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- 112 -

NOTE

ON

CORlli)SION

Co~.x;:~~.Q!l 'is the destructive

attack on a metal through

chemical and electrochemical-reactions


,,_.---.

-physical causes

'

~ '<, ...._Deteriora tio~)by

wear .. ie also included

1.

,
'?

attack. accompanies
. .

by the environment.

such as errosion, p;alling or

i~ corrosion.

In many cases, chemical

physical deterioration.

'( ~

f:

. -

some1 metals (e.g., the platinum, mercury) are

Although

found in the earth's crust in more or less pure state, others,


~such

--

02

..

normally found in combination with

Al. and Zn'are

-~--....c:-~

...

~~-

or other elements.

as.Fe,

These compounds are highly stable ther-

'

..

'

-modynamically
.

of .this

with respect to the pure metals. A consequence


-. . . . ....
stabili-ty
.Ls that once a pure m_etal has been extracted

it often exhibi~s.a
,.' atmo~pher,

tendency, when exposed to an oxi~izing

to rev:~r~ to. the combined state.

is .referred_. to as; metallic corrosion.

The l,atter process

In case of some impor-

.....

t~nt

metals,

e.g.,

~e}/ coz-r-oeLon represents a major

problem,

nd vast sums of money are being spent annually in attempts to


. .
. - , .. .
.
.I

pre~.~n~. or. minimi~e


. !

1.ts e.ffect

The products of metallic corrosion are ionic in nature,

and corrosion.mechanisms
thereto~~

b;-dl

They may

;~~-;sed in term~ of ~!~!!!~!!~!!!!~!_2!!~1?~~.

An understanding
corrosion

involve electron transfer.

of corrosion mechanisms is very necessary if

is to be effectively controlled~

Corrosion

mechanisms.

one example of corrosion that we have already met is y.iven


by.!!!

electrode

in the Daniell cell.

When this cell discharp,es

113 the zinc

dissolves:
eay that in the

we can

the zinc corrodes

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+; +

>

up bv~ the reduction reaction {in the Daniell cell,

the reduction

is the deposition of copper according to

Cu2+ + 2 e

Cu

I//
In aosence of th1.a reduction process, the corrosion oC zinc~-wou1d

not take place.

~~er,, etallic corrosion can occur when a single metal

in

is placed

a corrosive

environment: e.g., pure 'zinc in dilute

acid.
.

, .

It is now considered

that the surface of a corroding metal is

divided up into, sometimes numerous, anodic areas and cathodic


areas.

__ The coabi.nation-of'

one anodic and one cathodic reaction

forms vb.at is known as local galvanic cell of corrosion.

Numer-

ous~1oca1 cells thus occur' on the surface of a small piece of


meta1.

This shows that corrosion is electrochemical.

on an anodic area of Zn
disso1ation

the oxidation reaction (i.e anodic

vhi.ch leads to the loss of etal)


.

Zn2+ +

Zn

2 e

takes p1ace.
On

ca.thocli.e

place.

1..

area

a corresponding

2 u+

'-~- . ,_.. : ,.-</

2 e __

,.
r

..

,._

--

reduction

In d~lute acids the aoet li~elJ

reaction

reduction

... ta_k~_s

reaction is

~~

to the evolution of H2 gas.~

leading

'But why should these different anodic and cathodic areas exist
on the surface of the zinc?
In the baniell
cathodic

cell the tw~~different

because

of their different stnnclnrd electrode potJm_j;-

ials,\the metal witb th~_more


.

--~

~athodic

------

metals are anodic and

+ve potential (more noble) being_)


-

i8nd the one with the more -ve potential (more active)

- ~

being anodic.
In case

dr

a single piece of zinc, it might be expected to be

quite uniform

in its properties.

How, therefore could the sepa-

rate areas arise.J


t ';

1-

Metals

of
-

~--..-:ra~e
_,.

