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Note On Corrosion
Note On Corrosion
NOTE
ON
CORlli)SION
-physical causes
'
1.
,
'?
attack. accompanies
. .
by the environment.
i~ corrosion.
physical deterioration.
'( ~
f:
. -
Although
--
02
..
-~--....c:-~
...
~~-
or other elements.
as.Fe,
'
..
'
-modynamically
.
of .this
it often exhibi~s.a
,.' atmo~pher,
.....
t~nt
metals,
e.g.,
problem,
1.ts e.ffect
and corrosion.mechanisms
thereto~~
b;-dl
They may
An understanding
corrosion
is to be effectively controlled~
Corrosion
mechanisms.
electrode
dissolves:
eay that in the
we can
cell.en~ironment
to
Rive Znso4.
The rate of thi~ corrosion
i a liai ted by the rate at w-hich
- -- ., ....,.
--~
electrons
liberated
by the
oxidation reaction
--- ------~ -- - -~- - ~-- --~ ..... --
zn
are taken
zn2+; +
>
the reduction
Cu2+ + 2 e
Cu
I//
In aosence of th1.a reduction process, the corrosion oC zinc~-wou1d
in
is placed
a corrosive
acid.
.
, .
It is now considered
__ The coabi.nation-of'
Numer-
on an anodic area of Zn
disso1ation
Zn2+ +
Zn
2 e
takes p1ace.
On
ca.thocli.e
place.
1..
area
a corresponding
2 u+
2 e __
,.
r
..
,._
--
reduction
reaction
reduction
... ta_k~_s
reaction is
~~
leading
'But why should these different anodic and cathodic areas exist
on the surface of the zinc?
In the baniell
cathodic
because
--~
~athodic
------
i8nd the one with the more -ve potential (more active)
- ~
being anodic.
In case
dr
quite uniform
in its properties.
1-
Metals
of
-
~--..-:ra~e
_,.
-~:;~~g~~-~~~~t~~.~~il1
~~~!._E~.s~i-}~~atoms of
_7At"'~..J.'"""'.-.-lw.
areas
--
this
--....--::':-:..
..., ,
'-.C
-~--~----~--
--.....-.... -
--~..:~
! ~----
of corrosion.
~
. ! f
1
'i
'
,, .
whole
aerie~ _o~
.!!!.!:~!!~E!_~~~!~!!_!:!!~
(local
.
..
gal vnnic
~-ells)
In confirmation of this
envisaged
on'the
mechanism
2-
However,
' ! .
!!~~-!~-~h~-~~~~~~-~!-~~!~-~~!~-~~~~!_!~E~!!~!~~
-----------------------
be
~)
iess .rapid.
Th~s.can
One_important:
uniform,
. . .
r -., ....
;: ._.,.,. ..
faces exposed at
different
points at the
.:"';'_
po-tentials.
_ . . . . -. ~ -- ~ .....~ ....
~
..... ....
,_,,.
""':"'-.
.... ,"'!.~
..... .,,~)or"
..
....
~A
r
diEsolu-
in pure ;:cids.
since Zn (e0
'-~~~~~~~~~~~~~~~--~~-I
-0.1~V)
. ::.:..:....::.. .... .. .
is above
actiTe with
For
this
-~-----.
H2 (e0 =zero)
respect
reason
to hydrogen
chemical
the
sn .,_ 2 HCl
proceeds
that
reaction: .:
ZnCl2
in an e1ectr.oc}temical
on the
heterogeneous
+(Ii~)
The given
manner.
Zn surface the
the
anode
{act~Ye)
>s Zn2 + + 2 e
Zn
or
The activit7
atos
in
the
(A) is
in th:l.a part
the
Clat
above
part
due to the
fact
is not eai"isfied.
reaction
are
o'C the
valency of
in
On._(B)
2 e
leading
~
the
to
occurs
-+
(B).
the
transported
surface
that
to the evolution
of H2
- 116 Conclusion:
From above
it is clear
that corrosion
is composed
of
two reactions:
anodic
The
(or oxi~ation)
the loss
of met~~,~
cathodic
as the reduction
two reactions
released
b)
dissolu~ion
in thefi~st
tT_~--~-~?_ond reason
are exactly
are consumed
which leads to
of H+ ions.
fo~.~xample,
.r:
_a~ the
!I
I I
\.\-.
differs
.. ~......_~--;=:;y--~, .. ,- -.
potential
slightly
:-
.
unstrained
---- ~
. as .~n<:?.c!.e
...
parts.
Unstrained pa r t s
(cathodic areas\
the unstrained
~!
l:-~,"'...
(active
acid media
while
liberates.
