Chapter 5.

Corrosion Protection

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1
Learning Objectives

• To understand the principles of sacrificial anode and impressed current cathodic

protection systems.
• To develop basic skills of design for sacrificial anode and impressed current cathodic
protection systems.
• To have basic understanding the technique for cathodic protection monitoring.
• To understand the principle of anodic protection.
• To be familiar with other approaches to corrosion control: materials selection, surface
covering, environmental control and design.

Topics and Key Points

1. Sacrificial anode cathodic protection: types, theoretical energy density, backfill
2. Impressed current cathodic protection: system design, anodes, rectifier, stray current
protection, over-protection, protection monitoring
3. Anodic protection
4. Surface covering: anodisation, electroplating, hot dipping, cladding, enamel, painting
5. Environmental control: inhibitors
6. Design

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 http://www.pipe-design-
ltd.co.uk/acatalog/pipe-design-ltd-services.jpg

Chapter 6 Materials
Design
Environment
Protection

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Protection - Cathodic Protection
Corrosion protection may be achieved by polarizing the anodic structure
cathodically towards its open circuit position position in the environment. This is
able to reduce the corrosion rate of a metal to zero; thus the metal may remain
uncorroded indefinitely. To do so a cathodic current needs to be applied to the
structure, which may be provided from either of two sources:

1. By consuming another metal (which

is electrochemically more active) →
2e
-

ioH+/H2 + sacrificial anode protection

+

2H

H2/H+ 2. External power supply →

H
impressed current protection
2

2H +
+2
e-
(corrosion state)
H2 icorr
Potential

Ecorr
- impressed current
e
2+ +2
Zn
Zn/Zn2+ Eo
Zn
(open circuit state) Zn2+ + 2e - Zn

ioZn2+/Zn

Log, Current Density

4
Protection - Cathodic Protection
Cathodic protection is applied
to: steels, cast irons, copper alloys, aluminium alloys, etc.
for: underground pipelines, underground cables, water storage tanks,
solar systems, submarines, sea-going vessels, steel buoys, canal
gates, marine piling, highway and bridge structures, condensers,
chemical installations.
against: uniform corrosion, corrosion fatigue, stress corrosion cracking,
intergranular corrosion, dezincification of brass, pitting of stainless
steels in sea water.
Cathodic protection is often applied
in conjunction with surface coating.

The Royal Albert Bridge at Saltash, built

largely of steel in 1859, has been
successfully maintained and protected
against corrosion for more than 150 years
by means of surface coating and cathodic
protection, a testimony of good engineering. 5
1. Sacrificial Anode Protection
First attempted in 1820s by British Navy to protect copper ship
sheathing using iron. Abandoned later due to marine life fouling.

Anode selection:
• Engineering and economic considerations
• Mg (with 6%Al, 3%Zn), most widely used
• Al alloys
• high purity Zn
• Anode efficiency

Open circuit potential consideration:

e.g., potential difference of Mg to steel is ~ 1 V
• Limit of protection length
• Limit of anode interval
• risk of over-protection (risk of H damage)
• risk of stray current corrosion (discussed later)

Can you use the mixed electrode theory to

explain how a sacrificial anode may reduce
the corrosion rate of a steel? examinable 6
1. Sacrificial Anode Protection

Application under water:

• best with "heavy" waters (i.e. high concentrations of ionic species) for their higher
conductivity;
• only effective to sections submerged in water;
• Al anode passivation: alloying with 0.1%Sn reduces passivation when used in
seawater.

Al anodes for
under water applications

http://www.metrex.co.za/marine-anode-supplies/

7
1. Sacrificial Anode Protection

Application in soil:
• backfill is used to provide better electrical contact between the anode and soil;
• backfills contain coke breeze, gypsum, or bentonite;
• when applied in soils under water, such as river beds, bottoms of lakes, sea
shore, no backfill is needed.
• Al anode passivation: backfill helps prevent Al anodes from passivation.

Packaged Mg anodes
for land applications
8
1. Sacrificial Anode Protection

Sacrificial anodes

Sacrificial Theoretical energy density Typical anode efficiency Standard potential

anode (Ah/kg) (%) V vs SHE
Mg 2200 50 -2.363
Al 2977 60 -1.670
Zn 820 90 -0.762

Theoretical energy density (TED) Anode efficiency (η)

𝒏𝒏𝒏𝒏 𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴𝐴 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
𝑻𝑻𝑻𝑻𝑻𝑻 = η=
𝟑𝟑. 𝟔𝟔𝟔𝟔 𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇𝑇 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
n: number of valence electrons
W: atomic weight
F: Faraday constant
Cu-CuSO4 electrode: 𝐸𝐸 = +0.314 𝑉𝑉 𝑆𝑆𝑆𝑆𝑆𝑆
9
1. Sacrificial Anode Protection