-~:;~~g~~-~~~~t~~.~~il1
~~~!._E~.s~i-}~~atoms of
_7At"'~..J.'"""'.-.-lw.

areas

--

If very small amounts

m~t_a~ _at--~~-~- s.~r~~ce would const1_:.:i..!_e ~!~i~~~~E!~-~!!!!!~~~

this
--....--::':-:..

are seldom compl~tely pure.

..., ,

'-.C

-~--~----~--

--.....-.... -

and these could be quite sufficient to permit a measurable

--~..:~

! ~----

of corrosion.
~
. ! f
1

'i

'

If, ' e.g.,


impurities
were in the rorm or
.
.

,, .

copper, and the dilute


acid also contained copper ions then a
..
~
( ;

whole

aerie~ _o~

.!!!.!:~!!~E!_~~~!~!!_!:!!~
(local
.

..

surface of _the metal.

gal vnnic

~-ells)

In confirmation of this

envisaged

on'the

mechanism

we might note that zn will dis~olve much more readily

in HCl acid if a little CuS04 solution is added.


!

2-

However,

' ! .

!!~~-!~-~h~-~~~~~~-~!-~~!~-~~!~-~~~~!_!~E~!!~!~~

metalscan still corrode, though the rate o~ corrosion may

-----------------------

be
~)

iess .rapid.

Th~s.can

One_important:
uniform,

be for a variety of reasons:

reason being that metal aurraces are not

when considered at the microscopic level. There

. . .

r -., ....

;: ._.,.,. ..

- 115 will ' e.g., be different


crystal

faces exposed at

different

points at the

surface and these diffe~.


ent races will have slirn..
- .. '':-.
tly rli~ferent electrodr

.:"';'_

po-tentials.
_ . . . . -. ~ -- ~ .....~ ....
~

..... ....

,_,,.

""':"'-.

.... ,"'!.~

..... .,,~)or"

..

....

Thus consider the


tion of' zn

~A

r
diEsolu-

in pure ;:cids.

a~no d.a c area


cathodic area

In thi.s caee the etal


local galvRnic cell of corrosion
-~-~!:'..f~~.!:-1- .:'I. ~-~9.~--~-~~ g~.f_!~~_:>,

since Zn (e0

'-~~~~~~~~~~~~~~~--~~-I

-0.1~V)

. ::.:..:....::.. .... .. .

is above

actiTe with
For

this

-~-----.

H2 (e0 =zero)
respect

reason

in the electromotive series, Zn is more

to hydrogen
chemical

the

sn .,_ 2 HCl

proceeds
that

(which is more noble than 7,n).

reaction: .:

ZnCl2

in an e1ectr.oc}temical

on the

heterogeneous

+(Ii~)
The given

manner.

Zn surface the

d Lag r-ara shows

part (A) will act as


.

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

taken up b7 211+ :ions


cathodic) rea.ct:l.on
2 ..

and an anodic reaction occurs according to

valency of

in
On._(B)

the metal f'r-om (A.)

2 e

leading
~

the

to

the two electrons are

from the solution.and a reduction (or

occurs
-+

(B).

the

The electrons released

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.

balanced because the electron


in the second.

i_!.,~e presence of strain in the metal')

when rivets pass through a metal and extensive

fo~.~xample,

corrosion in these areas may represent a serious hazard.


Even stra~n

.r:

in the metal cause corrosion

to_ take_ 'pLace in

the area under ~ .,strain,


.::!.-.

_a~ the

of the strained area

!I
I I
\.\-.
differs
.. ~......_~--;=:;y--~, .. ,- -.

potential

slightly
:-
.

unstrained

---- ~

. as .~n<:?.c!.e

...

from the surrounding

parts.

Unstrained pa r t s
(cathodic areas\

$,trained area acts


or less noble) and in

they will ~issolve,

the unstrained

~!

l:-~,"'...

(active

acid media

Strained part (corroding)


(anodic area)

while

areas act as cathode

(more noble) at which hydrogen

liberates.

In the above mentioned


more

'
noble
metal)

(in which H2 evolves on the

ihe type of corrosion in this case is known as

-- --~---~ ~

evolution type of corrosion.

hydrogen

In the above.examples,
.

as an acid
corrosion

solution.

the envtronment

has been considered

Among

one may cite air:


,.

liquids

examples

used in industry.

the

(o2,'

0th.er environments which cause


tt2o,

co2),

see

water and va r-f ou s

-----

- 117 -

Corrosion
The

Of Iron

(Rusting of Iron)

iron

rusting of

iR a well

whteb w~ eee in our every-day

Anodic proceee:

Fe

Th" .. cnthorlic proce~A


if

iron

the

is vel.l known that

Fe2+

and

invo'lvied.

Thus

+ 2 e

could be the same RR described for zinc

in an acidic

1;on will

corrode

some other, cathodic

conditions

corrosion

of

life.

--\~

corroding

were

known example

environment

1t

or alkaline

unde r _neutral

must therefore

reactions

thie reaction involves

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

eube tanee.. of variable

equation

for

the

formation

composition

known -~s_

(in acid medium)

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

Pe(OH)2 part of which remains (unoxidized),

The H'ern8t

the

o2

complex

(contains

rld.e

at

theee0~~~one, prod~ced at ~b~- c~~~ode

.~e(Oll)3, Pe203 and ferric carbonate

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

formation of hydroxide ions

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

that the potential

pendent

on the concentration

,.

different

the_Q2_=-E!~_!!!!~
. ~~e

areas

of a cathodic
of dissolved

are exposed

to different

will be ~ore cathodic

22=~~f!!~!!~_!!~!!

( l~ss

noble)~

immersed' in water the

partially

corrosion
This type

o2.

If, therefore,

concentration

(more noble)

of 02,
than

a pt ece of Fe

o2=.concentration

1a

will be great-

of the water: this area of the metal will

est at the surface


therefore

If

area in water is de-

act as acathode

to the submerged area (anode) and

of the submerged

area will then take plnce.

of corrosion

is known as Differential

oxygenation

corrosio~~
The
iron

figure

below

corroding

shows anodic and cathodic areas on a piece

in water.

Corrosion

or

takes place below the

surface.

-===--

Fe rod

anodic area
Fe ~Fe2.+

+.2e

..
The prevention

of Corrosion.

This can be achieved

1.

The commonest
the metal

in several ways:

way of preventing corrosion is to insulate

from the corroding atoaphere by a suitable coat-

ing such as paint. So long as the paint completely covers


the surface is.not
will.not

occur.

porous and remains undamaged, corrosion

- 119 -

2.

Alternatively

a metal coating can be applied such as chrom-

ium or

Zinc, e.g., provides

zinc~

-reeiatant
being

3.

for iron,

coating

a very

the process of application

known as galvanizing.

A third

type

of protective

can be produced

coating

ing the metal wi_lli-.6_sui-ta-bl-e-~r-e.agent.


----------

resulting

. --

from expoeure

naturally

sometimes,
further

4.

corrosion

effective

sufficiciently

atmospheric

Oxide coatings,

-------~--~

often

