Corrosion Forms II

Pitting and Crevice Corrosion

Dr. Zuhair M. Gasem
ME, KFUPM

Dr. Z. Gasem
ME472-062
KFUPM

Forms of Electrochemical Corrosion

Four categories of corrosion forms:

General corrosion (uniform corrosion over the whole anode)

Localized Corrosion (corrosion at isolated areas in the anode)

Galvanic corrosion

pitting corrosion

Crevice corrosion
Metallurgically Influenced Corrosion (corrosion is related to
microstructure)

intergranular corrosion of stainless steel

Mechanically Assisted Corrosion (corrosion is accelerated due to
mechanical factors)

Erosion corrosion

Corrosion Fatigue
Environmentally Assisted Cracking (corrosion results in cracking)

Stress corrosion cracking

Hydrogen damage

Dr. Z. Gasem
ME472-062
KFUPM

Forms of Corrosion

Dr. Z. Gasem
ME472-062
KFUPM

Pitting Corrosion

Metals and alloys can be

active (no protective passive
film) or passive (passive film
10-30 nm in thickness)
Pits
Pitting corrosion : rapid
corrosion penetration at
small discrete areas where passive
passive film breaks down andfilm
appears as small diameter
holes (0.1-5 mm). The
remaining surface is not
attacked.
Pitting corrosion is common
in passive metals above
pitting potential (Ep)
Weight loss is negligible

Pitting Corrosion

Dr. Z. Gasem
ME472-062
KFUPM

Examples:

Pitting of stainless steel, Ni

alloys, Al alloys in aerated
seawater or acids containing Clions
Steel buried in the soil corrodes
with the formation of pits.
Pitting of steels and aluminum
in alkaline solutions containing
ClPitting can occur in any alloy
that form a protective film and
exposed to stagnant solution
containing ClExample: 316 SS centrifuge
head exposed to CaCl2 solution
showing deep pits

Dr. Z. Gasem
ME472-062
KFUPM

Pitting Corrosion

Right: pitting in carbon

steel pipe carrying
strong acid.
Below: deep pits on a
carbon steel in HCl.

Dr. Z. Gasem
ME472-062
KFUPM

Pitting Corrosion

Top: pits in
stainless steel
valve plate
(stagnant
solution).
Bottom: internal
pits in steel
pipeline carrying
water with
dissolved CO2

Pitting Corrosion

Dr. Z. Gasem
ME472-062
KFUPM

Conditions favoring pitting:

Stagnant solutions

pitting occurs during shutdown period more than during normal operation
During shutdowns, solutions in pipes, pumps, and tubes are stagnant and
allow pits formation.

Acidic solutions
Presence of Cl and Br ( halides)
High temperature
rough surface finish
Commonly occur in passive metals (such as stainless steels)
Presence of surface deposits (deposits form localized concentrated
environments around them)
Rupture of protective coatings
Pits form in gravity direction

Pitting Corrosion

Dr. Z. Gasem
ME472-062
KFUPM

Why

pitting corrosion is dangerous?

Pitting corrosion is not easily detected and

evaluated and thus more dangerous than
general corrosion or galvanic corrosion.
Pits can grow and become like cracks
Can lead to failure by perforation with
minimum weight loss
Pits formation may take place after a long
period of initiation (tricky)
Aluminum parts in the space shuttle Apollo
were rejected because they contained pits
having a diameter of a human hair.

Dr. Z. Gasem
ME472-062
KFUPM

Pitting Corrosion

Difficulty of detection

Different misleading
pit (hole) shapes
Small weight loss
Cant use thickness
measurement
Small pits are hard to
observe visually
Corrosion products
may mask pits

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Stages in Pitting Corrosion

Dr. Z. Gasem
ME472-062
KFUPM

Two stages in pitting: initiation and propagation

Pits initiation at film break downs due to

Mechanical scratch
Localized High Cl- concentration
Localized failure of coatings or paints
At metal microstructural inhomogenity (inclusions in SS)

Pits initiation at surface deposits or scratches of paints

Most initiated pits become unstable and do not grow if

the passive film reforms or the highly concentrated
environments are washed off
If passive film reformation is not possible (high
concentration of Cl-), then a pit will grow at faster rate
due to autocatalytic effect.

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Dr. Z. Gasem
ME472-062
KFUPM

Autocatalytic Nature of Pitting

In the propagation stage of pits in SS

in aerated salt water (seawater):

O2 + 2H2O + 4e- 4 OH-

Oxygen is depleted inside the pit

and oxygen reduction takes place
around the pit

Anodic dissolution of the metal

produces M+ ions inside the pit

Cl ions diffuse toward the pit to

neutralize cations charge.

Cl and M+ inside the pit combine

and produce more H+ by hydrolysis
(M++Cl)+H2OMOH+H++Cl

The electrolyte becomes more acidic

inside the pit and more corrosive d (Pit depth)
because higher H+ and Cl

Reach autocatalytic stage where pit

growth follows d = ktn.

k is a constant and n ranges from

0.3 to 0.8

Parabolic growth

initiation

Propagation
time

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Dr. Z. Gasem
ME472-062
KFUPM

Effect of Temperature

Pitting is strongly influenced by the service

Temperature
In stainless steels

there is a critical pitting temperature below which

pitting will not initiate for each stainless steel alloy
304SS (critical pitting temperature = -2.5 C)
317SS (critical pitting temperature = -0 C)
Pitting resistance is improved by increasing Cr
(>18%) and Mo (2-4%).

