A Seminar On Pitting Corrosion: Department of Metallurgical and Materials Engg. M.S.University, Baroda

A SEMINAR ON
PITTING CORROSION
Presented By. Guided By :

Sharadkumar Suhagiya Dr. Sunil Kahar
Roll No. 116013 Assistant Professor
M.E. (Met. & Mats.) (Weld. Tech.) Metallurgical & Materials Engg. Dept..
M.S.U. Baroda
Department of Metallurgical and Materials

Thursday, April 23, 2020 Engg. 1
Content
 Introduction
 Mechanism
 Factor influencing of Pitting
 Prevention of Pitting
 Case study
 References
Introduction
 Pitting is a localized form of corrosion by which cavities or "holes" are
produced in the material.
 Pitting is considered to be more dangerous than uniform corrosion damage
because it is more difficult to detect, predict, occurs rapidly.
 Pitting mainly observed in stainless steels and aluminium alloys, are useful
to reduce uniform corrosion.
 But S.S. and Al. alloy susceptible to localized breakdown, resulting in
accelerated dissolution of metal which cause the pitting corrosion.
Fig.1 Sewer explosion due to Pitting
An example of corrosion damages with
shared responsibilities was the sewer
explosion that killed 215 people in
Guadalajara, Mexico, in April 1992.
Besides the fatalities, the series of blasts
damaged 1,60 buildings and injured
1,500 people.
Mechanism
 Classical pitting corrosion caused by passive film breakdown will only
occur in the presence of aggressive anionic species, and chloride ions.
 The presence of oxidizing agents in a chloride containing environment is
usually extremely detrimental and will further enhance localized
corrosion.
 The pit environment becomes enriched in metal cations as a result of the
dissolution process in the pit (written for a general metallic element, M):
M → Mn+ + ne-
 Reactions by which oxygen reduction occurs is:
O2 + 2H2O + 4e- → 4OH-
 Due to localized Pit environment pit zone is more stagnant.
 That’s why Oxygen is depleted in pit zone and more oxygen outside of the
pit cavity, where this reactant is more plentiful.
Fig.2 Autocatalytic process occurring in a corrosion pit. The metal, M, is
being pitted by an aerated NaCl solution. Rapid dissolution occurs in the
pit, while oxygen reduction takes place on the adjacent metal surfaces[18].
 Potential of outside the pit cavity E2 higher than potential of Pit zone E1.
 So the Pit zone act as anodic zone and outside of pit zone act as cathodic
zone.
 Larger area of cathode and smaller area of anode, So unfavourable area ratio.
 Due to unfavourable area ratio more anodic dissolution would take place so
in this section higher metal ion concentration .
 For neutralization cl- ion come in pit zone and following reaction take place
Me2+ + 2H2O → Me (OH)+ + H++ H2O
→ Me (OH)2 + 2H+
Me2+ + Cl-+H2O →M(OH)2 + Hcl
 Due to above reaction Hydrogen concentration increase in Pit zone then PH
go down & also presence of chlorine ion adversely effect the passivity which
break the passive layer.
 Then Pitting become autocatalytic in nature; once a pit starts to grow, the
local conditions are altered such that further pit growth is promoted.
Corrosion Pit shape
THROUGH PITS SIDEWAY PITS
Narrow, deep Subsurface
Shallow, wide
Undercutting
Elliptical
Horizontal grain attack
Vertical Grain Attack

Factor influencing of Pitting
1. Effect of alloy –
 Increasing the concentration of nickel, which stabilizes the austenitic
phase, moderately improves the pitting resistance of iron-chromium.
 Molybdenum in stainless steels, can greatly reduce pitting susceptibility.
But Mo effective only in the presence of chromium.
 Such as Titanium and Tungsten, also have a strong influence on the pitting
resistance of stainless steels.
2. Surface Condition
 Samples prepared with a rough surface finish are more susceptible to
pitting and exhibit a lower pitting potential.
3. Velocity
 Pitting is usually associated with stagnant condition such as liquid in tank.
 Increasing velocity often decreases the pitting attack.
 For example, a stainless steel pump would give good service handling
seawater if it were run continuously but would pit if it were shut down for
extended period.
4. Environmental effects and local chemistry development –
 Pitting corrosion will only occur in the presence of aggressive anionic
species, and chloride ions are usually.
 The severity of pitting tends to vary with the logarithm of the bulk
chloride concentration.
 The presence of oxidizing agents in a chloride-containing environment is
extremely detrimental, and will further enhance localized corrosion
5. Physical /chemical heterogeneity –
 Pits almost always initiate at some chemical or physical heterogeneity at
the surface, such as inclusions, second-phase particles, solute-segregated
grain boundaries, flaws, mechanical damage, or dislocations.
 Pits in stainless steels are often associated with MnS inclusions, The role
of MnS inclusions in promoting the breakdown and localized corrosion of
stainless steels has been recognized for some time.
 Recent improvements in alloy production have led to steels with lower
sulphur content to improve pitting resistance.
6. Temperature
 Higher the CPT, the more resistant the
alloy is to pitting.
Prevention
 All of the factors described previously can be used to mitigate pitting
corrosion:
Environment – control oxygen level, chloride concentration.
Alloy composition and structure.
Good Surface finish.
Velocity and temperature.
 For stainless steels, heat treatment, grinding, and abrasive blasting have
been reported to be detrimental to pitting resistance, whereas pickling in
HNO3 + HF scales or passivation in HNO3 is beneficial.
 Various chemicals, when added to corrosive solutions, will inhibit pitting.
Common inorganic inhibitors include sulfates, nitrates, chromates, and
molybdates.
Effect of alloying element on pitting resistance of S.S. alloy
Chromium Increases
Nickel Increases
Molybdenum Increases
Silicon Decreases, increases when presence with Mo
Ti & Columbium Decreases resistant with FeCl3
Sulphur Decreases
Carbon Decreases
Titanium
Hastelloy C, Chlorimet 3
Hastelloy F, Neonel, Durimet 20
316 stainless steel
Increasing
pitting
resistance 304 Stainless steel
Case study
Title Pitting corrosion of pipeline steel weld zone
Material
Compo. C Mn P S Si Ni Cr Mo V Al Cu Nb Ti
PM 0.09 0.93 0.013 0.003 0.17 0.002 0.002 <0.01 0.005 0.036 0.01 0.034 0.013
HAZ 0.09 0.94 0.013 0.003 0.17 0.002 0.002 <0.02 0.005 0.036 0.01 0.034 0.013
WM 0.09 0.93 0.013 0.003 0.17 0.002 0.002 <0.03 0.005 0.036 0.01 0.034 0.013