Chemical compositions of sacrificial anodes

10
1. Sacrificial Anode Protection
Example problem:
Determine the theoretical energy density of Mg anode, 𝐹𝐹 = 96485 𝐶𝐶/𝑚𝑚𝑚𝑚𝑚𝑚
in Ah/kg 𝑒𝑒 = 1.602 × 10−19 𝐶𝐶
𝑁𝑁𝐴𝐴 = 6.022 × 1023 /𝑚𝑚𝑚𝑚𝑚𝑚
• Molar mass of Mg:
𝑊𝑊 = 24.3 (𝑔𝑔/𝑚𝑚𝑚𝑚𝑚𝑚)
• Number of moles of 1 𝑘𝑘𝑘𝑘 Mg:
1000/𝑊𝑊 = 1000/24.3 = 41.15 (𝑚𝑚𝑚𝑚𝑚𝑚/𝑘𝑘𝑘𝑘)
• Total electrical charge in 1 𝑘𝑘𝑘𝑘 Mg:
1000/𝑊𝑊 𝑛𝑛𝑛𝑛 = 41.15 × 2 × 96485 = 7941152 (𝐶𝐶/𝑘𝑘𝑘𝑘)
• Total electrical charge in 1 𝑘𝑘𝑘𝑘 Mg in terms of Ah/kg:
1000/𝑊𝑊 𝑛𝑛𝑛𝑛
= 7941152/3600 = 2206 (𝐴𝐴𝐴/𝑘𝑘𝑘𝑘)
3600

Theoretical energy density (TED):

1000/𝑊𝑊 𝑛𝑛𝑛𝑛 𝒏𝒏𝒏𝒏
𝑻𝑻𝑻𝑻𝑻𝑻 = =
3600 𝟑𝟑. 𝟔𝟔𝟔𝟔

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1. Sacrificial Anode Protection

Sacrificial Anode Selection

Fresh water Fresh water Brackish water Salt water
(clean) (polluted) (mixed salt/fresh)
Aluminium Mg / Al Al Al / Zn Al
Bronze Mg / Al Al Al / Zn Al / Zn
Steel Mg / Al Al Al / Zn Al / Zn

Potential of Sacrificial Anode vs. Conductivity of Medium:

• Active anode (e.g. Mg) for low conductivity medium
• Less active anode (e.g. Zn) for high conductivity medium

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1. Sacrificial Anode Protection – Case Discussion
Using the information below, discuss the corrosion condition of
carbon steel in seawater when protected with Zn sacrificial anode

Note: remember these polarization Chemical analysis of 1040 carbon steel

curves are measured under standard
Fe C Mn Si P S
conditions, and seawater does not
conform to these conditions. This is 98.6-99.0 0.37-0.44 0.60-0.90 - ≤ 0.04 ≤ 0.05
only an exercise of the method.

15
1. Sacrificial Anode Protection – Case Discussion
Using the information below, discuss the corrosion condition of
carbon steel in seawater when protected with Zn sacrificial anode

What to do?
(1) Superimpose the two figures into one;
(2) Draw the common potential line;
(3) Move it up and down vertically till total anodic currents equal to the total
cathodic currents (current, not current density!)

16
1. Sacrificial Anode Protection What assumptions have been
made in the following analysis?
• Corrosion Rate of Fe decreased 𝒊𝒊𝑭𝑭𝑭𝑭
from 𝒊𝒊𝑭𝑭𝑭𝑭 → 𝒊𝒊𝑭𝑭𝑭𝑭−𝒁𝒁𝒁𝒁
𝒊𝒊𝑭𝑭𝑭𝑭−𝒁𝒁𝒁𝒁 𝒊𝒊𝒁𝒁𝒁𝒁−𝑭𝑭𝑭𝑭
𝑬𝑬 𝑣𝑣𝑣𝑣 𝑆𝑆𝑆𝑆𝑆𝑆
𝒊𝒊𝒁𝒁𝒁𝒁
𝒊𝒊𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄
+0.2

+0.0

-0.2

𝑬𝑬𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄
-0.4

-0.6

-0.8
𝟏𝟏𝟏𝟏−𝟏𝟏𝟏𝟏 𝟏𝟏𝟏𝟏−𝟏𝟏𝟏𝟏 𝟏𝟏𝟏𝟏−𝟖𝟖 𝟏𝟏𝟏𝟏−𝟔𝟔 𝟏𝟏𝟏𝟏−𝟒𝟒 𝟏𝟏𝟏𝟏−𝟐𝟐
Current Density, 𝑨𝑨/𝒄𝒄𝒄𝒄𝟐𝟐
17
1. Sacrificial Anode Protection – Case Discussion
Based on the analysis above, discuss the following:

• Why is the corrosion rate of Zn anode increased?

• Why is the corrosion rate of the steel is decreased?

• Is the steel fully protected?

• If not, what can we do to make sure it is protected?

• What about area ratio effect?

• What about concentration effect (Fe2+ in water)?
• What about dissolved oxygen effect?
• What about passivation of Zn anode?

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1. Sacrificial Anode Protection – Case Study
Design a sacrificial anode protection system for a drilling platform
It is planned to place an uncoated steel drilling
platform in the sea. The immersed parts of the
structure will be protected with aluminium alloy
(Galvalum I) sacrificial anodes for cathodic
protection for a life time of 10 years. Each anode
is made with a steel core for welding to the
structure.
Calculate the number of anodes (neglect the steel
core and two ends) for the required protection.

