ANODIC PROTECTION

It was first suggested by

Edeleane in 1954. This technique was
developed using electrode kinetics
principles and is somewhat difficult to
describe without introducing advance
concepts of electrochemical theory.

Simple anodic protection is based

on the formation of a protective film
on metal by externally applied anodic
current.

Metal with active-passive

transitions such as nickel, iron,
chromium, titanium and their alloys,
if carefully controlled anodic currents
are applied to these materials, they
are passivated and the rate of metal
dissolution is decreased.

To anodically protect a
structure, a device called a potentiostat
is required. A potentionstat is an
electronic device which maintains a
metal at a constant potential with
respect to a reference electrode.

Figure.6-8 Anodic protection of a steel

storage tank containing sulfuric acid.

The potentiostat has 3 terminals

In operation, the potentiostat maintains
a constant potential between the tank and
the reference electrode, the optimum
potential for protection is determined by
electrochemical measurements.

Table 6 - 4 Anodic Protection Austenitic Stainless Steel at 30C

(Protected at 0.500 volt vs. Saturated Calomel Electrode)
Alloy
type

304
(19 Cr- 9Ni)

Corrosion rate, mpy

Environment
(air exposed)

Unprotected

Anodically
protected

N H2SO4 + 10-5 M NaCl

14

0.025

N H2SO4 + 10-3 M NaCl

2.9

0.045

N H2SO4 + 10-1 M NaCl

3.2

0.20

10N H2SO4 + 10-5 M NaCl

1930

0.016

10N H2SO4 + 10-3 M NaCl

1125

0.04

10N H2SO4 + 10-1 M NaCl

77

0.21

SOURCE : S. J. Acello and N. D. Greens, Corrosion, 18 : 286 (1962).

Table 6-5 Current Requirements for Anodic Protection

Temperature
Fluid and
concentration
F

Current density, ma/ft2

Metal

To passivate To maintain

H2SO4
1 molar

75

316SS

2100

11

15%

75

304

390

67

30%

75

304

500

22

45%

150

304

165,000

830

67%

75

304

4700

3.6

67%

75

316

470

0.09

67%

75

Carpenter
20

400

0.8

93%

75

Mild steel

260

21

SOURCE : C. E. Locke et al., Chem. Eng. Progr., 56 : 50 (1960).

Table 6-5 Current Requirements for Anodic Protection

Temperature
Fluid and
concentration
F
Oleum

Current density, ma/ft2

Metal

To passivate To maintain

75

Mild steel

4400

11

75%

75

Mild steel

38000

19000

115%

180

304SS

0.03

0.00014

75

304SS

4400

9.4

H3PO4

NaOH
20%

SOURCE : C. E. Locke et al., Chem. Eng. Progr., 56 : 50 (1960).

COMPARISON OF ANODIC AND

CATHODIC PROTECTION
Anodic and cathodic protection tend to
complement one another.
Anodic protection - weak-very agressive
Cathodic protection -moderately corrosive

It is not practical to cathodically protect

metals in very aggresive mediums.

Table 6-6 Comparison of Anodic and Cathodic Protection

Anodic protection

Cathodic protection

Applicability
Metals

Active-passive metals
only

All metals

Corrosives

Weak to aggressive

Weak to moderate

Installation

High

Low

Operation

Very low

Medium to high

Very high

Low

Relative cost

Throwing power
Significance of applied
current
Operating conditions

Often a direct measure

of protected corrosion rate
Can be accurately and
rapidly determined by
Electrochemica
Measurements

Complex-does not
indicate corrosion rate
Must usually be
Determined
by empirical testing

INSTALLATION
OPERATING COSTS

Throwing power or the uniformity of

current-density distribution.
Cathodic protection
Low and requires numerous closely
spaced electrodes to achieve uniform
protection.
Anodic protection
high throwing power-a single auxiliary
cathode.

