Lecture 6 - Pitting Corrosion

Pitting Corrosion
PITTING: Extreme localized attack, may perforate metal sheet/plate . . .

etc.

Pitting factor =

d = average penetration from weight
loss;
p = deepest penetration

Undercutting
pit opening usually < 1 mm.

Pits may overlap to give the
appearance of rough, general
wastage.
d
p
Pitting is an insidious and destructive form of corrosion:

difficult to detect (pits may be small on surface, but
extensive below surface from undercutting; may be
covered with deposit);

can cause equipment to fail (by perforation) with very little
weight loss;

difficult to measure as pit depth and distribution vary
widely under (nominally) identical conditions;

incubation period may be months or years.
Pitting of 18-8 stainless steel by acid-chloride solution
Pitting of stainless steel condenser tube
Pits usually occur on upward-facing horizontal surfaces,

and less frequently on vertical surfaces;

rarely on downward-facing surfaces;
pit growth
pit growth
pit growth
Gravity is involved
Mechanism: Has some features in common with CREVICE CORROSION....
consider metal M being pitted by aerated NaCl solution...
Autocatalytic processes
occurring in a corrosion pit
Remember:
inside pit - anodic, rapid dissolution;
outside pit - cathodic, O
2
reduction;
most M
+
will hydrolyse, form H
+
;
positive charges attract Cl
-
ions;
H
+
and Cl
-
accelerate metal dissolution;
high ionic concentrations in pit make O
2
solubility
very low;
high density of solution within pits means pits are
more stable when growing downwards;
static environment accelerates process.

At high pH (i.e. high OH
-

concentration), precipitation of
iron hydroxides and oxidation to
Fe
3+
oxides can lead to corrosion
product caps or tubes around
pits on steels.

Corrosion tube growth mechanism
Metals Susceptible to Pitting
Most often, passivating metals, especially stainless steels, often in
passivating environments (e.g., containing oxygen) but with agents
such as Cl
-
that attack the passive oxide film.

SENSITIZED SS particularly vulnerable (its heat treatment has
depleted the grain boundaries of Cr by precipitating chromium
carbide).

COLD WORKING increases pitting attack, perhaps dislocation
pattern is important.

DISCUSS
ETCHED or GROUND surfaces more likely to pit than polished
surfaces.
Stainless Steel more susceptible than Carbon Steel (though CS will
have more rapid GENERAL CORROSION).
Some alloys developed especially to resist pitting.

Effects of alloying on pitting resistance of stainless steel alloys

Element Effect on pitting resistance

Chromium Increases
Nickel Increases
Molybdenum Increases
Silicon Decreases; increases when present with molybdenum
Titanium and niobium Decreases resistance in FeCI
3
, other mediums no effect
Sulfur and selenium Decreases
Carbon Decreases, especially in sensitized condition
Nitrogen Increases

Pitting Environments

Usually, solutions containing chloride or chlorine-
containing ions (e.g., hypochlorites [bleaches]) have
strong pitting tendencies.

Bromides are also aggressive, but fluorides and iodides
are not.

Cupric, ferric and mercuric ions promote pitting . . .
easily reduced cathodically and do not require dissolved
O
2
; CuCl
2
and FeCl
3
are extremely aggressive (latter
used as a test solution).

Thiosulphate ion (S
2
O
3
2-
) may also promote pitting.
Relationship between pit depth
and the number of pits
appearing on a corroded surface
Evaluating Pitting Attack
Weight loss of test specimens no good ( . . . why ?).
Measurement of pit depth complicated because of statistical variations

Average pit depth of little use, since it is the deepest pit that causes
failure
MAXIMUM PIT DEPTH can be a useful way of expressing pitting
corrosion, and for comparing pitting resistance of standard test samples

HOWEVER, statistical nature of pitting means that sample size is
important

Should never predict lifetime of plant components from tests on small
samples
Pit depth as a function of
exposed area
Examples of pitting corrosion:

Alloy-800 SG tubes with phosphate
chemistrypitting severe pitting wastage
Point Lepreau had some pitting, switched to
AVT

SS cooling water H.X. left static under silted
conditionssevere pitting; replaced with Ti plate-
type

Others?

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Pitting Corrosion

PITTING: Extreme localized attack, may perforate metal sheet/plate . . .

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