~~~~t'ff!i?r

---

of. the metal. to air, are

hard and coherent to protect from

effect

.-_

. .

bl _reac~-=---

Other methods of corrosion control depend onpreventing


__ either
.. using

the

or

anodi~

~-

cathodic

reaction .f'rom taking place

'

'

substances known ae ' iilhi bi tore. Hal-ting one of thesre.. .reac-

tions preve.iiis the eiectron


essential

transfer

processes which

are

for the start oC the corrosion. There are

anodic
-------

nd cathodic inhibitors.
----- -~----=- ---=-

.;

'

------

'

Protection.

Cathodic

Protection
very

by

against

interesting

corrosion

application

or

is

done in

several

ways.

electrochemical princjples is

te be found in cathodic protec~ion of metals: this is used often


for buried etructuree nuch as ~pelinee. Cathodic protection may be

1- Galvanic

(1--,,.}t -.; t_J{,(

/'!!''l-' , . . ,

protection. In the galvanic

or

~ protection

~~-~-:.,... __ a~ti_V:e ttet~.l,

~ 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 -

an9de of a galvanic cell and iseacrificially

corroded,

the structure1.being ~hereby protected.

2.

PolarizationProtection.
In polarization

protection

'
ia a1soestabliehed

cell

but

'

in this case a' battery is


lntrL

included in the circuit (see


t

f'igure).