'
noble
metal)
-- --~---~ ~
hydrogen
In the above.examples,
.
as an acid
corrosion
solution.
the envtronment
Among
liquids
examples
used in industry.
the
(o2,'
co2),
see
-----
- 117 -
Corrosion
The
Of Iron
(Rusting of Iron)
iron
rusting of
iR a well
Anodic proceee:
Fe
iron
the
Fe2+
and
invo'lvied.
Thus
+ 2 e
in an acidic
1;on will
corrode
conditions
corrosion
of
life.
--\~
corroding
were
known example
environment
1t
or alkaline
unde r _neutral
must therefore
reactions
nu. t
since
02
iron
be
will
not
~!?!:!:~~~-!!!_!~!~!:_!f_Q2_!!!_~~!"!:!:~!!l_!:!~!~~~~.
}
.,
.. i
The cathodic
giv~ng
rise
a.a is
If'.
corroding
the
renction
to
the
of'ten
are
i;n the
{"~t~
anodic
ions
of" the
produced
: -.
'tation
reactions
. ":"',
of Fe(OH)2
are possible
If
suf'1"icient
leading to the
equation
for
the
formation
composition
known -~s_
cathodic
Eo _ RT ln [OH-) 4
ZiJ
[ o2
reaction is
(Z ~ 4)
by.. o;J~~?;~~fcn_{)3.
te(OH) 2 whl;h~le~~~i~iaed-..
reacts
oxide
is
The H'ern8t
the
o2
complex
(contains
rld.e
at
4 OJC
--)+
oa t hod Le areas
and
in c1ose __ pr~ximity0e~)
precipi
a aore
oC
the
". . '
present further
'-
caee,
anod~_,,r.ea~t-~1 th
resa.1ting
.... 4 e
the
iron
o2
2 H2o +
is:
with
Pe203
the
enrtronme.nt
With
--
co2
........ .. --.,_
to
f-:Perric
hydroin two waya: with 02 to form
for11 ferric
carbonate.
showing
pendent
on the concentration
,.
different
the_Q2_=-E!~_!!!!~
. ~~e
areas
of a cathodic
of dissolved
are exposed
to different
22=~~f!!~!!~_!!~!!
( l~ss
noble)~
partially
corrosion
This type
o2.
If, therefore,
concentration
(more noble)
of 02,
than
a pt ece of Fe
o2=.concentration
1a
will be great-
If
act as acathode
of the submerged
of corrosion
is known as Differential
oxygenation
corrosio~~
The
iron
figure
below
corroding
in water.
Corrosion
or
surface.
-===--
Fe rod
anodic area
Fe ~Fe2.+
+.2e
..
The prevention
of Corrosion.
1.
The commonest
the metal
in several ways:
occur.
- 119 -
2.
Alternatively
ium or
zinc~
-reeiatant
being
3.
for iron,
coating
a very
known as galvanizing.
A third
type
of protective
can be produced
coating
resulting
. --
from expoeure
naturally
sometimes,
further
4.
corrosion
effective
sufficiciently
atmospheric
Oxide coatings,
-------~--~
often
~~~~t'ff!i?r
---
effect
.-_
. .
bl _reac~-=---
the
or
anodi~
~-
cathodic
'
'
transfer
processes which
are
anodic
-------
nd cathodic inhibitors.
----- -~----=- ---=-
.;
'
------
'
Protection.
Cathodic
Protection
very
by
against
interesting
corrosion
application
or
is
done in
several
ways.
electrochemical princjples is
1- Galvanic
/'!!''l-' , . . ,
or
~ protection
~ af..\) ~ ; close
to
the
connected
(see
figure).
steel
structures
a more
e.g.
.!.!!- or~
ie buried
to. which it
structure
by an
e1ectrical
This
metal
ie
condttQ tor,
forms
the
e.
,. .,......
,...,..,rat)n
~ .,.. .te
- 120 -
corroded,
2.
PolarizationProtection.
In polarization
protection
'
ia a1soestabliehed
cell
but
'
f'igure).
e1ectrode:can-be
any conducting.material
r-,,_..: -,.
-- _...,.
the. battery
. ....,~------
leeh- .le
:. 6 f~)
such as graphite -
_.__
-~-
corrosion.
___,
~..-~..:..u:~.::__:-~~~
--~~
Corrosion
,.,. ... -
:r h<..
] ?]
,~~cntrq~<rxtt'tl'F.ir~rf,ft~~!!HAT;[QI
~ '. ~1._, ... C:'..)''.tt'"'c )-.',(.,.,-, ..
One ay
~usoed
summRri~~
in this cour~e.
e , fY..
tj
..
