit,

6063 110 0.01 - -
excellent

5050 110 0 0 0 Excellent

 To summarize, aluminum alloys 3003, 5052 and

6063 can be successfully used in a marine
environment by careful control of water chemistry,
oxygen and pH levels.
 Figure.6

Lower rate pitting corrosion of aluminium PREVENTION

immersion in sea water

IMERSION IN SEA WATER

Elimination pitting with choose material
which high resistance to pitting.
Al alloy 3003, 5052 and 6063 can be successfully used in a marine
environment by careful control of water chemistry, oxygen and pH levels.

Cathodic protection by ICCP

 aluminium equipment can be used for decades in Applying organic coating

certain natural environments ( sea air, sea water)
without any protection.
 5.
INTERGRANULAR
CORROSION
PREVENTION
Figure.7
 Intergranullar corrosion is caused
Intergranullar corrosion
by the difference in electrochemical Elimination sites of pitting or
crevice corrosion.
potential that can exist between the
actual grain and the grain boundary
zone Heat treatment for minimizing
difference potencial
 Intercrystalline corrosion spreads
from pits.
 The acid environment in the pit Selective tests that can be used
to detect the sensitivity of
leads to the attack on grain aluminium alloys to intergranullar
boundaries. corrosion.
 5. Figure.8
STRESS
CORROSION Optical microscope micrographs of SCC specimens of anodized 1050 Al-alloy in
CRACKING seawater with a concentration of sulphate, at various periods of time

 In stress corrosion cracking, the crack

follows the grain boundary, termed
intergranular.
 Over the years, high strength alloys of
the 7xxx series are known to be
sensitive to SCC in seawater.
 In alloys of the 5xxx series, the
formation of Mg2Al3 in alloys
containing more than 3% Mg,
promotes SCC
 Alloys of the 6xxx series show a strong
resistance to SCC
Table.5

Ranking of stress corrosion cracking of major

commercial aluminum alloys

PREVENTION OF SCC
Max. pit Avg. pit
Alloy
Temp (F) depth depth
designation
(inch) (inch)

1xxx Al 69-172 a Solution heat treatment

temperature and followed by
2xxx Al-Cu-Mg-Si (3-6% Cu) 379-517 b
slow quenching.
3xxx Al-Mn-Mg 138-276 a

5xxx Al-Mg (1-2.5% Mg) 138-290 a Choose material which high

resistance to SCC
5xxx Al-Mg-Mn(3.6% Mg) 290-379 a

6xxx Al-Mg-Si 152-379 a

Selection of suitable anodic
7xxx Al-Zn-Mg 379-503 b coatings
8xxx Al-Zn-Mg-Cu 517-621 b
∗(a) No known cases of SCC,
(b) SCC occurred in service but can be avoided
A study on the corrosion behavior of aluminum alloys in seawater

 In this study, the aluminum alloys AA5083 and AA1100 were tested at 23º and 60ºC in stagnant natural
seawater of pH 8.2 (measured at 23 ºC) with a salinity of about 35 g L -1

Alloy Si Fe Cu Mn Mg Cr Zn Ti Al Temper designation

1100 0.152 0.508 0.061 0.004 0.0015 0.0006 0.0016 0.015 Balance H14

5083 0.138 0.370 0.013 0.612 4.25 0.1613 0.005 0.015 Balance H16

Figure.9

Microstructure of aluminum alloys (1000·) etched in 0.5%

hydrofluoric acid: (a) AA1100 (H14) and (b) AA5083(H116).

 microstructure is characterized by irregularly shaped intermetallic

particles and their surface distribution is not very homogenous

(a) (b)
16
 A study on the corrosion behavior of aluminum alloys in seawater

 coarse typical constituents of AA1100 to be (Al, Fe) and (Al, Fe, Si) containing particles,

corresponding to Al12Fe3Si2, Al6 Fe or Al3Fe.

(a)  For AA5083, the finer particles are mainly Al–Mg, Al(Si, Mg), (Al–Mg–Cr) and Al(Mn, Fe, Cr)

 For AA1100 The Al6Fe, Al3Fe and Al12Fe3Si2 particles are known to be cathodic to the aluminum

matrix. When exposed to seawater, tend to promote pitting.

(b)
 For AA5083, Mg content exhibits continuous intergrannular beta-phase (Al8Mg5) precipitates, are

anodic to the aluminum–magnesium matrix, enhances susceptibility to stress corrosion cracking and

pitting corrosion

17
 Figure.9

Potentiodynamic polarization curves for aluminum alloys (type: AA1100 and

5083) in seawater at 23 and 60 C (scan rate is 1 mV/s).

 The potentiodynamic polarization curves

reveal that the AA1100 exhibited more
positive Epit values at both test
temperatures, indicating better pitting
corrosion resistance of this alloy in seawater
compared to alloy 5083
 The intensity of the pitting attack increases
with increasing test temperature from 23 to
ALLOY temp Ecorr (m V SCE) Epit (m V SCE) 60 C.
AA1100 23 -920 -575  The difference in pitting resistance is related
60 -1160 -615
to the difference in intermetallic particle
AA5083 23 1950 -680 characteristics present in the two alloys
60 -1185 -725
 Figure.10 Figure.11

Variation of seawater corrosion potential of aluminum alloys (type: AA1100 and

Variation of seawater corrosion rate of aluminum alloys (type: AA1100,
5083) with time.
AA5005 and 5083) with time

 Figure.10 presented reveal fairly low  Figure.11 indicates that the alloy 1100

corrosion rates, indicating the resistance shows more noble and stable corrosion

of these alloys to use in marine potential values than the alloy 5083. This

environments. result agrees with those of Fig. 9

Figure.11

Optical photographs (a · 50) of surface morphology of aluminum alloys specimen after the
potentiodynamic polarization experiment in seawater at room temperature: (a) alloy AA5083
and (b) alloy AA1100

 Pit morphology on potentiodynamically

polarized samples showed hemispherical
isolated pits on the 5083 alloys. The 1100
samples, however, revealed higher numbers
of shallow pits.
 The results obtained in this study indicate
that the type of intermetallic particles in
aluminum alloys plays a major role in
passivity breakdown and pit morphology of
aluminum alloys in seawater.

(a) (b)
REFERENCE

1  Ahmad. Z., Principles of Corrosion Engineering and Corrosion Control. Jordan Hill, Oxford, 2006.

2  Alcan . Corrosion behaviour of aluminium in marine environments. Chapter 10

3  H. Ezuber et al . A study on the corrosion behavior of aluminum alloys in seawater. Materials and

Design 29 (2008) 801–805.

4  P. Spathis and E. Papastergiadis. Influence of seawater composition on SCC behavior of anodized

1050 Al-alloy. Anti-Corrosion Methods and Materials, Volume 60 · Number 1 · 2013 · 45–50

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