Data:
• wetted surface area of the structure: 2500 m2
• current required for protection: 110 mA m-2
• dimensions of Galvalum I: 200x200x1000 mm
• maximum current output of Galvalum I: 6.5 A m-2
• volume consumption rate of Galvalum I: 1180 ml A-1y-1
• anodic efficiency of Galvalum I: 60 %

19
1. Sacrificial Anode Protection – Case Study
Design a sacrificial anode protection system for a drilling platform
Data:
• wetted surface area of the structure: 2000 m2
• current required for protection: 110 mA m-2
• maximum current output of Galvalum I: 6.5 A m-2
• volume consumption rate of Galvalum I: 1180 ml A-1y-1
• anodic efficiency of Galvalum I: 60 %

Step 1: Determine the total current for the required

protection Note:
𝐼𝐼𝑑𝑑 = 𝑖𝑖𝑖𝑖𝑑𝑑 = 0.11 𝐴𝐴𝑚𝑚−2 × 2500 𝑚𝑚−2 = 275 𝐴𝐴 𝐼𝐼𝑑𝑑 : total protection current required for the
drilling platform
Step 2: Determine maximum current each anode 𝐴𝐴𝑑𝑑 : total wet surface area to be protected;
can provide 𝐴𝐴𝑑𝑑 = 2000 + 500 = 2500 𝑚𝑚2
𝐼𝐼𝑎𝑎 : maximum current each sacrificial anode
𝐼𝐼𝑎𝑎 = 𝑖𝑖𝑎𝑎 𝐴𝐴𝑎𝑎 = 6.5 𝐴𝐴𝑚𝑚−2 × 0.8 𝑚𝑚2 = 5.2 𝐴𝐴 can provide
𝑖𝑖𝑎𝑎 : maximum current density output of each
Step 3: Determine the minimum number of anodes sacrificial anode
required: 𝐴𝐴𝑎𝑎 : exposed surface area of each anode
ignoring ;
𝐼𝐼𝑑𝑑 275 𝐴𝐴𝑎𝑎 = 4 0.2 × 1 = 0.8 𝑚𝑚2
𝑁𝑁𝑎𝑎 = = = 52.88 → 53 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
𝐼𝐼𝑎𝑎 5.2
But how long can this protection last?
- How long can this structure be adequately protected?
- How long will the anodes last before they are fully consumed?
20
1. Sacrificial Anode Protection – Case Study
Design a sacrificial anode protection system for a drilling platform
To ensure the structure is still under adequately protection in 10 years of time, extra anodes
are required to account for the anode consumption so that by the end of the 10th year, the
remaining anodes can still meet the minimum protection current requirement.

Step 4: Determine the total volume consumption of Note:

anodes in 10 years 𝜂𝜂𝑎𝑎 : anode efficiency; 𝜂𝜂𝑎𝑎 = 60% = 0.6
𝑅𝑅𝑎𝑎 : volume consumption rate of anode;
∆𝑉𝑉𝑎𝑎 = 𝑅𝑅𝑎𝑎 � 𝐼𝐼𝑑𝑑 � 𝑡𝑡 𝑅𝑅𝑎𝑎 = 1.1 × 10−3 𝑚𝑚3 𝐴𝐴−1 𝑦𝑦 −1
= 1.1 × 10−3 𝑚𝑚3 𝐴𝐴−1 𝑦𝑦 −1 × 275 𝐴𝐴 × 10 𝑦𝑦 𝐼𝐼𝑎𝑎 : maximum current each sacrificial anode
can provide
= 3.025 𝑚𝑚3 𝑖𝑖𝑎𝑎 : maximum current density output of each
sacrificial anode
Step 5: Determine the number anodes consumed in 𝑉𝑉𝑎𝑎 : volume of each anode;
10 years, taking into account of limited 𝑉𝑉𝑎𝑎 = 0.2 × 0.2 × 1 = 0.04 𝑚𝑚3
efficiency
∆𝑉𝑉𝑎𝑎 3.025 𝑚𝑚3
𝑁𝑁𝑎𝑎,𝑐𝑐 = = = 126.04 → 127 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
𝑉𝑉𝑎𝑎 𝜂𝜂𝑎𝑎 0.04 𝑚𝑚3 × 0.6

Thus the total anodes required for the protection is 𝑁𝑁𝑎𝑎 + 𝑁𝑁𝑎𝑎,𝑐𝑐 = 53 + 127 = 180.

21
2. Impressed current cathodic protection (ICCP)

2e

-
ioH+/H2 +

+
2H

H2/H+
H
2

2H +
+2
e-
(corrosion state)
impressed H2 icorr Principle of impressed
Potential

current current cathodic protection

Ecorr
-
e-
+ 2e
2+
Zn
Zn/Zn2+ Eo
Zn
(open circuit state) Zn2+ + 2e - Zn

ioZn2+/Zn

Log, Current Density

22
2. Impressed current cathodic protection (ICCP)

• First attempts in Britain and USA in early

1910s
• Requires a DC source and an auxiliary
electrode (as an anode)

http://www.westcoastcorrosion.com/images/5b%20rectifiers.jpg
Rectifier to
convert AC to
Connection: DC
• + for auxiliary anode
• - for the structure
• insulate the electrical
cables to prevent
current leakage
Pipeline Soil needs to
to be Graphite as
conduct via
protected an inert
ionic species
anode
23
2. Impressed current cathodic protection (ICCP)
Anode considerations:
• scrap iron, graphite, Ti alloy, etc…
• distance from the structure
• intervals
• self-consumption
• backfill requirement
DC source:
• low-voltage DC batteries (Australia standard)
• rectifier from power lines
• motor generators
• windmill generators
• solar panels Anodes for ICCP in seawater
Noble metal anodes for
ICCP systems

ICCP rectifier

http://www.offshore-
technology.com/con
tractor_images/abd
ulla/2-impressed.jpg 24
2. ICCP – Impressed-current anodes