13

Temperature effect

Dr. Z. Gasem
ME472-062
KFUPM

Three alloys are tested for

pitting resistance by
immersion for 24 hr in very
aggressive solution.

All alloys have high

resistance to pitting at 25 C
Alloy G: Ni-20Fe-22Cr-6Mo

Alloy 625: Ni-22Cr-9Mo

Shows pitting at 70 C
Shows pitting at 102 C

Alloy C-276: Ni-16Cr-16Mo4W

No pitting until 102 C

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Dr. Z. Gasem
ME472-062
KFUPM

Use of standard charts to

estimate pitting density
(number of pits per cm2
of metal surface)
Pitting evaluation is given
according to standard
charts

Pitting Evaluation and Control

A-4 pit
density=100,000/m2
B-3 pit surface size = 8
mm
C-2 Pit depth = 0.8 mm

Use pit opening diameter

Average pit depth

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Dr. Z. Gasem
ME472-062
KFUPM

Control and Prevention of Pitting Corrosion

Reduce Cl- content in the electrolyte
Lower acidity of solution, lower O2
Shot peen the surface.
Passivate stainless steels (SS) by washing with 20%
HNO3 to give it a strong passive film.
Replace 304 SS with 316 which contains higher Mo
Avoid stagnant solutions in tanks, tubes, and pipes
Redesign to ensure proper drainage

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Dr. Z. Gasem
ME472-062
KFUPM

Concentration Cells

Variation in the electrolyte in:

dissolved ion concentration
dissolved O2
pH
temperature
create a concentration cell in the
electrolyte where some region of the
electrolyte will favor cathodic
reactions and others favor anodic
reactions.
Corrosion of storage tanks: corrosion
will be localized at the boundary
between two electrolytes having
different ion or O2 concentrations.

The electrode potential

becomes more +ve as the
metal ions concentration
increases (see Nernsts
equation)

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Dr. Z. Gasem
ME472-062
KFUPM

In oxygen concentration cell, for example,

cathodic reactions are favored in region having
high concentration of Oxygen.
Example 1 : a drop of water on a metal surface.
The cathodic reaction is:

O2 + 2H2O + 4e- 4 OH-

In neutral solution (pH=7)

Oxygen Concentration Cell

e=0.82+0.059/4*log PO2
e is more +ve PO2

The drop surface dissolves O2 from the air and

will have high concentration of O2.
At the center of the drop, the O2 concentration is
low.
The metal at the periphery of the drop (high O2)
will act as the cathode (more +ve e).
The metal at the center of the drop (low O2) will
act as the anode.
This creates an oxygen concentration cell or air
differential cell which localizes corrosion.
Oxygen concentration cell is responsible for many
corrosion problems.
Example 2: oxygen concentration cells on the legs
of offshore steel structure

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Dr. Z. Gasem
ME472-062
KFUPM

Differential aeration cell

Corrosion is frequently
caused by concentration
difference in O2 from air.
Oxygen solubility in water
at RT is very small (8
ppm) and decreases with
temp.

Cathodic reaction:
O2 + 2H2O + 4e- 4 OHCathode: at
high conc of
O2 near the top
surface of tank
or sea surface
Anode at low
conc of O2
below the
surface

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Dr. Z. Gasem
ME472-062
KFUPM

Differential aeration cell

corrosion in stainless steel

thermometer pocket in
sea water cooled steam
condenser.
A stagnant layer of sea
water formed along the
stem on the downstream
side
Differential aeration cell

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Crevice Corrosion

Dr. Z. Gasem
ME472-062
KFUPM

Crevice: narrow opening or small

gap between two contacting
surfaces.
(0.025-0.1 mm)
Crevice corrosion: localized
corrosion resulting from a
concentration difference b/w the
electrolyte within the crevice and
the electrolyte outside the crevice
due to stagnation of electrolyte.
Possible concentration difference in:

O2
H+ (acidity)
Cl-

High PO2 ,low

[Cl-] and H+

Low PO2 , high

[Cl-] and H+

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Dr. Z. Gasem
ME472-062
KFUPM

Crevice Corrosion

22

Inside the crevice: low concentration of O2, and

high concentration of H+, and ions such as Cl(more ve Ecorr anode)
Outside the crevice: high concentration of O2,
and low concentration of H+, and ions such as Cl(more +ve Ecorr cathode)
A concentration or differential cell develops
between the electrolyte inside and outside the
crevice.
Accelerated corrosion occurs inside the crevice
while the outside is protected.

