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5eminor Possivity ond lts Mechonism

Nome uinkor u kokje
ko// No 910
locu/ty of 1ech nqq M5u

Possivity ond lts Mechonism

Possivity
Meto/ is possive when its corrosion in course of chemico/ or
e/ectrochemico/ reoction is /ower ot hiqher offinity of reoction thon
ot /ower offinity of chemico/ or e/ectrochemico/ process
MeLals LhaL normally fall vlcLlm Lo corroslon wlll someLlmes exhlblL
passlvlLy Lo corroslon 9f ls Lhe characLerlsLlc of a meLal
exhlblLed when LhaL meLal does noL become acLlve ln Lhe corroslon
reacLlon asslvlLy ls caused by Lhe bulld up of a sLable Lenaclous
layer of meLal oxlde on Lhe surface of Lhe meLal 1hls oxlde layer ls
formed by corroslon on a clean meLal surface where Lhe corroslon
producLs are lnsoluble ln Lhe parLlcular envlronmenL Lo whlch Lhe
meLal ls exposed Cnce Lhe layer or fllm ls formed lL acLs as a
barrler separaLlng Lhe meLal surface from Lhe envlronmenL lor
furLher corroslon Lo occur Lhe reacLanLs musL dlffuse Lhrough Lhe
oxlde fllm Such dlffuslon ls very slow or nonexlsLenL Lhus corroslon
elLher decreases markedly or sLops MeLals such as zlrconlum
chromlum alumlnlum and Lhe sLalnless sLeels form Lhln Lenaclous
oxlde fllms when exposed Lo Lhe aLmosphere or Lo pure waLer aL
room LemperaLure ln some cases Lhe fllm ls exLremely Lhln and
may be lnvlslble Lo Lhe unalded eye buL lL ls sLlll very effecLlve ln
glvlng Lhese meLals a marked passlvlLy lf Lhere ls a neL converslon of
reacLanLs Lo producLs ln a sysLem Lhe sysLem wlll be chemlcally
unsLable and Lhe reacLlon wlll conLlnue unLll a sLable sLaLe ls
aLLalned 1hls sLable sLaLe ls known as equlllbrlum



lncreose in Possivity
There are two ways oI increasing the passivation and the corrosion
resistance oI metal systems by alloying, i.e. introducing components
which directly Iacilitate passivity (Ior instance Cr, Si, Mo when added
to iron) or introducing components which lower the cathodic
polarization (Pt, Pd and other noble metals Ior stainless steels and
titanium).
Experimental data on increasing the passivity and corrosion resistance
oI metal by means oI alloying with cathodic metals and by other
methods, in particular by the use oI anodic protection, are considered.

Corrosion of passive alloys

)Stress Corrosion







2)Pitting corrosion















)Inergranular corrosion












echanism of Corrosion

1)&niform Corrosion
2)
Uniform .4774843 occurs when there are local
anodic and cathodic sites on the surface of the
metal. Due to polarization effects, these
locations shift from time to time and a given
area on a metal will be act as both an anode
and as a cathode over any extended period of
time. The averaging effect of these shifting
local action cells results in a rather uniform
attack and general loss of material and
roughening of the surface.

2) ntergranular Corrosion

The selective attack of grain boundary material
due to its high energy content. Metal crystals
form in an ordered arrangement of atoms
because this ordered arrangement has a lower
energy content than a disordered arrangement.
Grain boundaries are highly disordered as they
are at the boundaries of crystals which, although
they are internally ordered, have random
orientation with respect to each other. The
disordered grain boundary is often 10 to 100
atoms wide and these atoms have a higher
energy than the surrounding atoms. Higher
energy material can be more chemically active
than lower energy material and thus, the grain
boundary material can be anodic with respect to
the surrounding grains. When this occurs, the
anodic area is small and the cathodic area is
large, thus, rapid attack can occur. The result is
that the individual grains are no longer joined
with the strong grain boundary "glue and
disintegrate leaving a powdery residue and rough
grainy surface.

)Calvanic Corrosion Bimetallic Corrosion
The relative area oI the anode and cathode has a
pronounced eIIect upon the amount oI corrosion that occurs
due to Galvanic Corrosion. A small anode (the less noble
metal, such as aluminium) joined to a large cathode (the
more noble metal, such as stainless steel) will result in a
high current density on the aluminium, and hence a high
rate oI corrosion.The corrosion is concentrated by the area
diIIerence. Conversely iI the area oI the anode is large
compared to that oI the cathode this dilutes the corrosive
eIIect, in most cases to the extent that no problem occurs.

)!itting & Crevice Corrosion
&nder certain speciIic conditions, particularly involving
chlorides (such as sodium chloride in sea water) and
exacerbated by elevated temperatures, small pits can Iorm in
the surIace oI the steel. Dependent upon both the environment
and the steel itselI these small pits may continue to grow, and
iI they do can lead to perIoration, while the majority oI the
steel surIace may still be totally unaIIected.
What is Crevice Corrosion?
Crevice Corrosion can be thought oI as a special case oI
pitting corrosion, but one where the initial "pit" is provided by
an external Ieature; examples oI these Ieatures are sharp re-
entrant corners, overlapping metal surIaces, non-metallic
gaskets or incomplete weld penetration. To Iunction as a
corrosion site a crevice has to be oI suIIicient width to permit
entry oI the corrodent, but suIIiciently narrow to ensure that
the corrodent remains stagnant. Accordingly crevice corrosion
usually occurs in gaps a Iew micrometres wide, and is not
Iound in grooves or slots in which circulation oI the corrodent
is possible.