Chapter 5

Corrosion Protection

Remember
The five essential components of the corrosion cell (or
Requirements for Electrochemical Corrosion )are:
1- Anodic Zones (A)
2- Cathodic Zones (C)
3- Electrical Contact Between Them
4- Ionically Conducting Solution
5- Cathodic Reactant (1+4 cathodic Reactions)

Electronic Path

i
ANODE (A)

Where Corrosion
Occurs!!!!

CATHODE (C)

Ionic-Current Path

Cathodic
Reaction

Metal or alloy
Anode + Cathode +
Current Path

Corrosive Environment

Cathodic Reactant (1+4 !) +

Ionic Current Path (moisture)

= Corrosion

The Five Methods For Control Corrosion

Material Selection
Design
Changing the Environment

Changing the Metal Potential

Surface Coating (Zn, Sn, Plastic Paints etc)

1- Corrosion Control by Material selection

(selection of proper material for a particular
corrosive service depend on the environment)

Metallic

[choose the proper metal or alloy]

Nonmetallic (use isolating joints and seals ) [rubbers

(natural and synthetic), plastics, ceramics, carbon and
graphite, and wood]

Metals and Alloys

No Environment

Proper material

Nitric acid

Stainless steels

Caustic

Nickel and nickel alloys

Hydrofluoric acid

Monel (Ni-Cu)

Hot hydrochloric acid

Hastelloys (Ni-Cr-Mo) (Chlorimets)

Dilute sulfuric acid

Lead

Nonstaining atmospheric exposure Aluminum

Distilled water

Tin

Hot strong oxidizing solution

Titanium

Ultimate resistance

Tantalum

10

Concentrated sulfuric acid

Steel

2- Control Corrosion by Design Modifications

Corrosion Control must be properly addressed

during the design, installation, and subsequent
operation of systems.

Design Dos & Donts

To avoid SCC, you must avoid any excessive stresses.

To avoid galvanic corrosion, you must (1) avoid any contact between dissimilar
metals, (2) electrically isolate the two metals & (3) use high surface area anode.
To avoid erosion corrosion, you must avoid any sharp bends in piping systems
especially when high velocities and/or solid in suspension are involved.
To avoid crevice/pitting corrosion, you must (1) avoid stagnant water/electrolyte (2)
use good welding practice (weld rather than rivet) (3) use properly trimmed seals,
rubbers, and gaskets.
To avoid I.G.C, you must control the grain size and temperatures during the
manufacturing steps.
Avoid sharp corners where paint tends to be thinner and often starts to fail.
Prevent solutions from drying/concentrating and ensure complete drainage of tanks
to avoid any differential aeration (conc.) corrosion.
Consider using paints & ceramics.
Consider cathodic protections (1) zinc plating (galvanization), (2) use of sacrificial
anodes of Zn or Mg on steel ship hull (3) use of impressed voltage from a battery.
Design to exclude air except for active-passive metals and alloys, they require O2
for protective films.
Most general rule : AVOID ANY HETEROGENEITY !!!
2014 - I

2014 - I

3- Corrosion Control by Changing the Environment

Removal of O2 from the system
Control of pH (H+ions)

Reactants of the cathodic

reaction accompanying the
corrosion process

Addition of complexing agents to remove (mask) the aggressive

ions
Addition of inhibitors to decrease the rate of oxidation and/or

reduction reactions

4- Control Corrosion by Changing the Metal

Potential
Cathodic Protections
Shifting the metal potential to a
more cathodic value. This shift in
potential can be done by two different
methods.
(a) Cathodic protection with
impressed current
(b) Cathodic protection with sacrificial
anodes

Anodic Protection
Shift metal potential into a
range
where
passivation
occurs. This is done by
applying an external DC current
to the anode (prior to its use) to
form a protective passive film.

Anodic Protection
If an active-passive alloy is
maintained in the passive region
with a potentiostat, its corrosion
rate will be reduced to ipass. This
technique is based on the
formation of protective film on
metals by externally applied
anodic currents.

Anodic protection is based on passivation of the metal surface by an

application of an external DC current.

Cathodic Protection CP
Cathodic protection is achieved by supplying electrons to the
metal (anode) to be protected to force it to act as a cathode
instead of acting as an anode. This applied negative current
should be the positive corrosion current.
The CP is widely used in :

1) long pipe lines,

2) gas and oil transmission lines,
3) ships,
4) chemical processing equipment.

Cathodic Protection Methods

(a) Sacrificial Anode Method

Current is supplied by connecting the
object to a more reactive (easily
corroded) metal as a sacrificial anode. i.e.
formation of galvanic cell in which the
sacrificial anode is consumed (sacrificed).