Hence, th~ positive

e1ectrode:can-be

any conducting.material

p'lati_num, . or, scrap metal,


-

r-,,_..: -,.

-- _...,.

the. battery
. ....,~------

leeh- .le

:. 6 f~)

such as graphite -

maintaining the stru--

_.__

cture at a sufficiently negative potential to prevent


,. _:.=-.--~

-~-

corrosion.

___,

~..-~..:..u:~.::__:-~~~

--~~
Corrosion

,.,. ... -

will be studied in detail in a separate course.

: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

prnc~R~~~ previou~ly rtln-

These nre:

on the type of metRl and the nature of solution,

Dependent
nn nno~~

mny hr.hnv~ nct1vP.ly

vhen Cu is

nn~ di~~olv~ in the elPctroJyte.

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:

overpotential when the slov

3tep is either the

of a metal atom from the Metal lattice, or a

transfer

is represented
cteristic

(1 )

+ 2 e

rencti.on.

In

thi!l cane , the

ove r-po t.e n t t a I

by a Tafel line and a Tafel equation chara-

of acti.vation-control
. I

b)

Concentration
si~n

or

polarization

when the ~low step is the diffu-

the metal cation fro the solution near the anode

to the bulk oC solution.

Gas .EW'olu tion

: Such

as 02 and

the halogens.

This

occurs

on inert electrodes (e.g., noble metals like Pt) which are


not
~-

active, and do not undergo anodic dissolut]on.

Anodic

Oxidation Of Inorganic Compounds: also on inert

.electrodes.

4.

~nod~c Oxidation

or

Organic Compounds: also on inert electrodes.

- 122 Anodic

5.

Of Fuel Gae

Oxidation

i~ a fuel cell, such as the

oxidation of H2 to H+ ions in the 112/02


6.

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~

solves spontaneously (anodic reaction) and the cations


more

noble

metal

are reduced

and deposited

(cathodic

of the

reaction).

This is a displacement reaction. Such a displacement reaction


is the basis

of co r r-o a Lon which involves.

a) a partial

anodic

metal dissolution reaction (corrosion),

like the dissolution


b) a pa~tial

of Zn in acid solutions~

--

~~d

...

cathodic reaction which exactly balances the anod-

ic ~eaction.

e.g., the cathodic reduction of H+ ions to form

H2 gas as in the case of the corrosion of Zn jn acids.


Howaver.
been

mentioned

another

important anodic.~eaction,

which

ha~ not

before, still exists, and this is the anodic

oxidation oC metals
When exposed

to form oxide films on the anode surface.

to air, metals undergo atmo~pheric oxidation


I

and oxides
dependent

oC various

thickness are produced on the surface

on the nature of the metal and the composition of

a~r (apart Crom B2, 02, H20 vapour, air may contain other ga~es
resulting

rrom'various

industrial plants).

When thin oxide

rtims or other thin films (e.g. silver sulphide) are formed on


the metal in

air,. . the reaction ia called a tarnishing reaction .


Kuch thicker oxide films can be produced as a result of corrosion,~~~

the rusting of iron.

It is believed that the

- 123 -

oxidation of metals (thin and thick oxides) proceeds

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.

In Auch an introductory couree, one may concentrate


ox\dc

flle

sui.tRblc

rormed

hy

polarizJn~

el-ectrolvte.

Dependent

the met~l

on the

nR nn anode in a

on the type of metal and nature

. of eolut1nn one may have:


t:

,.

'

-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
!____

~....

...

,., ..sJcJ~;,._th1-ck oxide


-:-

..

Note th.Rt:

or more.

1 Jl (micron)

.'.

l m~ter

io-6

met.er

100 c
10-6

lOOxlo-

1010

104

= 1010

.A

-----------

f"l.l.lft~ are ~~rm~d on cer~tn mPtRl~~

t.!:.

''.such as nfo.bi

Wll

~!~.b) and tantalum

(Ta)_:___.-/

. . --::-.------:-------- --=:~. - . ~----------=.-::::::


..!~-

=::

A pa~sive metal does


not und~r~o d1.ssolutton

or corrosion.