25
2. ICCP – Typical current requirements

Typical current requirements for cathodic protection of steel

𝑚𝑚𝑚𝑚/𝑚𝑚2

11-33

54-108
11-33
65-86
1-5

Note:
The goal of cathodic protection is to suppress the potential of a corroding metal to
its reversible potential, and the approach to achieving that is to provide a sufficient
(electron) current density to the metal 26
2. ICCP – Extra reading on noble anodes
• Platinum (Pt) is one of the six metals in the "Pt" group of precious metals.
• Pt is conductive, chemically stable and highly resistant to oxidation and corrosion, thus an excellent anode
material.
• Due to its high cost, Pt is not practical for direct use by itself, but is electroplated as a thin surface layer on
to a high corrosion resistance substrate, such as titanium (Ti), niobium (Nb) and tantalum (Ta).
• Pt may suffer from electrochemical damage/consumption when subjected to low frequency AC currents of
<50 Hz. The repeated oxidation/reduction processes result in the formation of a brownish layer of platinum
oxide.
• Some organic impurities such as sugar and diesel fuel may also cause damage to platinized layer on
anodes.
• Ti, Nb and Ta substrates have the ability to form an insulating oxide film under anodic conditions. They are
commonly used as anodes in ICCP. Among them, Ti is the least expensive; however, its oxide has a much
lower breakdown potential than those of Nb or Ta. The TiO2 breaks down at above 12 V anodic potentials.
In marine or chloride containing environment, the recommended safe operating voltage for Ti anodes is
9.5 V and for platinized Ti anodes it is 8 V. Voltages in excess of 10 V will result in severe pitting of Ti
anodes.
• For cathodic protection systems where the operating voltage is high, Nb and Ta anodes are used. The
breakdown potentials of their oxides are >100 V in chloride containing electrolytes. The wastage rate of
platinized anodes is approximately 8 mg A-1 y-1.
• Platinized titanium anodes take advantage of the low consumption rate and high current density of Pt
without the high cost.
• Typical Applications of Platinized Anodes:
Gold or rhodium plating in jewellery, printed circuit board industries, chrome plating, fuel cell, anodising
plant, electroplating of Fe, Ni, Zn, Tin, Cu, Ag, Au, Pd, ohmic heating of food, sensing elements, gold
electroforming, electro-refining, galvanizing, cathodic protection, electrodialysis, electro chlorination.

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 http://www.dimondelectric.com/images/layout/Picture-022.jpg

2. ICCP – Case Study 1

Design an ICCP system for under ground pipeline

Rectifier Ω
‘pumping’ 𝒆𝒆−
electrons 𝒊𝒊
to pipeline
so that it is
protected

• Current density (usually in mA/m2)

• Rectifier (to supply DC power, in multiples)
Q: the current density distribution curve shown above is
• Voltage very rough, can you determine the curve yourself?
• Anode material (life span, cost)
Current: to provide adequate current density
• Anode-to-structure distance (e.g., 10~300 mA/m2) to polarize the structure to
• Anode interval be slightly below its open circuit potential.
• Soil conductivity (field measurement if necessary) Voltage: adjusted to provide adequate protection
• Post-installation survey (needed for final adjustment) current, depending on distance between anode
and structure and soil conductivity (or resistivity).28
2. ICCP – Case Study 1
Design an ICCP system for under ground pipeline
• Pipeline: carbon steel; Φ 400 mm (OD); length 20 km 1
𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚 𝑖𝑖
• Required protection current density: 15-50 mA/m2 2 𝑚𝑚𝑚𝑚𝑚𝑚
• Rectifier: 50 V, 60 A max
• Anode: Ti
• Soil resistivity: 100 Ωm wet; 400 Ωm dry d 𝑑𝑑′ 𝑈𝑈
𝐷𝐷
Example calculations, for dry season: Note:
𝜌𝜌: soil resistivity
Step 1: Determine anode distance 𝑑𝑑 for 𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚 𝑈𝑈: voltage provided by the rectifier
𝑑𝑑 𝐴𝐴𝑜𝑜 : an elemental surface area
𝑈𝑈 = 𝐼𝐼𝑅𝑅 = 𝑖𝑖𝐴𝐴𝑜𝑜 𝜌𝜌 = 𝜌𝜌𝑑𝑑𝑑𝑑 𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚 : maximum protection current density
𝐴𝐴𝑜𝑜
𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚 : minimum protection current density
𝑈𝑈 50 𝑉𝑉 𝑑𝑑: anode – to – structure distance at 𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚
𝑑𝑑 = = = 2.5 m
𝜌𝜌𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚 400 Ω𝑚𝑚 × 0.05 𝐴𝐴𝑚𝑚−2 1
𝑑𝑑′ : anode – to – structure distance at 2 𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚
𝐷𝐷: anode interval length
Step 2: Determine the anode interval, 𝐷𝐷 𝐿𝐿: total length of pipeline being protected
𝑈𝑈 2 × 50 𝑉𝑉 1
𝑑𝑑 ′ = = = 16.7 m Q: why 𝑑𝑑′ corresponding to 𝑖𝑖 ?
2 𝑚𝑚𝑚𝑚𝑚𝑚
𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚 400 Ω𝑚𝑚 × 0.015 𝐴𝐴𝑚𝑚−2
𝜌𝜌 2

