Cathodic protection

Introduction
Electrochemical
• one of the most widely used methods
• works almost all the time on all
Cathodic and Anodic
thermodynamics
Electrochemical
kinetics metals and environments
Corrosion rate
• first used in 1820s to combat marine
Protection measurements
Various forms of
corrosion
corrosion
Corrosion mitigation • now used primarily to coated protect
 cathodic and
anodic protection
carbon steel in neutral environments
 coatings and
inhibitors • examples: pipelines, oil and gas
 material selection
and design
wells, offshore structures, seagoing
ship hulls, marine pilings, water
tanks, some chemical equipment

1 2

Principles of cathodic protection:

impressed current method Impressed current method
Introduction
Electrochemical
Eapplied = Erev − ηc iapplied = ic − ia ≈ ic Introduction
Electrochemical
• example:
thermodynamics thermodynamics – mild steel in strong acid
2e
Electrochemical Electrochemical
– corrosion current: icorr ≈ 10 A/m2
+

kinetics
2+
+ kinetics
Corrosion rate
Fe Corrosion rate – corrosion rate: CR ≈ 11.5 mm/y
measurements Æ measurements
Various forms of
Ecorr
Fe Various forms of – apply cathodic polarization: ηc=120 mV
potential / V

corrosion corrosion
Corrosion mitigation Corrosion mitigation – reduces corrosion current to: icorr ≈ 0.1 A/m2
H
 cathodic and
anodic protection
+
+
 cathodic and
anodic protection
– reduces corrosion rate to: CR ≈ 0.1 mm/y
e
 coatings and -
Æ
 coatings and
– impressed current density: iapplied ≈ 150 A/m2
inhibitors
H inhibitors
 material selection
Eapplied  material selection – impressed current per m2: Iapplied ≈ 150 A
and design and design
– not practical
ia≈ 0 icorr ic≈ iapplied
– need coating
|

log i / (A m-2)
– hard to find one for strong acids
3 4

1
 Impressed current method:
steel in neutral aerated water Impressed current method
Introduction
Electrochemical
Eapplied = Erev − ηc iapplied = ic − ia ≈ ic Introduction
Electrochemical
• example:
thermodynamics thermodynamics – mild steel in aerated neutral seawater
Electrochemical O Electrochemical
2 +2 – corrosion current: icorr ≈ 1 A/m2

+
kinetics HO kinetics
2
Corrosion rate +4 Corrosion rate – corrosion rate: CR ≈ 1.1 mm/y
e -
measurements Æ measurements
apply cathodic polarization: ηc=120 mV
4O
Various forms of H- Various forms of –
potential / V
e
corrosion
2+ +2 corrosion
– reduces corrosion current to: icorr ≈ 0.001 A/m2
Corrosion mitigation Corrosion mitigation
Ecorr Fe
 cathodic and Æ  cathodic and
– reduces corrosion rate to: CR ≈ 0.001 mm/y
anodic protection Fe anodic protection
 coatings and
inhibitors
 coatings and
inhibitors
– impressed current density: iapplied ≈ 1 A/m2
 material selection
Eapplied 2H
 material selection – impressed current per m2: Iapplied ≈ 1 A
and design and design
2O – practical
+2
ia≈ 0 ic≈ iapplied icorr e -
Æ – works even better with coating
|

H
2 +2
OH - – alkaline conditions lead to scale precipitation
log i / (A m-2)
5 6

Impressed current method: Principles of cathodic protection:

steel in neutral aerated water sacrificial anode method
Introduction Introduction
Electrochemical
can one overdo it ? Electrochemical -
e
thermodynamics thermodynamics 2+ +2

+
O u
Electrochemical +2 Electrochemical ÆC
Cu
2
+

kinetics HO kinetics
2
Corrosion rate +4 Corrosion rate Cu
e - Ecorr
measurements Æ
4O
measurements H + tota
+e l ca

potential / V
Various forms of H- Various forms of couple - thod
Ecorr Æ
potential / V

e H ic =
corrosion
2+ +2 corrosion H+ +e - on C nod
ic
Corrosion mitigation
Ecorr Fe
Corrosion mitigation Zn
Ecorr ÆH u
tal a
 cathodic and Æ  cathodic and on Zn = to
anodic protection Fe anodic protection

+ 2e
 coatings and  coatings and
2+
Zn
inhibitors inhibitors

Zn Æ
 material selection  material selection
and design 2H and design
2O
+ 2e Cu , coupled Cu
Eapplied icorr I corr I corr Zn
I corr Zn , coupled
I corr
|
-
Æ
|

H
2 +2
ia≈ 0 OH - log I / A
log i / (A m-2) ic≈ iapplied
7 8

2
 Sacrificial anode method Solution resistance problem
Introduction
Electrochemical
• sacrificial anode continuously “consumed” Introduction
Electrochemical -
e
thermodynamics by corrosion and needs replacement thermodynamics 2+ +2

+
u
Electrochemical Electrochemical ÆC
kinetics • good candidates: kinetics Cu
Corrosion rate Corrosion rate
measurements – zinc: used broadly,e.g. galvanized zinc measurements
Cu , Ω
Ecorr tota
l ca

potential / V
Various forms of
coating is a common distributed sacrificial Various forms of couple thod
corrosion corrosion Ecorr I applied RΩ ic = ic
anode for steel nod
Corrosion mitigation Corrosion mitigation
total a
 cathodic and  cathodic and =
anodic protection – magnesium: used for underground pipeline anodic protection

+ 2e
Zn ,Ω
 coatings and
protection, i.e. in soil and other low  coatings and
Ecorr 2+
Zn
inhibitors inhibitors
 material selection conductivity environments  material selection
Zn Æ
and design and design
– aluminium: improved life in seawater and Cu , coupled
I corr Cu , Ωcoupled
I corr Zn , Ω coupled
I corr Zn , coupled
I corr

|
other high conductivity environments because
it polarizes less than zinc and magnesium log I / A
9 10

Anodic protection by
Anodic protection
impressed current
Introduction
e -
Introduction
• suitable for active-passive alloys (e.g.
Mn+ + n
Electrochemical Electrochemical
pitting

stainless steel, nickel alloys, titanium)

+

thermodynamics M Î thermodynamics
Electrochemical Electrochemical
kinetics kinetics • requires a broad potential range for
Corrosion rate Eapplied Corrosion rate passivity
passive
potential / V

measurements measurements
Various forms of Various forms of • need sizable/expensive electrical
corrosion
Corrosion mitigation Epp
corrosion
Corrosion mitigation
equipment
 cathodic and
anodic protection
Ecorr
 cathodic and
anodic protection
• risky if potential “slips” into the
active/pitting region
active

 coatings and  coatings and

inhibitors inhibitors
 material selection icorr icorr  material selection
• used often for very aggressive solutions
and design icrit and design
|

log (current density) / (A m-2)

when other methods fail, e.g. for
protection of tanks storing of strong
acids (e.g. sulphuric, phosphoric, nitric)
11 12

3
 Common issues
Introduction
Electrochemical
• potentiostatic vs. galvanostatic control
thermodynamics
Electrochemical
• reference electrodes
kinetics
Corrosion rate
• current distribution and throwing power
measurements
Various forms of
• complex geometry, crevices
corrosion
Corrosion mitigation
• stray currents
 cathodic and
anodic protection • rectifiers
 coatings and
inhibitors • cost
 material selection
and design

13