Tvo types of pasgivity

are ~oosldered:

Wh<'n a piece

------ ---

or

iron iR 1-ereed
---

occurs. and the aebll disso1Tes

~--=----

in dilate HN03

corrosion

-------~-

giving rise o ~as evolution.

- 124 However, .. when

iron ie put in

HN03 (70

concentrated

o~
'

more), no reaction occurs


(no gas is evolved),
metal

surface

Fe

J Fe /

and the -

10/ HN03

dil HN03

bi
r ght

remaine

Corrosion

Therefore, it is said that

passivity

HNOT~ causes the

concentrated

passivity of Fe. This pansjvity


arises

as a result

bf a thin ( a b ou t

SO')
A,

transparent
the entire

oxide
metal

vents .the metal


oxide

coherent,

film which covers

Metal

from contacting the solution.

is

surface and pre-

fi~m protects

of passivity

oxide

of formation

Therefore, this

the metal against corrosion.

caueed by a chemical

(cone

HN03)

it

Since this type


ie cnlled

passivity.

chemical

-~--- -=- -

_..._ -- ---------

*'~~~.l$.~~'ft~}1l

---

type

~.:.,;.-Thie

of pasei vi ty is produced by polarizing the metal to

be passivated
For
ions.

ae an anode in a cell using the proper

exe.mple, when we passi va t e


the

line (ab)

electrolyte.

iron anodically in H2so4

solut-

metal starts by dissolving actively along the Tafel


as

shown

in

the follow:i.ng

fil is formed (similar to that

figure.

At (b)

an

oxide

formed in chemical passivity)

Thie oxide causes a resistance to the passage of current,


the-result that

the current (and

ws abruptly along (be).

with

consequently the c.d.) decreas-

The potential corresponding to this


I

sudden decrease in c.d. is called the paasivating potential (EP).


Thie potential is sometimes known as the Flade potential.
-

- 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-

cterized by a constant low c.d. although the potential increas-

es '"'"to

more poei ti ve values.

The

(cd) is called the passivity region

--

( Pe.e~)

e_es-ts

electrons

~;,.,,....,;;;.._-.,-,.xr-

.. - ..;

..

. .. ~

line

wher~ a stable oxide film


-----

on the surface. (Thi~- o~~~~---~a

-.=::..-:.:::::-...::::::::___

or

-1 -

region represented by the

_,,____

a good conductor
~

------

Therefore. when the anode po~ential

- . . - -- -- - ---

,j_

until the eYolution of 02 becomes thermodynamically possible,

02

evolution starts and becomes visible to the naked eye at

the poi~t (d).


(de)

o2

eYolution r~leee the c.d. along the line

vh~ch represents what

evolution

reeulte fro the paeeage of electrons from OH- ions


...t:.7:'-.. r...."'.;.;.';::.'.1"1.--

to
'-

........... ~rod"4:,00.

the
....

o2

is known as transpasaive region.


;

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-

The ~xy~en gae ta evolved on the

- 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).

Thie is because the paeaage of current

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).

When a typical valve metal (Nb or Ta)

is made the anode.in an electrolyte which does not dissolve


the_ metal
--

--

or oxide, the thin oxide film already .formed on the


'
metal by tarnishing Teactions grows to a considerable thickness.

Conside~ a three-phase
system (metal/oxide/solution) with

metal

two phaee

boundaries the Ciret

phaoc

betwee~ metal and oxide,

ox i de

boundary
(1)

phnao

ao l u t t on

houndnry
(2)

and the second between


oxide and solution (see figure).

The passage o.f an anodic cur/

rent in thie system is brought about by:


atom info a cation which is ____
transported
o t a me t a 1 ..,.

1) The oxidation
across
_,

boundary
(or interface), then through
the me tal/oxide
~
~-

the~ide in the direction of the solution.


1

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.

:::::::::=:

3) Cations and anions (e.g.

0--) have their characteristic

,,

... ''

..

,J

- 127 -

Therefore,

the growth of oxide occurs in the middle of the

. -----------------=~oxide

phase.

This

ia

illustrated

in the follo..,1.ng. figure.