𝐷𝐷 = 2 𝑑𝑑𝑑2 − 𝑑𝑑 2 = 2 16.72 − 2.52 = 33.0 m

29
2. ICCP – Case Study 1
Design an ICCP system for under ground pipeline
1
Step 3: Determine number of anodes required to 𝑖𝑖𝑚𝑚𝑚𝑚𝑚𝑚 𝑖𝑖
2 𝑚𝑚𝑚𝑚𝑚𝑚
protect the pipeline of length 𝐿𝐿
x
𝐿𝐿 20000 𝑚𝑚
𝑁𝑁𝑎𝑎 = = = 606.06 → 607 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎 d 𝑑𝑑′ 𝑈𝑈
𝐷𝐷 33.0 𝑚𝑚
𝐷𝐷
Step 4: What about the number of rectifiers?
This depends on total current required for protection!
Note:
𝐴𝐴𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 𝜋𝜋Φ𝐿𝐿 = 3.14 × 0.4 × 20000 𝑚𝑚 = 25120 𝑚𝑚2 𝐿𝐿: total length of pipeline being protected
𝑁𝑁𝑎𝑎 : total number of anodes required
𝐼𝐼𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 𝒊𝒊𝒑𝒑𝒑𝒑𝒑𝒑𝒑𝒑 𝐴𝐴𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 = 40 × 10−3 × 25120 = 1000 𝐴𝐴 𝐴𝐴𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 : total pipeline surface area
𝐼𝐼𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 : total current required for protection
𝐼𝐼𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 1000 𝐴𝐴 𝑁𝑁𝑟𝑟 : total number of rectifiers required
𝑁𝑁𝑟𝑟 = = = 16.67 → 17 𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟
𝐼𝐼𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟𝑟 60 𝐴𝐴 𝑖𝑖𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 : a ‘selected’ current density within the
required protection range.
Step 5: Anything else have we not considered? Note that the protective current
• How large is the anode? (surface area, max current output) density on the pipe varies along its
length, and not linearly. So 𝑖𝑖𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 is
• How long will the anode last? (self-consumption rate)
not a simple mean of the range. In
• Where to put the rectifiers? addition, we also need to consider
• Wet season? (low soil resistivity, over-protection) the protection safety factor.
• Pipeline initially painted?
• Monitoring?
• ……
30
2. ICCP – Case Study 2
Design an ICCP system for re-bars in
concrete structure
Noble metal
ICCP system for anode strips
re-bars in concrete
structures

Concrete resistivity measurement

31
2. ICCP – Case study 3

British Standard BS-1377:

ρ > 100 Ωm: slightly corrosive
50 < ρ < 100 Ωm: moderately corrosive
10 < ρ < 50 Ωm: corrosive
ρ < 10 Ωm: severe corrosive

ICCP system is designed to protect the base of the tank!

Precious
metal anodes Distance to
Insulated
spread current
wires

• Four-electrode
measurement of soil
Filled with soil resistivity.
• Self-reading required:
Schlumberger and
Wenner methods. 32
2. ICCP – Case Study 4
Design an ICCP system for re-bars in
concrete structure

𝐴𝐴: total rebar surface area to be protected

𝑖𝑖: designed average protection current density
𝑑𝑑: average anode-to-rebar distance
𝜌𝜌: resistivity of concrete (wet)
Rectifier current: 𝐼𝐼 = 𝑖𝑖𝑖𝑖
Rectifier voltage: 𝑉𝑉 = 𝐼𝐼𝐼𝐼 = 𝑖𝑖𝑖𝑖ρ
Corrosion of re-bars causes
significant volume expansion
+ (to Ti anode) (due to formation of Fe2O3
rust) and cracks the
- (to rebars) concrete.

30V

28V
25V
22V

19V

Voltage drop along the line 33

2. Cathodic Protection – Monitoring
How do we know if we have adequate protection?
• We know whether or not we have enough current by measuring the potential of the steel
against a standard reference electrode, e.g., Ag/AgCl (0.230V ± 10mV SHE).

• An electron flow to a metal shifts its potential in the negative direction. Experience shows
that if a steel is polarized to -0.950 V vs. Ag/AgCl electrode, the corrosion is stopped.

E vs Ag/AgCl
Protected Unprotected + 0.23

- 0.23

- 0.43

- 0.63

- 0.83

- 1.03
http://www.cathodicprotection101.com/

Question: we know Fe/Fe2+: -0.44 V vs SHE, Ag/AgCl: +0.230V vs SHE, thus the difference
between the two electrodes is 0.67 V. Why it takes 0.95 V for the steel to stop corrosion?
34
2. Cathodic Protection – Monitoring
How do we know if we have adequate protection?

E vs Ag/AgCl
Ag/AgCl
+ 0.23 V

- 0.23

- 0.67 V
- 0.43
- 0.44 V
- 0.63

- 0.83

- 1.03

35
2. Cathodic Protection – Monitoring

https://www.sci
encedirect.com
http://www.pipe-st.com/elektrody-sravneniya /science/article/
abs/pii/S09589
46516305054

https://stoprust.com/products-and-
services/v-string/

https://cathwell.com/tech-categories/need-design/harbours/harbour-design/
36
 http://www.stoprust.com/img/8fig1.jpg
2. Cathodic Protection – Monitoring

http://www.ff-
automation.com/images/C
athodicProtection.jpg
37
2. Cathodic Protection – Potential Risks
Stray current corrosion:
• corrosion of nearby structures
caused by escaped current
from a cathodic protection
system.
• The problem can be easily
avoided by a simple electrical
connection of the protected
structure and the nearby
structure.

