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Corrosion - Module 4

The document discusses different types of corrosion including dry corrosion caused by chemical reaction with gases like oxygen and wet corrosion caused by electrochemical reaction when a metal is in contact with a conducting liquid. It describes various forms of wet corrosion including galvanic, pitting, and stress corrosion. Standard electrode potentials are provided to show the propensity of metals to corrode in galvanic pairs when joined in a conductive environment.

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Akash Savaliya
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91 views23 pages

Corrosion - Module 4

The document discusses different types of corrosion including dry corrosion caused by chemical reaction with gases like oxygen and wet corrosion caused by electrochemical reaction when a metal is in contact with a conducting liquid. It describes various forms of wet corrosion including galvanic, pitting, and stress corrosion. Standard electrode potentials are provided to show the propensity of metals to corrode in galvanic pairs when joined in a conductive environment.

Uploaded by

Akash Savaliya
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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Module 4

Corrosion

 Types and mechanism


 Dry and wet corrosion
 Forms of corrosion:
 Differential Aeration
 Pitting
 Galvanic
 Stress

AMS Professor VIT 1


AMS Professor VIT 2
Corrosion
“Gradual eating away (or) disintegration (or) deterioration of a
metal by chemical or electrochemical reaction with the
environment”
Reasons for corrosion:
o As compounds, metals are more stable thermodynamically.
o Metal will always have a strong tendency to convert itself into
more stable compound state.
o Hence, metals will try to go to lower energy states through
formation of compounds and thus attain stability.
Corrosion (oxidation)
Metal Metallic compound + energy
Extraction of metals

AMS Professor VIT 3


Examples
• Fe…………….Fe2O3 Reddish layer

• CU…………………..CuCO3,Cu(OH)2 green film

• Corrosion problems?
• Though process is very slow, loses incurred are
enormous.

AMS Professor VIT 4


Types of corrosion
Chemical corrosion Electrochemical corrosion
(dry corrosion) (wet corrosion)

Dry corrosion (chemical): Classified depending on the corroding agent


i) oxidation corrosion
o Oxygen present in the atmosphere attacks the metal forming oxide layer on the
surface of the metal.
M M2+ + 2 e-
½ O2 + 2e- O2-

M + ½ O2 M2+ + O2-

o Oxidation corrosion will lead to an oxide film which may be porous or non-porous.

AMS Professor VIT 5


Types of corrosion……
Pilling-Bedworth Rule:
o “If the volume of metal oxide is equal to or greater than the volume of the
metal getting corroded, then the oxide film is non-porous and protects the
metal from further corrosion; If the volume of the metal oxide is less than the
volume of the metal getting corroded, it will promote further corrosion of the
metal”.
o Cu, Al, Ni, Cr form non-porous oxide layers
o while Li, Na, K, Mg form porous oxide layers.

o Types of oxide layers: i) Stable oxide layer:


o It is a fine grain of oxide layer which is non-porous and adheres strongly to the
metal.
o Oxides of Al, Sn, Cu forms such impervious layers which prevents oxygen from
diffusing through the metal and hence further attack is stopped.
AMS Professor VIT 6
Types of corrosion…
ii) Unstable oxide layer:
o These are produced on noble metal surfaces and these oxide layers decompose
back to the metal.

Metallic oxide Metal + Oxygen


o Pt, Ag etc. form such oxide films.

Unstable
Exposed surface metal oxide

+ O2 Metal oxide
metal Of air metal metal + O2
decomposes

Unstable oxide layer


AMS Professor VIT 7
Types of corrosion….
iii) Porous oxide layer:
o These oxide layers have minute pores and are not impervious layers.
o Oxygen will diffuse through the pores and promote further corrosion.
o Fe is a good example of this type of corrosion.

Exposed Porous
surface metal oxide

Further Attack
metal + O2 through pores &
Of air metal
cracks continues

Porous oxide layer


AMS Professor VIT 8
Types of corrosion….
iv) Volatile oxide layer:

o These are oxide layers which evaporate as soon as they are formed and
hence further corrosion is facilitated.

o After some time the metal itself will disappear.

o Molybdenum is an example of volatile oxide layer corrosion.

Exposed
Volatile Fresh surface
surface
metal oxide Exposed for
Further attack
+ O2 Metal
metal oxide
Of air metal volatalizes metal

Volatile metal oxide


AMS Professor VIT 9
ii) corrosion by other gases: Types of corrosion ……
o CO2, Cl2, SO2, F2 etc. are gases which can attack the metal and corrode
o Extent of corrosion depends on the affinity of the metal to the gas.
o These gases chemically react with the metal forming either porous or non-
porous layers of films.
2Ag + Cl2 2AgCl nonporous
Sn + 2Cl2 SnCl4 volatile
o Hydrogen corrosion: Hydrogen gas attacks the metal to make them brittle
(Hydrogen embrittlement)
Fe + H2S FeS + 2H (atomic hydrogen)
iii) liquid metal corrosion:
o Flowing liquid metal (Hg) can penetrate through another metal to corrode.
o Gold (Au) can be corroded by mercury (Hg).
o Such corrosion is found in nuclear devices
AMS Professor VIT 10
b) Wet or Electrochemical Corrosion: Types of corrosion…….
o this type of corrosion occurs when a conducting liquid is in contact with
a metal
o or two dissimilar metals or alloys either immersed or dipped in a
solution.
o One part becomes anode and the other part cathode.
o At the anodic part corrosion (oxidation) occurs while reduction takes
place at the cathode.
At the anode: M Mn+ + ne-
o Mn+ either dissolved in solution or forms compounds such as oxides.

