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Pi#ng

Corrosion
and
Crevice Corrosion
(Corrosion Engineering)

Pi#ng Corrosion
Lecture Outline
Deni:on
Examples
Observa:on
Mechanism
Eect of Environment
Eect of Alloy Composi:on
Pi#ng Corrosion Other Alloys
Impacts

Types of Corrosion

Uniform
Galvanic corrosion
Pi#ng corrosion
Crevice corrosion
Intergranular corrosion
Selec:ve leaching
Erosion corrosion and fre#ng
Environmentally induced cracking
Hydrogen damage

Pi#ng Corrosion Deni:on


Highly localized aNack occurring at a
rapid penetra:on rate due to breakdown
of a passive metal.
The local sites of breakdown are oQen
associated with microscopic defects in
the metal or alloy.
ASM deni:on:
Corrosion of a metal surface conned
to a point or small area that takes the
form of cavi:es

Example of Pi#ng Corrosion


Requirements for pi#ng
corrosion:
Alloy composi:on
(stainless steel, nickel
alloys, aluminum alloys,
:tanium alloys, copper
alloys)
Passive lm
Solu:on composi:on (Cl-,
Br-, I-, F-)
Surface heterogenei:es

Observa:on of Pi#ng Corrosion


Visual observa:on:
Density
Diameter/Area
Depth

Pit vs. general


corrosion

Observa:on of Pi#ng Corrosion - 2


Electrochemistry:

Log(icorr)

Addi:on of
chloride Transpassive

Pi#ng
corrosion

Passive

MS-

SHE

Change in
environment
aects the current
response
Higher passive
current
Signicant current
increase before
transpassivity

Pi#ng Poten:al and Signicant Values


Current response as a func:on of the
poten:al applied
Transpassive
Log(icorr)

Ac:ve
pi#ng
Metastable
pi#ng

Erep

Epit

MS-

SHE

Use of Pi#ng Poten:al


Determine occurrence of pi#ng
knowing the corrosion poten:al
in the environment of interest

Log(icorr)

Transpassive
1.
4.

2.
3.
Erep

Epit

MS-

SHE

Mechanism Pit Chemistry


The anodic reac:on (release
e-) and cathodic reac:on
(consume e-) are separated.
Cathodic reac:on on passive
lm:
O2+2H2O+e-4OH-
Anodic reac:on in pit:
FeFe2++2e-
Hydrolysis of metal ion:
Fe2++2Cl-+2H2OFe(OH)2+2HCl
Hydrolysis acidies the pit
solu:on

Mechanism Ini:a:on 1
Mul:ple mechanisms suggested:
Chloride adsorp:on.
(a)

FeOOH Fe3+ + 3OH-



(b)
FeOOH + Cl- FeOCl +
OH-

FeOCl + H2O Fe3+ +


Cl- + 2OH-

(c)
Fe Fe2+ + 2e-

Mechanism Ini:a:on 2
Structural defects (grain boundaries or disloca:on pile ups).
Weaken passive lm.
Preferen:al passive lm dissolu:on exposing the bare
material and ini:a:ng pi#ng corrosion.
Passive lm

Passive lm

Passive lm

Passive lm

Mechanism Ini:a:on 3
Chemical heterogenei:es. Such as Manganese
Sulde (MnS) in Stainless Steels.
Weak passive lm
Suggested mechanism:
MnS dissolve
preferen:ally
Bare surface exposed
Pi#ng corrosion ini:ates

OR
MnS/Matrix galvanic cell
Matrix dissolve and
undercut MnS
Bare surface exposed
Pi#ng corrosion ini:ates

Passive lm

Passive lm

MnS

Passive lm

Passive lm

Eects of Environment Chloride


Pi#ng corrosion is highly dependent on the
chloride concentra:on
Pi#ng poten:al increases
Repassiva:on poten:al stays constant

Erep

Pi#ng Poten:al

Poten:al

Epit

Eect of Environment Temperature 1


The pi#ng poten:al decreases as the
temperature increases.
Materials resistant to pi#ng corrosion at low
temperature may become suscep:ble at high
temperature

Eect of Environment Temperature 2


Cri:cal pi#ng temperature CPT: temperature
above which a signicant current density is
measured when a xed poten:al is applied
CPT
Temperature

Current

density

100 A/cm2

Time

Eect of Alloy Composi:on 1

Pi#ng Resistance
Equivalent Number
(PREN) empirical
equa:on to rank
stainless steels

PREN= Cr+3.3(Mo+0.5W)+16N

Eect of Alloy Composi:on 2


Alloy composi:on impact microstructure and
defects.
Alloy composi:on changes the pH of the pit
solu:on.
Room temperature pH of concentrated salt
solu:ons
Salt

