Prof.

Marco Ormellese
Politecnico di Milano, Dipartimento di Chimica,
Materiali e Ingegneria Chimica “G. Natta”
(marco.ormellese@polimi.it)

Corrosion Engineering

Lect. 01 – Introduction to corrosion

Corrosion: definition

• Physical-chemical interaction between a

metal and its environment
– changes in the properties of the metal
– loss of the function of the metal
– pollution of environment

1
Corrosion

• is a natural phenomenon
– must be controlled at a reasonable cost
• is inherently probabilistic by nature
– affected by a great variety of parameters,
– frequently difficult to be predicted in detail
• has consequences that can be catastrophic
and tremendously expensive

Anti-metallurgical process

mine
ENERGY
(iron oxides)

Environment
Iron & steel atmosphere
industry sea water
soil
fluids

ENERGY
RUST
(hydrated
iron oxides)

2
Morphology

• Related to the metal, environment, to geometric,

mechanical and metallurgical features
• Generalised

Morphology

• Related to the metal, environment, to geometric,

mechanical and metallurgical features
• Localised

3
Morphology

• Related to the metal, environment, to geometric,

mechanical and metallurgical features
• Cracking

Corrosion mechanism

Me + water + oxygen  corrosion products

Corrosion is an electrochemical process

Four processes in series

1. anodic reaction Me  Mez+ + ze
2. cathodic reaction O2 + 2H2O + 4e  4OH-
3. current into the solution
4. current into the metal

4
Corrosion mechanism

Ia Anodic Im
process
Ia = Iel = Ic = Im
Current = Current
flowing in ICORR in
the electrolyte the metal

Iel Cathodic Ic
process

Faraday Law

e Ych My
ΔW  e Yech  Q  Q  It
F zF
Corrosion penetration rate
ΔW 1 e i
vp    eech  Q  ech a
ρSt ρSt ρ
1
vp  Δm
ρAt

Mass loss rate

1
vm  ∆m
At

5
 Corrosion rate units

• Mass loss rate

mdd = mg/dm2.d

• Penetration rate
m/y
mils/y = 24.5 m/y

1 mdd  5 m/y (for steel)

Iron: ia = 1 mA/m2 → vp = 1,17 μm/y → vm ~ 0.234 mdd

→ vp ~ 1 μm/y → vm ~ 0.2 mdd

Current density (ia) vs corrosion rate

Considering an anodic current density of 1 mA/m2

Metal or Oxidation Density Equivalent Penetration

alloy state (g/cm3) weight (My/z) rate (μm/y)
Iron Fe2+ 7.87 27.92 1.17
Nickel Ni2+ 8.90 29.36 1.09
Copper Cu2+ 8.96 31.77 1.17
Aluminum Al3+ 2.70 8.99 1.09
Lead Pb2+ 11.34 103.59 2.84
Zinc Zn2+ 7.13 2.68 1.50
Tin Sn2+ 7.30 59.34 2.67
Titanium Ti2+ 4.51 23.95 1.75
Zirconium Zr4+ 6.50 22.80 1.91
AISI 304 Fe2+, Cr2+, Ni2+ 7.90 25.12 1.04
AISI 316 Fe2+, Cr2+, Ni2+, Mo2+ 8.00 24.62 1.04

6
Corrosion mechanism

• It is determined by the slower of the four partial

processes
• It is negligible if one of the following occurs:
– the anodic process is slow because of the metal
is in passive conditions
– the cathodic process is slow because of oxygen
diffuses slowly
– the electric (ionic) conductivity of the
electrolyte is low
– the electr(on)ic conductivity of the metal is low

Anodic reactions

• Anodic (metal dissolution)

– Ag → Ag+ + e−
– Fe → Fe2+ + 2e−
– Cu → Cu2+ + 2e−
– Zn → Zn2+ + 2e−
– Al → Al3+ + 3e−
– Al + 2H2O → AlO2− + 4H+ + 3e−
– Mg + 2OH− → Mg(OH)2 + 2e−
– Ag + Cl− → AgCl + e−

7
Cathodic reactions

• Hydrogen evolution
– 2H+ + 2e- → H2
– 2H2O + 2e- → 2OH− + H2

• Oxygen reduction
– O2 + 4H+ + 4e− → 2H2O
– O2 + 2H2O + 4e− → 4OH−

• Chlorine reduction
– Cl2 + 2e− → 2Cl −

Corrosion: prevention

• Design
Knowledge of • Monitoring
corrosion phenomena • Maintenance

Proper material • Corrosion Resistant Alloys (CRA)

selection

• Organic coating
Corrosion resistant • Metallic coating
coatings • Surface treatment

• Inhibitors
Chemicals • Oxygen scavenger
• Biocide

Electochemical • Cathodic protection

techniques