The rate of the electrochemical corrosion will depend on:


a) If the corrosion product is soluble in the medium, rate of corrosion will
be high.
b) If the corrosion product is insoluble in the medium, rate of corrosion
AMS Professor VIT 11
will be very low.
Electrochemical corrosion is present in the following types: Types of corrosion…..
1. Hydrogen evolution type corrosion
2. Oxygen consumption type corrosion
3. Galvanic corrosion
4. Concentration cell corrosion
5. Pitting corrosion
6. Stress corrosion
1. Hydrogen evolution type corrosion
occurs when base metals are in contact with an acidic solution.
Eg. Anode : Fe Fe2+ + 2e- (oxidation)
Cathode : 2H+ + 2e- H2
The overall reaction is:
Fe + 2H+ Fe2+ + H2
Simultaneously, metal ion will be produced at the anode while hydrogen will evolve
at the cathode
AMS Professor VIT 12
Mechanism of wet corrosion by H2
evolution

AMS Professor VIT 13


2.Oxygen absorption type corrosion:

Occurs when base metals are in contact with neutral solutions like water with
Dissolved oxygen (DO).
Rusting of iron is an example of this.
Anode : Fe Fe2+ + 2e- (oxidation)
These electrons move from anode to cathode and react with the electrolyte and oxygen
Cathode : ½ O2 + H2O + 2e- 2 OH- (Reduction)

The Fe2+ at the anode and OH- at the cathode diffuse and react to produce
Fe(OH)2: Fe + 2 OH- Fe(OH)2

If sufficient oxygen is present, Fe(OH)2 gets oxidised to ferric hydroxide (rust)

4 Fe(OH)2 + O2 +2H2O 4 Fe(OH)3 or 2(Fe2O3.3 H2O)

AMS Professor VIT 14


AMS Professor VIT 15
3. Galvanic corrosion:
Occurs when two dissimilar metals
in the electrochemical series are
in contact with each other
(Joined by rivetting or welding)
and exposed to corroding
environment.
o The metal with more negative
potential will become anode and
corrodes.
o This can be avoided or minimized
by:
a) coupling metals which are close in
the electrochemical series.

b) Making the cathode metal smaller


in area than the anodic metal.
AMS Professor VIT 16
Standard electrode potential of metals
Standard potential at 25oC

System Potential in V
Noble end
Increasing propensity to dissolve Au / Au3+ +1.5
Ag / Ag+ +0.80
Cu / Cu2+ +0.34
H2 / H+ 0.0
Pb / Pb2+ 0.13
Ni / Ni2+ 0.25
Fe / Fe2+ 0.44
Cr / Cr3+ 0.74
Zn / Zn2+ 0.76
Al / Al3+  1.66
Active end Li / Li+ 3.05
AMS Professor VIT 17
4. Concentration cell corrosion: (Differential aeration corrosion)

o When a metal is exposed to different concentration of oxygen or any


other electrolyte, a concentration cell is formed.
o The part of the metal exposed to lower concentration of oxygen (or)
electrolyte becomes Anode and the one exposed to higher
concentration becomes Cathode.
o Corrosion starts at the anode (dissolves).
o This type of corrosion occurs when metals are partly dipped in
solutions, partly covered with dust, oil marks, sand etc.
o Eg. Zinc rod dipped in brackish water solution, water line corrosion.

Anode: Zn Zn2+ + 2e-


½ O2 +H2O + 2 e- 2 OH- Zinc rod
More oxygenated part Cathode:½O2+ H2O+2e- 2 OH-
(Cathode)
Water-line

e- Flow of electrons
Zn2+ NaCl solution
Corroding anode
Zn2+
Zn2+ Zn
AMS Zn2+ + 2 e- (less oxygenated part)
Professor VIT 18
(Anode)
Cathode
(Protected part)
Anode Cathode Sand

Anode
Metal Metal (Less
Oxygenated
part)
Scale
(a) (b)

Metals partly covered with dirt, dust, sand, scale, oil marks become
oxygen deficient areas – Anodes

M Mn+ + 2e-

The other area which is more exposed to oxygen becomes oxygen


rich and acts as cathode

AMS Professor VIT 19


5. Pitting corrosion:

o Due to rapid penetration of oxygen through some cracks in the


oxide film or pin holes on metallic surfaces, pitting takes place
leading to corrosion.

o Eg. Al, Ti and stainless steel undergo pitting corrosion in acidic


environment.

6. Stress corrosion (cracking):

o Caused by the effect of local corrosion and tensile strength in a


particular environment.

Eg. Brass in the presence of ammonia

Stainless steel in the presence of NaOH at high temperature

AMS Professor VIT 20


Factors influencing corrosion

a) Nature of the metal


b) Nature of the corroding environment

AMS Professor VIT 21


a). Nature of the metal:

i) Position in the galvanic series:

ii) Relative areas of cathode and anode:

iii) Purity of the metal:

vi) Physical state of the metal:

vi) Nature of surface film: (Pilling-Bedworth rule):

vii) Passive character of the metal

viii) Solubility of corrosion product:

ix) Volatility of the corrosion product:


AMS Professor VIT 22
b) Nature of the corroding environment:

i) Temperature:

ii) Humidity in environment:

iii) Presence of impurities in the atmosphere:

iv) Conductance of the corroding environment:

v) Formation of oxygen concentration cell:

vi) Presence of suspended solids in the environment:

vii) Effect of pH

viii) Nature of ions present:


AMS Professor VIT 23

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