38
2. Cathodic Protection – Potential Risks

Over protection:
where a more-than-necessary current density is
imposed onto the protected structure, causing, e.g.,
excessive hydrogen evolution (thus hydrogen
embrittlement, blistering), debonding of coating,
waste of electricity and extra consumption of anode

https://www.polyguardproducts.com/wp-
content/uploads/2015/06/FBE-coating.jpg

39
3. Anodic Protection
Suitable metals: readily passivated when anodically polarised
• effective for Ni, Al, Ti, Fe, Cr and their alloys, stainless steels
• ineffective to Zn, Mg, Ag, Cu and their alloys
Principle: increasing anodic current to above a critical value
causes passivation to active-passive transition metals
Key to successful protection: constant potential
Application environments:
• best in handling sulfuric acid
• applicable to other acids, such as H3PO4 Pitting

• applicable to alkaline and salt solutions

Epit
• ineffective in HF, HCl and other acidic
chloride solutions
Passive

Potential
Eprot

Active

Log, Current Density

40
3. Comparison of Anodic and Cathodic Protection

Anodic Protection Cathodic Protection

Metals Active-passive metals only All metals
Applicability
Corrosives Weak to aggressive Weak to moderate

Installation High Low

Relative cost
Operation Very Low Medium to high

Throwing power Very high Low

Significance of applied Often a direct measure of protected Complex – does not indicate
current corrosion rate corrosion rate
Can be accurately and rapidly Must usually be determined by
Operating conditions determined by electrochemical empirical testing
measurements
Corrosion rate Low Nil

Protection current Low High

Easy monitoring of corrosion rate;

Monitoring since current consumed equals to the
corrosion rate;

41
4. Surface Covering – Electrodeposition
Surface covering provides barriers between metal and
environment.

Electrodeposition (electroplating)
• It is an industrial process to coat a thin layer of a more
noble (or passivation) metal to the surface of another
metal, typically for the purposes of corrosion protection,
aesthetic, abrasion resistance, or lubricity.

http://upload.wikimedia.org/wikipedia/
commons/thumb/b/b6/Copper_electro
plating.svg/471px-
Copper_electroplating.svg.png

http://upload.wikimedia.org/wikipedia/commons/e/e8/PCB_co
Copper coated steel wires for electric arc welding pper_layer_electroplating_machine.jpg
http://www.sanghvioverseas.net/sta http://img.diytrade.com/cdimg/94070/113583
inlesssteel-copperwire-ropes.html 49/0/1260251162.jpg

42
4. Surface Covering – Electrodeposition
• Common metals used for plating: Zn, Ni, Sn, Cd, Cr
• Electrolyte: commonly aqueous
• Quality depends on:
- deposition temperature
- deposition time
- electrolyte concentration
- current density
- thickness of the plating; thick plating can be rough and porous
- single layer or multilayer plating

Automobile Bumper: A Cu inner layer is firstly plated to assure good adhesion (known as the
strike layer). Then a Ni intermediate layer is deposited to give good corrosion resistance. Finally
a Cr layer of 50~500 nm thick is plated to give the shinny finish after polish.

http://lmchromeplating.com/gorillas-chrome-inc-
vehicles/electroplating-decorative-automotive-car-parts-
chrome-plating.jpg 43
 http://www10.aeccafe.com/blogs/arch-
4. Surface Covering – Hot Dipping showcase/files/2011/11/facade_option_galvanized_steel.jpg

• Suitable for low melting point metals; such

as Zn(420°C), Sn(232°C), Pb(327°C),
Al(660°C)
• Low cost and simple operation
• Low specification applications (fence posts,
re-bars, H-columns and I-beams, building
cladding materials) Architect design of a facility
(power grid in Denmark)
http://www.gaa.com.au/uploads/images/Welding%201.JPG

Hot dipping of carbon steel

I-beam in molten Zn, known
http://www.corrosionclinic.com/images/An_Adva
as galvanizing nced_Course_in_Hot-Dip_Galvanizing.jpg 44
4. Surface Covering – Cladding
Cladding is to (physically) add a thin surface
layer of a metal or cermet onto another.
Three common industrial cladding processes:
• laser cladding (fusion cladding)
• explosion welding
Explosion welding
• rolling welding of sheet materials
Cladding metals:
• usually ductile
• SS304L, Al, Co, Ni, Ti, etc.

Laser cladding

http://www.metalwebnews.com/howto/explosive-welding/fig1.gif

Tantalum

304L stainless steel

http://www.hardchrome.com.au/wpcontent/themes/theblock/im
ages/hardchrome/laser-cladding-01-500x375.jpg

45
4. Surface Covering – Cladding

CermaClad is a fusion
cladding process for
corrosion resistant
alloy (CRA) or cermet
pipe internal claddings.

http://mesocoat.com/cladding_process.html

Extrusion cladded CRA -

carbon steel pipes for oil
Sheet metal rolling cladding & gas industry

http://www.wickeder.de/en/product-groups/clad-
materials/product-description.html
46
4. Surface Covering – Ceramic Coating

Vitreous enamel coating:

• Vitreous enamel, also called porcelain enamel, is a material made by fusing powdered
glass to a substrate (often metal) by firing, usually between 750 and 850 °C. The powder
melts, flows, and then hardens to a smooth, durable vitreous coating.
• As a coating, enamel is protective to the base metal against corrosion in many
environments, mostly due to it is virtually impenetrable by water and oxygen.
• Its main weakness is the susceptibility to mechanical damage and thermal crack.
• Main applications: bathtubs, cooking pots, advertising panels, traffic signs, gasoline pump
casings, etc.