When a valve metaJt-~~~~~~~~~~....,,,_,.--~~~~~~~~


is nnodically

polari?.-

which favours
growth)
c.d.,

solution

metal

e d (in a solution
oxide

at constant

i.e. fralvanooxi 1fr p:rowth


(new oxide

etnticnl1y. nnd itn

=cation

potential. (E) as

easured ap;ainst a

-'

suitable

ref"erence

the f'ol lovlng


rises

'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

linearl.7 with time along

the region (A) reaching very


high potentials

200

(e.g. 200 V

vit.h
Th
with

E
the

appearance

on the

surface of a Yariery of interference coLeu.re

{golden yellow,

blue, pink. etc).

cqnstant c.d.

These colours

indicate

that an oxide film is


.:;:;:

formed on the surface Rnd that


-..-- -

ti-"e

"J.

{,i)

------'7.....

its thickn~se increasefl when the potential inan?lJ.M~. The rate


-

oC increase oC potential with time at constant

c..

(i)

in region

- 128 -

(A) is known as the oxide formatiori'rate


(dE/dt)i

=oxide

~hie can be explained

In the electrical

formation

in the ~ollowing

( 2)

rate
manner:

circuit, the. reference electrode remains the

same, and if we assume that the po~~ntials (~1 and 2)


two phase boundaries remain constant
current,
(~ '<f-J...<'c>-?te

(1'.Y"' is

due

during the passage of

of the measured potential

the increase
j

to

the

at the

(E) with time


-~

inc reaee

in

the .!'oten tial

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

(&)

suggests thnt the electric field Atrengtb

the

increase

(Potent1Rl

(ff)

divided by dietnnce) Rcroes the oxide phaRe:


( 5)
in r~_g1on (A)

~~-~-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 )

Note that the expon~nt1nl

hrcnun~

dealing vith an Rnodtc

thickness

can be determined

th/

~--

the ~olution.
wear~

'\

electric

the

j~

The

film growth ie a

(A) i~ rxpresf'ec't by e e v er-a I e:x-~onei.~ie1 lawe.

rPP;ion
of

anodic

c.d .. (i) remains

.//.-------------j

process.

field

~implP.ot

R.R

(l))

of

the

hR~ n positiv~ sign

pronees:

ox Id e .film

formed

by several me tb od s among which

in
one

(>.)

region
may

cite:

1. TntP-rferometry
2. Ellipsometry
3.

Coulomctry

Let un consider
time(_!) during
the

uses the amount of

which

the coulometric

oxide

growth

electricity

(electrochemical)

the t h i ck ne s n ([)

oum of the pre-polartztion thickness

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

in thickness (66) cauAed by the p~esnge of current (coulometric


increeae of

oxide

thickness)
( 7)

- 130

When

all

the

anodic current

gets f'or (bb)

le used ~for

oxide

one

formation,

= ( 8 n F) 1. t

- . ri t

rQ

(8)

ft

molecular weight of oxide

l!I

density.of

number of faradays required for the formation of one mole

oxide

oxi.de, e.g.'

10 for

Ta205.

J"araday, 96500 coulomb.

'F

= Tolume of oxide formed per coulomb

= amount of' electricity

The units can be introduced in equation (8) thus (note that i


is

in A/cm2).

= (gf!im)(
cm3)(
~
gram

co

:1le )(coulomb)=
omb

cm2

cm

( 9)

The value of (r) is given by:

cm3 /coulomb (10)

It muet. pe emphaaized that only cationa and anions are trans-

ported in region (A), i.e. the conductance

The situation

electronic conductance occurs.


region (B)

is ionic, and no
is different

in

of the galvanoatatic curve.

of' the galvanoeta.tic curve showa that breakdown


Region ( B )
t

occur

This

Ls known as

dielectric

of the oxide film st~j"J


o .
.
martlfe~ted by oacilla
tiona
:in the valve potenbrea.kdown and 1 s
by sparking between the electrode and solu-

tial, and sometimes

region

tion.

Furthermore,
i

time relation,

.e.

(8)

a decrease

shows a bend-down

of the potential/

i n the slope of the potential/time