1--;P. ....'l'/.z
z.ea
LI
the Bnorlic
These nre:
Dependent
nn nno~~
vhen Cu is
mnrle an an nnode
in acidified
cuso,.
~olu-
onn
Cu~
Cu
of Rn()d i c dissol
ThP. rroeefHJ
n t f.on
vi th an overpotential which
ciated
a) ActiYalion
detochaent
charge
of a
r:t('
t-.n l
Et node
1 ~ :tr.~o-
may be:
transfer
is represented
cteristic
(1 )
+ 2 e
rencti.on.
In
of acti.vation-control
. I
b)
Concentration
si~n
or
polarization
: Such
as 02 and
the halogens.
This
occurs
Anodic
.electrodes.
4.
~nod~c Oxidation
or
- 122 Anodic
5.
Of Fuel Gae
Oxidation
Spontaneous
fuel
cell.
Anodic Dissolution
This occurs when an active metal is immersed in a solution of a salt of a more nohJ.c
metol.
The actJ.ve
metRl din~
noble
metal
are reduced
and deposited
(cathodic
of the
reaction).
a) a partial
anodic
of Zn in acid solutions~
--
~~d
...
ic ~eaction.
mentioned
another
important anodic.~eaction,
which
ha~ not
oxidation oC metals
When exposed
and oxides
dependent
oC various
a~r (apart Crom B2, 02, H20 vapour, air may contain other ga~es
resulting
rrom'various
industrial plants).
- 123 -
atmoApheric
by electrochemical
The
re~ctlonA.
subject of atmospheric
oxide
film formation io usually dealt with under the subject or r.orro1 n 111A.ny 111onogrnphn
nion
nnd
t;e.xt bo ok a on corrosion.
flle
sui.tRblc
rormed
hy
polarizJn~
el-ectrolvte.
Dependent
the met~l
on the
nR nn anode in a
,.
'
-r:.,
,... ..,.
,.,,,
-----Here
.,,,,.....
tt)
Formntion
. -~.
P.tttdi~ct
of
very thin
under
the
t Les ;
po e e f. bill
we \ha,;.e tvo
, ,..
_,_.
oxide
f,
(50 1).
films
euh.1ect
cf
t ion
of'
thick
oxide
:fi l~
and
the
rroc~!l~
is
rassivity.
..
b) Pormn
mr..y reA.~h
whi.ch
thl clrn~m1
of
\:
r~
108
1 .
.. .
A: (Rn~trom),
. 1 ~
.- (-~ic~on
since
'
:;-}-._.;.~--~-~
,. 'v ,
.
.-
.. "\
~;
,.
valve' metals
!____
~....
...
..
Note th.Rt:
or more.
1 Jl (micron)
.'.
l m~ter
io-6
met.er
100 c
10-6
lOOxlo-
1010
104
= 1010
.A
-----------
t.!:.
''.such as nfo.bi
Wll
(Ta)_:___.-/
=::
or corrosion.
are ~oosldered:
Wh<'n a piece
------ ---
or
iron iR 1-ereed
---
~--=----
in dilate HN03
corrosion
-------~-
iron ie put in
HN03 (70
concentrated
o~
'
surface
Fe
J Fe /
and the -
10/ HN03
dil HN03
bi
r ght
remaine
Corrosion
passivity
concentrated
as a result
bf a thin ( a b ou t
SO')
A,
transparent
the entire
oxide
metal
coherent,
Metal
is
fi~m protects
of passivity
oxide
of formation
Therefore, this
caueed by a chemical
(cone
HN03)
it
passivity.
chemical
-~--- -=- -
_..._ -- ---------
*'~~~.l$.~~'ft~}1l
---
type
~.:.,;.-Thie
be passivated
For
ions.
line (ab)
electrolyte.
solut-
shown
in
the follow:i.ng
figure.
At (b)
an
oxide
with
- 125 -
~
~
~
'>-t .
~
c
a
Thermodymudc
.
to he
caleulation<have
f'orwed
on iron
the most
""'
.: . . tic
pnnf!ivntinP,-potentinl
at the
~~,
. _,. . -..;;:,. --- - .=-: ~-~ -.: _:_ - ~-"~,~.--.
remaina
The meta1
shown t~
JlR.fHtive
alonP. the
line
~i
likely
Pe o
is
--.:.:- ..~~:-~~ -
( cd)
is
which
oxide
chara-
es '"'"to
The
--
( Pe.e~)
e_es-ts
electrons
~;,.,,....,;;;.._-.,-,.xr-
.. - ..;
..
. .. ~
line
-.=::..-:.:::::-...::::::::___
or
-1 -
_,,____
a good conductor
~
------
- . . - -- -- - ---
,j_
02
o2
evolution
to
'-
........... ~rod"4:,00.
the
....
o2
ortde.
