v

O
CORROSION

V'

""

C/

,/

~/

'-..{'

\.,yJV();/
Iv

Corrosion can be generally defined as "Degra1ation of a metal by chemical or EI ctro-chemical

~
..~
,~_.~
~

means " .

From this definition it is obvious that two mechanisms are involved, firstly an electrical circuit
and secondly a chemical reaction.
Electrical Circuit

( In a corrosion circuit the current

is alwa s D.C. Direct Current).) It is conventionally thought

'that a current passes from positive + to negative ., i.e. om anod( to cathode. In fact electrons
are flowing in exactly the opposite direction, from cathode to anode. For corrosion circuit to
exist three things are needed:

-'~

Anode

An anode is a positively charged area. It becomes positively charged because the atoms release
two electrons each, thus causing an imbalance between protons and electrons, positive and
negatively charged units. In it's passive state, the iron atom has 26 of each, protons and
electrons, when the two electrons are released the atom still has it's 26 protons, but now only 24
electrons. In this state the atom is now an ion, overall positively charged by two units and
written as Fe++. ~n ion is a charged particle, and can be positive or negative, a single ~t()_rnor a ..
H
+
\ .
gr9~P.i>{~!~"!~!.J'~Q~
a~
a-moie~~le.)fhrS1osiiig"oferectfonsc'anl5e"shown
-as:
-Fe'
-+
Fe
"'.'"
'I-is called a positive iron ion. An ion can be positive or negative and is a charged
'.' ."--)2e. The Fe
.,.... q
"""-'
...
/
particle,

."'''-'''-

- --'-'--'--'-

an atom
--,

or a group

,~-~

o'