(b) Impressed Current Method

Here, an external current is applied
from a DC source (e.g. a battery) and
auxiliary anode. i.e. an electrolytic cell
is formed where corrodible or inert
auxiliary anode can be used

cathode

anode

Cathodic Protection Methods

(a) Sacrificial Anode Method
Protection of Steel Structure
By connecting a piece of Zinc, Al or other
anodic material to the steel, in this case,
the zinc or other anodic metal is termed
Sacrificed Anode.

Cathodic protection of a
ship hull using a zinc
sacrificial anode

Cathodic protection of an underground pipeline

using a zinc sacrificial anode

Cathodic Protection Methods

(b) Impressed current Method

Stray current corrosion

-

Power +
supply

- Power
supply
Ground
level

Steel
tank

Current

Anode

+
Ground
level

Anode

Steel
tank

Anode

Localized
corrosion
Steel pipe

Insulated
connection

Steel pipe

It results from stray currents, i.e., current flowing through passes other than
the intended circuit, e.g., from electrical railways, ground DC sources, etc.
Stray current corrosion is basically independent of such environmental
conditions as O2-concn or pH. Depending on the intensity of stray current (that
is frequently higher than those produced by galvanic cells), corrosion may be
very rapid.
In contrary to galvanic-type currents, stray currents operate over long
distances and seek for the least resistant path causing severe corrosion where
it leaves the line.
Knowing where stray currents are present is highly important when remedial
measures are undertaken (Impressed Cathodic Protection) .

5- Corrosion Control by Surface Coatings

Normally, it is the first line of defense against corrosion: provides barrier between
a corrosive environment and the structure.
No coating is perfect and usually contains of holidays (voids) often resulting from
improper application and/or damage.
Coatings may act as sacrificial anode or release substance that inhibit corrosive
attack on substrate.

Coatings

Non-metallic coatings
Metallic coatings
Inert Barrier
Cathodic coatings Inert Barrier
Anodic coatings Sacrificial Barrier
Inorganic coatings
Application
Organic coatings
Electroplating,
Conversion coating
(Painting)
Chemical reduction
Portland cement coatings
(electroless plating),
Vitreous enamels
Hot dipping (galvanization),
Metal Spraying, etc.

Metallic coatings: (a) Cathodic coatings (Inert Barrier)

The coating metal is more noble than the substrate metal.
i.e. the coating metal is cathodic with respect to the substrate.
e.g. the coating of iron with silver, copper, nickel, Co, Sn, Pb on steel.
This coating should be free of pores/discontinuity which creates small
anode/cathode area leading to rapid enhanced attack at the damaged
sites.

Coating metal

Substrate metal

Metallic coatings: (B) Anodic coatings (Sacrificial Barrier)

The coating metal is less noble than
the substrate metal.
i.e. the coating metal is anodic with
respect to the substrate
e.g. the coating of Fe with Zn, Al.
Exposed substrate will be cathodic &
will be sacrificially protected.
Coating metal will form protective
passive layer

It is the use of Cathodic Protection in

conjunction with coatings to protect
the holidays or voids in the coating
system.

Methods of application of metallic coatings

Anode

cathode

(A) Electroplating: In this method the object to be coated

is made the cathode in an electrolytic cell in which the
electrolyte contains the coating metal in the form of ions.
Mz+ + ze M
N.B. In electrolytic cell electrodes have signs opposite to
those in a galvanic cell
+

Plating bath

(B) Chemical plating:

In this case the metal deposition can take place by:

(i) Displacement
An example of metal plating by displacement is
copper on steel according to the following reaction

Fe

Fe + Cu2+ Cu + Fe2+
More active metal

Plating bath Cu2+

More noble metal

This method is cheap but the coating is thin and

porous and not adhere very well to the steel.

(ii) Chemical reduction (Electroless):

In this case the deposition of the metal is carried
out with the aid of reducing agent which is added to
the bath. For example, nickel is plating from an
acidic hypophoshite bath according to
Ni2+ + H2PO2 + H2O Ni + H2PO3 + 2H+
This method gives good throwing power and
smooth deposits.

M
Plating bath Ni2+
+ reducing agent

(C) Hot- dip metal coating:

In this process the metallic object is dipped
into a bath of the molten coating metal.
Intermetallic compounds are formed at the
metal-coating interface with the object so
that an alloy layer is produced in the region.
For example coating steel with zinc by
dipping steel in molten zinc (hot-dip
galvanization).

Substrate

(D) Metal spraying

Material Feedstock

Heat Source

Accelerated
Droplet

Or

Coating

Metal spraying is carried out

with a spraying gun where the
coating metal is melted and
projected in the form of drops
towards the object surface. In
flame spraying, the coating metal
is melted with oxygen-acetylene
flame. In plasma spraying, the
coating metal is melted by
plasma beam (as ionized argon).