Thie
is
l'W'~fl..__~"'e:""-~
ca1 to ~orm
o2
oxide surrace.
gae and
followed
n2o.
'"""'r~ ..
by
.~he
~-
..,,_.. - -~ ..--.
combination
.::-.
is increased
"'
1.-""
of' OH radi-
- 126 -
...
The name valve metals is given for a number of metals which
allow the free passage of current in one direction (cathodic
direction) and hinders the current passing in the other direction (anodic direction).
in the anodic direction requires a higher free energy of activation than that required for~the cathodic direction. Typical
valve ~etalo are Nb (niobium) and Ta (tantalum). Lesa typJcnl
valve metals include Ti (titanium), Zr (zirconium), Al (aluminium) and W (tungsten).
--
Conside~ a three-phase
system (metal/oxide/solution) with
metal
two phaee
phaoc
ox i de
boundary
(1)
phnao
ao l u t t on
houndnry
(2)
1) The oxidation
across
_,
boundary
(or interface), then through
the me tal/oxide
~
~-
2)
ii
n (resulting from the decomposition
Th~- _tr~~~_po~~=-<?:-~-~ ~
~
of water at the oxide/so~ution boundary) through the oxide
--
in the direct.i.D.ILQ_f
- -
~---the metal.
:::::::::=:
,,
... ''
..
,J
- 127 -
Therefore,
. -----------------=~oxide
phase.
This
ia
illustrated
polari?.-
which favours
growth)
c.d.,
solution
metal
e d (in a solution
oxide
at constant
=cation
potential. (E) as
easured ap;ainst a
-'
suitable
ref"erence
'iR
f'ollowed
curve from
whi.ch
es
e. function
of" time.
it
a ppenr-s that
we ohta.1 n
po t e n t La l
the
200
(e.g. 200 V
vit.h
Th
with
E
the
appearance
on the
{golden yellow,
cqnstant c.d.
These colours
indicate
ti-"e
"J.
{,i)
------'7.....
c..
(i)
in region
- 128 -
=oxide
In the electrical
formation
in the ~ollowing
( 2)
rate
manner:
(1'.Y"' is
due
the increase
j
to
the
at the
inc reaee
in
difference
Q Ef") -"'_':'.'"."
the growing oxide. phase with time due to th~_ consu~ption ~f the
~current
in oxide growth
(see figure).
Solution
oxide
metal
-}-~---------t-:-----~~---
reference
cathode
f!f 2
~~f~~---
~---6
>
Hence:
The increase
increase
+constant
id th1cknesa
(6) is directly proportional
to
of ox e~~"---~-~
(or growth)
) .--:-:.i-herefore, the oxide formation
--------
rate m-;;;
in
( 3)
{Er
be expressed
or
by
(4)
,,
,,.
.;.'
'.
~;
\,.:,
- 1?~ -
..
The proportionality
or(Er)
betv~en
the
of
1ncreAB~
end
(&)
the
increase
(Potent1Rl
(ff)
~~-~-ns constant
e orrs t nn t ,
conAtant
Long aa the
The:refore, r,RlTnnoetatic
-------
---
relation
1'he
- . -------.. . . . __
-------
bPtveen
which
the
<,
c , d. ( i)
and
f"ield
(6)
A e:xp ( RH )
hrcnun~
thickness
can be determined
th/
~--
the ~olution.
wear~
'\
electric
the
j~
The
film growth ie a
rPP;ion
of
anodic
.//.-------------j
process.
field
~implP.ot
R.R
(l))
of
the
pronees:
ox Id e .film
formed
in
one
(>.)
region
may
cite:
1. TntP-rferometry
2. Ellipsometry
3.
Coulomctry
Let un consider
time(_!) during
the
which
the coulometric
oxide
growth
electricity
(electrochemical)
the t h i ck ne s n ([)
formed
in
nir
(very
passed.
thin, nbout 20
t.
of
(60)
method. At any
the
ox f d e is
due
to the film
o; Lo n s ) plua
the increase
oxide
thickness)
( 7)
- 130
When
all
the
anodic current
le used ~for
oxide
one
formation,
= ( 8 n F) 1. t
- . ri t
rQ
(8)
ft
l!I
density.of
oxide
oxi.de, e.g.'
10 for
Ta205.
'F
in A/cm2).
= (gf!im)(
cm3)(
~
gram
co
:1le )(coulomb)=
omb
cm2
cm
( 9)
The situation
is ionic, and no
is different
in
occur
This
Ls known as
dielectric
region
tion.
Furthermore,
i
time relation,
.e.
(8)
a decrease
shows a bend-down
of the potential/