Portland cement covering:

• It is applied mostly to protect underground water tanks and pipelines.
• It has the advantages of low cost, a coefficient of expansion similar to that of steel, and
ease of application and repair.
• It can be applied by centrifugal casting or spraying. 47
4. Surface Covering – Organic Coating
• Paints, varnishes, lacquers and similar coatings protect more metals on a tonnage basis
than any other method for combating corrosion.
• Paints are a mixture of insoluble particles of pigment suspended in a continuous organic or
aqueous medium.
- pigments usually consist of metallic oxides (e.g. TiO2, Pb3O4, Fe2O3, BaO) or salts (e.g.
ZnCrO4, PbCO3, BaSO4, clay, etc).
- medium may be of natural oil, which dries by oxidising and polymerising to solid when
exposed to air, or synthetic resin, which dries after the evaporation of the solvent or
polymerizes upon the application of heat.
• Paints in general are not suitable for protecting buried structures due to the following:
- mechanical damage to thin coatings by contact with the soil.
• Paints are not suitable for high temperature applications
- organic compounds rarely stay stable at temperatures above 250 °C.

A paint consists the following:

• Binder: this is the essential part, or the base. It forms the body of
the paint, providing the impermeability, the strength and adhesion
of the paint to the substrate, and pigments
• Solvents (and thinners and dispersing agents), which evaporate
after application to leave behind the film of bound pigment.
• Pigments: which provide opacity, colour, gloss
• Additives: e.g., tiny metal flakes to make a metallic paint, glass
beads for reflective road signs
48
4. Surface Covering – Organic Coating
Success of corrosion protection by painting relies on three basic factors:
• Proper preparation of metal surfaces: surface preparation basically
involves cleaning (chemically if necessary) to remove dirt, grease, oil,
wax, rust, etc. and roughening to improve mechanical bonding;
• Proper selection of paints: the selection of coats is a complex task 1. Grease
requiring substantial knowledge. It is recommended to consult 2. Wax
reputable producers of organic coatings for the application of organic 3. Paint
coating in services; 4. Zn (Galvanising)
• Proper application of the paints: similarly, proper application of paints 5. Plastic
is also a complex task requiring substantial knowledge; 6. Vitreous Enamel
7. Ceramic
• Application of a primer layer 8. Anodising (Al)
• Application of an undercoat layer
• Application of a topcoat

49
5. Environmental Control
Common corrosion environments:
• atmosphere
• water - domestic, industrial, rain, ground
• sea water

Atmosphere - costal, tropical, desert, industrial, rural, urban

• moisture
• pollutants
• solid deposits

Aqueous - natural fresh, salty, domestic, industrial, rain

• temperature
• velocity
• solid suspension
• dissolved gases
• chemical concentration
• inhibitors, additives

50
5. Environmental Control – Atmospheric environment
It is basically an oxidation problem; complications due to:
• Moisture: many metals react with H2O+O2 combination more
rapidly than with either in isolation
• Chemically active pollutants (e.g., acid rain):
common pollutants in urban, marine, industrial atmospheres
include CO2, SO2, HS, NH3, NaCl, HCl
- cause side reactions
- lower the critical humidity for condensation; e.g., 70% in
clean moist air becomes 50% when 0.01%SO2 is present
• Metal dust corrosion (galvanic corrosion)
• Salt dust (chemically active) http://www.detailman-car-
detailing.com/brake-dust-repellant.html
• Inert particle dust (adsorbing moisture, deposit corrosion)
Brake dust corrosion
of alloy wheel

Acid rain
corroded stone
http://science.howstuffworks.com/nature/cli
mate-weather/atmospheric/acid-rain2.htm angle face 51
5. Environmental Control – Aqueous environment

Temperature (T):
• Generally, increasing T increases corrosion rate.
• When dissolved O is the principal cause of corrosion, however, increasing T
decreases the solubility of oxygen, thus decreasing the corrosion rate due to oxygen
depletion. The following are thus observed:
- boiling seawater is less corrosive than warm sea water;
- the combined effects of T and [O] cause the corrosion rate to increase with T initially to
reach a maximum and then decrease at higher temperatures, due to the reduced [O].

Fluid velocity: http://docs.engineeringtoolbox.com/docu

ments/639/oxygen-solubility-water-2.png
• Generally, increasing velocity increases
corrosion rate;
- erosion corrosion
- pitting attack of stainless steels

52
5. Environmental Control – Aqueous environment
Dissolved oxygen and other gases: http://academic.keystone.edu/jskinner/Limnol
• O2 and CO2 are the most frequently detected gases in water ogy/Water_Chemistry_LectureNotes.htm

• SO2 and HS are also found in circulated industrial waters

• Deoxygenation: common corrosion control technique
- vacuum treatment
- purging inert gas (Ar or N2)
- boiling
• Caution: metals that rely on passivity require O2 to form and
repair surface films. Deoxygenation may protect mild steels
but may cause more corrosion to stainless steels and
aluminium alloys.