1N

3N

Saturated

NiCl2

3.0

2.7

2.7

FeCl2

2.1

0.8

0.2

CrCl3

1.1

-0.3

-1.4

Pi#ng Corrosion Other Alloys


Nickel alloys are highly resistant to pi#ng
corrosion
Aluminum alloys: light alloys used for aeronau:c
and automo:ve. Pi#ng ini:ates at
microstructures (e.g. Cu-rich phases) linked to
micro-galvanic cells
Copper: annealed or half-hard tubes in cold tap
water. Other possible as a func:on of pH,
material condi:on and temperatures
Other materials: Titanium, Zinc, Tin, Cadmium,
Zirconium, Magnesium

Impact
High localized stress
leading to fracture
(failed axle)

Leaks with low amount


of materials damage

Explosion if under
pressure

Lecture Review
Require passive alloy and chloride solu:on
Pi#ng poten:al:
Ecorr<Epit : no corrosion Ecorr>Epit : corrosion
anode in the pit and cathode outside
Solu:on in the pit contains chloride and low pH
Compe::on:
Crea.on>Diusion: corrosion
Crea.on<Diusion: no corrosion
Chloride, temperature and alloy composi:on greatly
aect pi#ng corrosion
Nickel alloys, aluminum alloys, copper and others may
suer pi#ng corrosion

Small damages result in big failures

Crevice Corrosion

Crevice Corrosion
Lecture Outline
Deni:on
Examples
Observa:on
Mechanism
Eect of Environment
Eect of Alloy Composi:on
Pi#ng Corrosion Other Alloys
Impacts

Crevice Corrosion Deni:on


Breakdown of passivity on a metal or alloy at a
:ght crevice site due to the development of
an aggressive crevice solu:on.
ASM Deni:on:
Localized corrosion at or immediately adjacent to
an area that is shielded from full exposure to the
environment due to close proximity between the
metal and the surface of another material

Example of Crevice Corrosion


Requirements for crevice
corrosion:

Creviced system combined


to exposed area
Alloy composi:on
(stainless steel, nickel
alloys, aluminum alloys,
:tanium alloys, copper
alloys)
Passive lm
Solu:on composi:on (Cl-,
Br-, I-, F-)

Observa:on
Visual:
Expose creviced specimens and
perform visual assessment of
crevice corrosion
Amount of feet having
corroded
Extent of corrosion

Observa:on 2

Electrochemically:

Crevice poten:al to iden:fy when crevice will


ini:ate
Can crevice corrosion or pi#ng corrosion ini:ate?

Log(icorr)

Transpassive

Passive
Ecrev

Epit

MS-

SHE

Mechanisms
Three models suggested:
Acidica:on: similar to pi#ng corrosion
IR drop: poten:al drop due to solu:on resistance
Stabiliza:on of metastable pi#ng

Mechanism Acidica:on 1
1. Deple:on of oxygen
M O OH
in crevice
M
2. Separa:on of the
anode and the
cathode
3. Chloride diusion M(OH) + aH M
and hydrolysis of
M
metal ion
4. Aggressive
environment
M(OH) + aH
M
depassivate crevice
+

O2

M
Cl-

O2

OH-

e-

Cl-
O2

OH- M+

e-

OH-

Mechanism Acidica:on 2
Chloride
diusion

Hydrolysis
Reduc:on
Cathodic

Oxida:on
Anodic

Mechanism IR Drop
1. Current is owing
through the crevice
from inside to the
mouth
2. Due to the solu:on
resistance, the
poten:al drops:
E=IR
3. As the poten:al
decreases, it
reaches the ac:ve
peak

Mechanism Stabilization of metastable pitting


Metastable pits die
because the pit
solu:on diuse out
in innite bulk
solu:on
Crevice ini:ate
because the
metastable pit
solu:on diuse out
in a small crevice
solu:on

Neutral pH
Low Cl-

Acidic pH
High Cl-

Crevice Former Proper:es eect


Porous crevice former:
Solu:on diuse out
Small crevice length:
Solu:on diuse out
Wide crevice gap:
Lower corrosion rate
ANack near the mouth

Pi#ng vs. Crevice Corrosion


: Epit in 1 M NaCl
: Ecrev in 0.5 M NaCl
: Ecrev in 1 M NaCl (ne)
: Ecor in 1 M NaCl


Can pi#ng corrosion
occur?
Can crevice corrosion
occur?
Which one is more
likely?

Eect of Environment
Chloride

What is the likeliness of crevice


corrosion when you increase the
chloride content?

Temperature/pH

What is the likeliness of


crevice corrosion when you
decrease the pH?
How do the cri:cal
temperatures compare?

Examples of Crevice

Flanges
Rivets
Rocks
?

Lecture Review

Requirements: crevice, passivity, chloride


Observa:on: visual or electrochemical
Crevice poten:al above which crevice corrosion occurs
Mechanisms: acidica:on, IR drop or metastable pit
Compe::on:

Crea:on (dissolu:on, hydrolysis) vs. Diusion

Small crevice former: less crevice corrosion


Loose crevice former: less crevice corrosion
Ecrev < Epit : if possible, crevice corrosion ALWAYS occur
before pi#ng corrosion
High chloride
High temperature BAD
Low pH