of atoms.-'
~~~--

-.-

A passive iron atom Fe 26 protons and

26 electrons.

An iron ion Fe++, 26 protons and only

24 electrons

Nucleus

.
Figure 1.1 iron atoms

Painting Inspection Grade 3/2. Rev 1 April 2004

Corrosion
1.1
r"

: L. t;::\ "'t/'\I\"" rrn"

TWI

rrT7.
V If /I

WORLD CESTRE FOR

MATERIALS JOINING
nWl-INnl nr.v

Cathode

A cathode is a negatively charged area where there are more electrons than needed in its passive
state. These are electrons released from the anode. At the cathode the electrons enter into the
electrolyte to pass back to the anode.

--4

Electrolyte

. \ ""

An electrol e is a substance which will conduct a current and be broken do~ b~(diSSociate
into Ions). Water is the most abundant electrolyte and also very efficient.
CI s, alkalis and
salts in solution are also very efficient electrolytes. As the electrons pass into the electrolyte it is
dissociated into positive and negative ions, as shown by the formula:
Simultaneously the electrons couple back with the Hydrogen ions to form two full Hydrogen
atoms, which join together diatomically to form Hydrogen gas. This is termed as being evolved,
or given off from the cathode. The hydroxyl ions return to the anode through the electrolyte
carrying the electrons.

The corrosion triangle, as shown below, can illustrate the electrical circuit. The electron circuh.
can be seen to be from anode A, to cathode C, through the electrolyte E, back to A.
E
~/'

A
Figure 1.2 The corrosion triangle
The Chemical Reaction

From the above we can see that no chemical reaction, (combination of elements) has occurred at
the cathode, or in the electrolyte. The chemical reaction, the formation of corrosion products,
only occurs at the anode. The positive iron ions, Fe++, receive the returning hydroxyl ions and
ionically bond together to form iron hydroxide, which is hydrous iron oxide, rust, and is shown
by the formula: Fe+++ 20tt7 Fe (OH)2 It is now apparent that corrosion only occurs at the
anode, never at ~erm
cathodic protection. If a structure can be made to
be the cathode in a circuit, it will not corrode.

\~,.

...The corrosion triangle shows t~eJh!ee ele..~~_.neede.!Lfor corrgsio~ to occur,~~~?- catp-oge.._~n!!.elec~o~yt~ It anyone oftnese threels-i'einoved from the triangle, corrOSIoncannol"Occur.
:~e one mos commonly eliminated is the electrolyte. Placing a barrier between the electrolyte
and the anodic and cathodic areas, in the form of a coating or paint system does this. Q If
electrolyte is not in direct contact with anode and cathode, there can be no circuit, and so no
corrosion.
\.
Painting Inspection Grade 3/2. Rev 1 April 2004
Corrosion
1.2
"'

:--L~ G:\ ..,1\1\")

Tn",

TWI

rTT7.

V/I/.

WORLD CENTRE FOR

MATERIALS JOINING
Tl'rHN()1

()r.v

V.

The basic corrosion reaction, as explained above, occurs fairly slowly at ambient temperatures.
In common with all chemical reactions certain factors can increase the reaction rate, listed.~l~~d_'
j)
'\
~._w,
\:fAr'~~esome~
c---Steel, in common with most metals, is thermodynamically unstable. The
\..1 ~
,~.
hotter the steel is the faster the corrosion will occur.

:
vi

~\

.J

~~ )~
\.1

\.J

H}'~
~lts. A hygroscopic salt is one, which will attract water and s Ive in it.
When salts are present on a substrate and a coating IS app ied over em, water will be
wn
ou the fi an t e resu tm so utlon builds up a pressure-u-ruJer the filf.1i.,Eventually the film is forced up to form blisters.
ese Isters are called os tic r
hy oscopic blisters, and are defined as 'pinhead sizedWater
'. Sulphates
and
es
0 most common sa
on es pre
ant in marine
,...-....
environments, and sulphates in industrial areas and somet~ltural.
Mrobi., conditi~s,
oxygen). By introducing oxygen into the cathodic
reaction the number of Hydroxyl ions doubles. This means that double the number of iron
ions will be passivated and therefore double the corrosion rate. Shown by :2H2O+ O2 + 4e ~ 40H-

.Presence

of some types of bacteria on the metal surface, for example Sulphur Reducing

Bacteria, better known as SRBS:or1.1EMs, Metal EanngMicrobes.

5
Acids and alkalis
_.6 ~t.
Otherwise known as Bi-Metallic Corrosion.

.~

. ,,' _/-1

-Me~lscan ~.list~

in order of nobilitY-:A noble metal is one, which will not corrode. In

descending order, the lUrtfierdowiitheiist the metal is, the more reactive it is, and so, the more
anodic it is, the metal loses its electrons to become reactive ions. The degree of activity can be
expressed as potential, in volts. The list can be called a Galvanic List, but when the free
potentials of the metals are known it can also be called the,EIe.!!"9M9ti.:v.~lorcesseries or the
Electro-CQemi9~1.series. Below is a list of some metals in order of nobility '\.vitJ1potenti<ikas''measllred using a copperkopper sulphate half cell reference electrode, in seawater at 25oc.
MATERIAL

KNOWN POTENTIAL AV. VALVES

Graphite
Titanium
Silver
Nickel
200
Lead
AdmiraltyBrass
Copper
Tin
MillScale
LowAlloy Steel

+ 0.25 v
0.0 v
- 0.1 v
- 0.15 v
-0.2 v
- 0.3 v

- 0.35v
- 0.35v
- 0.4 v

- 0.7v
- 0.7v
- 0.9v
- 1.0v
- 1.6v

MildSteel
Aluminium Alloys

Zinc
Magnesium

Painting Inspection Grade 3/2. Rev I April 2004

Corrosion
~

: I... ~ ""on.., 'T"11T" I

1.3

TWI
7I
V .f 101
rTT7J

WORLD CENTRE FOR

MATERIALS

JOINING

n=rHNnI or,v

From the list above it can be seen that millscale is immediately above steel on the galvanic list.
This means that millscale is cathodic to steel, and if left on the surface of steel will accel~

corrosionofThesteel sub~

r.t'
-\ -:::;
:

'~

'~iIlscale is fonned durin the rolling 0 oration of steel sections e.g. RSC. RSA, RSJ. 1rhe

oxides 0 iron onn very qUIC y at temperatures

in excess 0

80c.A

e first oxide fonned is

FeO, iron oxide, the next is Fe304 and last of all Fe2OJ.~mmon names in or.drare WustiteL.
~agnetite and Haem~ite.J These oxide
com ressed urin the ro.
0
tion to produce
blue milIscale., The thickness 0 millscale varies fi'om 25 to 100 um. Because millscale is onl
produced aut1Bg rolling, when it has been removed by anysurface preparation method, it can
never re-cur.

)~,
~t,
U~

'}
"~

\
.
:-\'.1

"..,

'" j

"\.,

,\

\
,,'

l
\

i..r1~

"

"

'''"'

/
I
/

"./
_,I""'

./
"

./

,1/

'"

,'I

\..,i

"

~_..J

<,""

./

"

"

'I,j
,

":\

"

)
'.-.'

"-

'\.'\

, )'

'J

\.'."

"'---- ---'....

//

\\,\'"

:.,"\..,("j'.
~

~-.J

f)"

.'.1

"1

- /

<,)

"j")

,)'

'..)

"
r-!"

/
'\.

,; r-"

,J "-

, \..:/
.,,"I
'-..
~'"'

"
"'

"

..r)

I
\

"\\'

f'

/'-

'~V~

Painting Inspection Grade 3/2. Rev 1 April 2004

1.4
Corrosion
,
,

.-: .-1... r.::\""(\{\") Tn Tf

TWI
rT7f7.
1.1/I II

WORLD CENTRE

FOR

MATERIALS JOINING
n'rHNn( nr,v