Crevice Corrosion

Dr. Z. Gasem
ME472-062
KFUPM

23

Crevice corrosion commonly occurs in three

different ways:

Geometric crevices: metal-to-metal tight contact

where the solution can get between the two
contacting metals

Metal-to-nonmetal absorbent: the nonmetal absorbs

the solution and continually moisten the metal

Threaded parts
Bolted and lap joints

Wood/metals
Paper gasket/metals
Sponge rubber gaskets in metallic pipe joints

Deposit corrosion: deposits that are porous and

absorbent of the solution such as sediment, lime, and
rust on metal surfaces

Dr. Z. Gasem
ME472-062
KFUPM

1. Geometric crevices

Example of a crevice
corrosion of a bolted joint.
The threads in the nut and
bolt will experience crevice
corrosion.
Examples of crevices
created in pipe
connections:
a.
b.
c.
d.

Incomplete penetration of
a butt weld
A threaded joint
A socket connection
A flange connection with
foamed rubber gasket

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Dr. Z. Gasem
ME472-062
KFUPM

2. Metal-to-nonmetal absorbent

Crevices are created by design

such as gaskets in flanges, Orings, washers, and insulations.

Crevice corrosion at
the flange/gasket
contact

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Dr. Z. Gasem
ME472-062
KFUPM

3. Deposit corrosion

Thick calcium carbonate

(CaCO3) deposits on a
condenser tubes

Thick greasy deposits on

steel tank. Corrosion
attack is due to crevice
effect.

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Dr. Z. Gasem
ME472-062
KFUPM

Alloys susceptible to crevice corrosion

Crevice corrosion can attack active

and active-passive metals and alloys
but active-passive metals are more
susceptible as stainless steels and
aluminum.
Example:

stainless steel universal joint showing

crevice corrosion beneath the rubber
grommet
Crevice corrosion at the washer-bolt
contact in SS fastener in seawater

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Dr. Z. Gasem
ME472-062
KFUPM

Crevice Corrosion

Materials resistance to
crevice corrosion is
tested using Teflon
blocks in very
corrosive electrolyte:

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Dr. Z. Gasem
ME472-062
KFUPM

Alloys susceptible to crevice corrosion

316 SS is more resistant

to crevice and pitting
corrosion than 304 SS.

304 SS is pitted badly in

very corrosive electrolyte
(acid condensate) which
prevented crevice
corrosion (figure a)
316 SS is not pitted in the
same environment but
crevice corrosion is evident
(figure b)
304 SS in mild aggressive
environment showing
Crevice corrosion (figure c)

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Dr. Z. Gasem
ME472-062
KFUPM

Alloys susceptible to crevice corrosion

Cast iron and steel

show excessive
crevice corrosion
beneath rubber orings
Often times crevice
corrosion is masked
by uniform corrosion
in carbon steels

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Dr. Z. Gasem
ME472-062
KFUPM

Development of Crevice Corrosion

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Dr. Z. Gasem
ME472-062
KFUPM

Initiation and Propagation in C.C.

Propagation of crevice corrosion (SS in

neutral aerated NaCl solution):
Anodic (MMn++ne-) and
cathodic reactions (O2 + 2H2O + 4e- 4
OH-)occur inside and outside the crevice.
Oxygen is consumed inside the crevice
Oxygen can be supplied at the outside of
crevice.
A differential aeration cell develops.
Oxygen reduction occurs only outside the
crevice
Anodic reaction inside the crevice
produces more +ve ions by (MMn++ne-)
Cl- migrate to the crevice for charge
neutrality
Mn+ and Cl- react and produce high
concentration of H+ inside the crevice by
hydrolysis (M++Cl)+H2OMOH+H++Cl
The pH inside the crevice 2 (acidic)
The pH outside the crevice 7
More anodic reaction inside the crevice

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Dr. Z. Gasem
ME472-062
KFUPM

Pitting and Crevice Corrosion

Pitting

and crevice corrosion are

Different in initiation
Similar in propagation (autocatalytic or self
sustained corrosion)

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Dr. Z. Gasem
ME472-062
KFUPM

Crevice Corrosion Control

34

Crevice corrosion is controlled by the same

methods used for pitting and

Reduce crevices in design

Use welding if possible instead of bolting two
surfaces in contact. Use continuous welds instead of
skip welds.
Avoid electrolyte stagnation
Use none-absorbent gaskets such as Teflon instead
of absorbent gaskets such as fiber and wood gaskets.
Cleaning to reduce local concentrations of acids,
chlorides, ext

Dr. Z. Gasem
ME472-062
KFUPM

Condensate corrosion

Hot gases containing H2O

vapor and other vapors such as
SO2, CO2, or H2S may
condensate in droplets on
cooler metal surfaces
producing localized corrosion
which appear as severe pitting.
Prevention

maintain the metal temp

above the dew point of the
hot gasses to prevent
condensation.
Apply insulation on pipes
carrying hot gases
Avoid attaching bare metal to
hot pipes which may act as
cooling fin.

Insulated hot pipe

Connection pipe
(no insulation)

Flow of hot gases

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Dr. Z. Gasem
ME472-062
KFUPM

Filiform corrosion

A crevice can be
created due to breach
in protective paints.
This type of crevice
corrosion is very
common and called
filiform corrosion.

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