Non-metallic coatings
Inorganic coatings

Conversion coating

In this process, the metal reacts with a compound so

that a thin insoluble coatings are formed on the metal
surface.
The surface is converted into the coating with a
chemical or electro-chemical process.
They are used for corrosion protection, increased
surface hardness, to add decorative color and as paint
primers. Conversion coatings may be very thin, on
the order of 0.25 m. Thick coatings, up to 50 m,
are usually built up on aluminium alloys, either by
anodizing or chromate conversion.

Non-metallic coatings
Inorganic coatings

Conversion coating
(A) Phosphating (Chemical Conversion)
Phosphating is usually used on steel
before painting.
Phosphate coatings are usually applied to
carbon steel, low-alloy steel, and cast iron. They can
also be applied to zinc, cadmium, aluminum, and tin.

pH 4.0-5.5

H2PO4H2PO4H2PO4-

H2PO4-

insoluble highly adhere Iron

Phosphate
Fe2
+

Fe2
+

Fe2

Fe2
+

Fe

Fe

Non-metallic coatings
Inorganic coatings

Conversion coating
(B) Chromating (chemical conversion) :

Chromating is used for example on Zn,

Al and brass. The treatment is carried
out using an aqueous solution of
chromic acid or chromate salt where a
chromate coating is formed on the metal
surface.

coatings usually have good atmospheric corrosion resistance.

It has good electrical conductivity.
It is good base coating for subsequent coatings.
Chromate coatings are widely used in protecting common household products
and many hardware items with the yellow-brown appearance.
The

Non-metallic coatings
Inorganic coatings

Conversion coating
(C) Oxide Coatings

4Al + 6H2SO4 = 2Al2O3 + 6SO3 + 3H2 + 6H+ + 6e- + 1250 kJ

Thin coatings, 2 m to 25 m can be coated on most

aluminums. Thick coatings from 25 to 75 m are more
durable and abrasion resistant than above chemical
conversion coatings.
This oxide layer can be made in different colors depending
on the dye present in the bath.

Al anode

e.g. Anodizing (electrochemical conversion )

Thickening of the naturally occurring oxide layer
The anodizing process, usually performed on Al for
protection and cosmetic purposes.

cathode

The oxide coatings are in fact corrosion products which are thin, usually less than 2.5
m oxide with good adhesion. The oxide treatments are done by heat, chemicals, or
+
electrochemical reactions.

H2SO4 OR H2CrO4
Solutions

SEM image of porous alumina anodized

in 4 wt.% H2C2O4 at 45 V.
The pore diameter is ~ 44 nm.

The coatings usually have good atmospheric corrosion resistance.

It has good electrical conductivity.
It is good base coating for subsequent coatings.
Chromate coatings are widely used in protecting common household
products and many hardware items with the yellow-brown appearance.

Non-metallic coatings
Inorganic coatings

Portland cement coatings

Portland cement can be used to coat the metal (steel) and minimize
corrosion.
The coatings are usually several centimeters thick.
They often act as a diffusion barrier and raise the pH to more
alkaline levels.
The disadvantage is their sensitivity to mechanical damage.

Non-metallic coatings
Inorganic coatings

Vitreous enamels
They are hard glassy outside layer and protect
the inside metals by acting as an efficient barrier
to the corrosive environment
enamel (or vitreous enamel or porcelain enamel
in U.S. English) is the colorful result of fusing powdered
glass to a substrate by firing, usually between 750 and
850 degrees Celsius.
The powder melts and flows and hardens to a smooth,
durable vitreous coating on metal, glass or ceramic.

Non-metallic coatings

Organic coatings

Organic coating : paints, lacquers, varnishes.

Coating liquid generally consists of solvent,
resin and pigment. The resin provides
chemical and corrosion resistance, and
pigments may also have corrosion inhibition
functions.

Paints are composed of:

1. Pigments
2. Binder
95% of paints are (polymer + oils)
3. Solvent
Water based solvent or Oil based solvent

Corrosion preventing painting implies that the metal is covered

with a coating system which is able to minimize the corrosion
of the metal.
Painting includes the following steps:
1)
Cleaning the surface (degreasing and removal of corrosion products
as scale and rust from the surface).
2)
Application of primer: primer must have good adherence to the metal
surface and provide corrosion protection.
The following primers are usually used :
i.
ii.
iii.
iv.

3)

Red lead (Pb3O4) as pigment and linseed ( ) oil as binder.

Zinc chromate as pigment and alkyd resin as binder.
Zinc phosphate as pigment and alkyd resin as binder
Titanium dioxide (TiO2).

Top paint is designed to protect the primer against the effect of

moisture and sunlight as well as give the surface its appearance and
colour. The chief components of the top paint are pigment organic
binder and colouring material.

Properties to consider the

quality of coating

Average thickness of coating

Porosity or continuity
Adherence
Uniformity of thickness
Inert or passive