Concentration of corrosive species:

• Corrosiveness of the solution generally decreases with decreasing concentration of
corrosive species; however
• Active-passive transition materials, such as stainless steels, achieve passivation in
solutions of higher oxidizing power. In these cases increasing the concentration of oxidizing
corrosive species may decrease corrosion rate.

53
5. Environmental Control – Corrosion Inhibitors
Adding inhibitors into environment is a frequently applied and an
effective technique of environment control for corrosion prevention.
• Inhibitors may be added directly into the solution, applied as surface coating, or even alloyed
into the metal (the inhibitor is released into the environment when the metal is corroded; e.g.,
inhibited copper alloys and stainless steels).
• There are many types of inhibitors, each works for a particular metal-environment conditions
in different ways.
• Most inhibitors are identified by empirical experimentation and their inhibition mechanisms are
relatively less understood.
• Many inhibitors are natural substances.
• The compositions of many industrial inhibitors are often not disclosed – proprietary products.

https://isalama.wordpress.com/article/corrosion-inhibitors-in-the-oilfield-3uf3kbfllnswt-4/
http://verituscorp.com/

54
5. Environmental Control – Corrosion Inhibitors

Corrosion inhibitors may work by:

• forming a physical film on the surface of a corroding metal; the film may act simply as a
physical barrier (isolating metals surface to the corrosive environment), or as a passive
film on the metal surface, or as a surface deposit increasing the resistance of the circuit).
• directly influencing anodic and cathodic reactions.
• changing characteristics of the environment either by removing or deactivating aggressive
constituents.

• increasing polarization Tafel constant of the anode → anodic inhibitor

• increasing polarization Tafel constant of the cathode → cathodic inhibitor
• increasing polarization Tafel constants of both anode and cathode → mixed inhibitor

55
5. Environmental Control – Classification of Inhibitors
There are many different classifications and each has its own arguments. Nonetheless,
corrosion inhibition are targeted on both metals to be protected and the environments there
are being subjected. The following is an example classification:

Corrosion Inhibitors

Interface inhibitors Environmental inhibitors

Vapour Liquid Scavengers Biocides

phase phase
e.g. e.g.
VCI or VPI oxygen to control
see slide 57 scavenger microbiologically
such as influenced
Anodic Cathodic Mixed
Na2SO3 corrosion (MIC)
(Passivator) in seawater.
Inhibiting anodic Inhibiting cathodic Inhibiting both anodic
reaction; usually reaction or and cathodic reactions
inorganic limiting cathodic via precipitates
substances: area; inorganic (inorganic) or
e.g. substances: adsorption (organic)
Chromates e.g. e.g.
Nitrates Phosphates Phosphates
Molybdates Carbonates Silicates
Organic substances 56
5. Environmental Control – Corrosion Inhibitors

Some common corrosion inhibitors include the following:

• Amines, Hydrazines:
- these are strong reducing agents, thus reductive inhibitors; note that hydrazine is
highly toxic, check out its MSDS.
- e.g., O2 can be removed by hydrazine solution; e.g., 𝑂𝑂2 + 𝑁𝑁2𝐻𝐻4 → 2 𝐻𝐻2𝑂𝑂 + 𝑁𝑁2

• Chromates (𝐶𝐶𝐶𝐶𝐶𝐶42− ):
- chromate loaded organic coatings are effective in preventing corrosion of metals; e.g.,
Na2CrO4 in concentrations of 0.04-0.1% is widely used in circulating-cooling-water
systems of internal combustion engines and cooling towers.
- but chromate inhibitors are toxic and are of environmental concerns.

• Molybdates based Corrosion Inhibitors

Applications Molybdates (𝑀𝑀𝑜𝑜𝑜𝑜42− ):
Steel, aluminium, copper
Central heating systems Sodium molybdate
Automobile engine coolant
Paints Zinc molybdate
Plastics Calcium molybdate
Strontium molybdate
Rubber Lead molybdate+lead chromate (Orange Molybdate)
Ceramics Phosphomolybdate, 𝑃𝑃 𝑀𝑀𝑀𝑀3 𝑂𝑂10 4 3−

57
5. Environmental Control – Corrosion Inhibitors
Volatile Corrosion Inhibitors (VCI) or
Vapour-Phase Inhibitors (VPI)
• VCIs are used to inhibit atmospheric corrosion of metals
without being placed in direct contact with the metal surface.
• VCIs are particularly useful to provide temporary protection
to metals during shipping or in storage, and are more
effective in closed spaces.

Examples of various
forms of VCI products https://www.protectivepackaging.
net/volatile-corrosion-inhibitors

Paper VCI Foam VCI Foil VCI

58
6. Design

Plant Design
• plant location: coastal locations are troublesome;
• waste management: fume removal, sewer treatment, dust collection,
environmental legislation;
• working environmental control: both equipment corrosion and work place
safety;

Equipment Design
• against galvanic corrosion: avoid using metals of large difference in galvanic
series in couples, apply insulation when they have to be used together, avoid
large cathode-anode area ratio;
• against crevice corrosion: avoid tight crevice, sharp corners and stagnant
areas, design for easy and complete drainage, use welded instead of riveted or
bolted joints, use butt welding instead of overlap welding whenever possible,
assure full penetration;
• design to exclude air: oxygen reduction is one of the most common cathodic
reactions during corrosion - particularly with agitators, liquid inlets, etc.

59