Pitting
corrosion in
pipeline
steels welds
after 148
weeks

Microstructure
1.P.M. (5 mi.)
2.H.A.Z
(Elong.)
3.W.M.
(Equiaxe)
Steel pipeline
samples
exposed
continuously to
natural pacific
ocean seawater
after 3.5 year

Observation

CONCL. 1. The maximum pit depth in the heat affected zone for longitudinal welds on
pipeline steels is about 25% greater than for the adjacent parent metal and
weld metal zones.
2.The variability in maximum pit depth changes with increased period of
exposure, from relative small in the period 0-55 weeks to much larger
immediately thereafter but then tending to a steady state after 3 years
exposure.
3.HAZ is the result of the development of anoxic corrosion conditions in
localized niches that have developed from earlier micro-structural defects that
are significantly more numerous and clustered in the HAZ. Also Micro
stuructural gradient exist within the HAZ, due to different time temperature
cycle experience & Compositional gradient on the scale of few micron
referred to as microsegregation due to solidification So Pitting is more in
HAZ.
References
 H.P. Leckie and H.H. Uhlig, J. Electrochem. Soc., Vol.113, 1966, p 1262
 H.-H. Strehblow, in Corrosion Mechanisms in Theory and Practice, P. Marcus
and J. Oudar, Editors, p. 201, Marcel Dekker, Inc., New York (1995).
 T. P. Hoar, Corros. Sci., 5, 279 (1965).
 H. H. Uhlig, J. Electrochem. Soc., 97, 215C (1950).
 N. Sato, Electrochem. Acta 16,1683 (1971)
 J.A. Richardson and G.C.Wood, Corros. Sci., 10,313 (1970)
 H.-H. Strehblow, "Nucleation and Repassivation of Corrosion Pits for Pitting
on Iron and Nickel," Werk. Korros., 27, 792 (1976)
 H. P. Leckie and H. H. Uhlig, J. Electrochem. Soc., 113, 1262 (1966).
 J. R. Galvele, Corros. Set, 21, 551 (1981).
 ASM Handbook, 13(a) Corrosion : Fundamental, Testing and Protection
 Annual Book of ASTM Standards, G48-92, p. 189, ASTM, Philadelphia, PA
(1994).
 Z. Szklarska-Smialowska, Pitting Corrosion of Metals, NACE, 1986
 J. Horvath and H.H. Uhlig, J. Electrochem. Soc., Vol. 115, 1968, p 791
 A.J. Sedriks, Effects of Alloy Composition and Microstructure on the Localized
Corrosion of Stainless Steels, Advances in Localized Corrosion, Vol NACE-9,
NACE, 1990, p 253
 A.J. Sedriks, Corrosion of Stainless Steels, Wiley-Interscience, 1996
 S.B. deWexler and J.R. Galvele, J. Electrochem. Soc., Vol 121, 1974, p 1271
 Pitting corrosion in pipeline steel weld zones, Igor A Chaves and Robert E
Melchers, Centre for Infrastructure Performance and Reliability, The University
of Newcastle, Australia
 G. S. Frankel, Pitting Corrosion of Metals A Review of the Critical Factors,
Journal of the Electrochemical Society, Vol. 145, No. 6, 1998, pp. 2186-2198.

A Seminar On Pitting Corrosion: Department of Metallurgical and Materials Engg. M.S.University, Baroda

Uploaded by

Copyright:

Available Formats

A Seminar On Pitting Corrosion: Department of Metallurgical and Materials Engg. M.S.University, Baroda

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

A Seminar On Pitting Corrosion: Department of Metallurgical and Materials Engg. M.S.University, Baroda

Uploaded by

Copyright:

Available Formats

A SEMINAR ON

Presented By. Guided By :

Department of Metallurgical and Materials

Narrow, deep Subsurface

Horizontal grain attack

Vertical Grain Attack

You might also like