ANODIC PROTECTION
has 2 advantages.
1. The applied current usually equal to the

corrosion rate of the protected system.

not only protects but offers a mean for
monitoring instantaneous corrosion rate.
2. Operating conditions can be precisely
established by laboratory polarization
measurements.

Anodic protection can be classed

as one of the most significant
advanced in the entire history of
corrosion science.

COATINGS
Metallic and Other Inorganic Coatings
Relatively thin coatings of metallic
and inorganic materials can provide a
satisfactory barrier between metal and
its environment.
The chief function of such coating is
to provide an effective barrier.

Metal coating are applied by

- electrodeposition, flame spraying,
cladding, hot dipping and vapor deposition.
Inorganics are applied or formed by
- spraying diffusion or chemical conversion.
Porosity or other defects can result in
accelerated localized attack.
EX. Automobile bumpers, silverware,
galvanized steel, tin cans.
bathtubs ceramic coatings.

 Electrodeposition called electroplating

consists of immersing a part to be
coated in a solution of the metal to be
plated and passing a direct current
between the part an another electrode.

- Character of the deposite depends on

temperature, current density, time,
composition of the bath.
Thick (20 mils), thin (1/1000 mils),
dull or bright, soft or hard, ductile or
brittle.

 Hard plating combat erosion

corrosion.
Single metal, layers of several metals,
or even an alloy composition.
Zinc, nickel, tin, cadmium, gold, silver,
platinum.

Ex. Automobile bumper.

inner flash plate of copper, (for
good adhesion)
intermediate nickel, (corrosion
protection).
top layer chromium (primarily for
appearance).

Flame spraying also called metallizing,

consist of feeding a metal wire or powder
through a melting flame so the metal in
finely divided liquid particles is blown on
to the surface to be protected.

Oxygen and acetylene or propane

melting flame.
Coatings are usually porous not
protective under severe wet corrosive
conditions.

 Porosity decreases with the melting

point of the metal. zinc, tin and lead
are better from this standpoint than
steel or stainless steel.
The surface to be sprayed must be
roughened (sandblasted).
Mechanical bond.

 Sometimes paint coating is applied

over the sprayed metal to fill the voids
and provide a better barrier.
Porous metal makes a good base for
the paint.
Flame spraying is an economical way.
Applications include tank cars and
vessels of all kinds, bridges, ship
hulls and super structures.

Cladding a surface layer of sheet

metal usually put on by rolling two
sheets of metal together. Example, a
nickel and a steel sheet are hot
rolled together to produce a
composite sheet with say, 1/8 in of
nickel and 1 in of steel.

 High strength aluminum alloys are

often clad with a commercially pure
aluminum.
Sometime a thin liner is spot
welded to the walls of a steel tank.
Nickel, aluminum, copper, titanium,
stainless steels and other materials
are often used as cladding for steel.

 Cladding presents a great economic

advantage in that the corrosion
barrier or expensive material is
relatively thin and is backed up by
inexpensive steel.
A high pressure vessel 1/16 or 1/8
in clad on 3 in of steel.

Hot dipping Hot dip coatings are

applied to metals by immersing them
in a molten metal bath of low
melting point metals, chiefly zinc, tin,
lead and aluminum.
Thickness of the coating is much
greater than electroplates.
Coated parts can be heat treated to
form an alloy bond between the
coating and the substrate.

Vapor Deposition. This is accomplished

in a high vacuum chamber the coating
metal is vaporized by heating
electrically, and the vapor deposites on
the parts to be coated.
This method is more expensive than
others and generally limited to critical
parts. Example, high-strength parts for
missiles and rockets.
Deposite aluminum on steel.

Diffusion. Diffusion coatings involve

heat treatment to cause alloy
formation by diffusion of one metal
into the other. Also termed surface
alloying. Part to be coated are
packed in solid materials or exposed
to gaseous environments which
contain the metal that forms the
coating.

 Sherardizing (zinc coating),

chromizing (chromium), calorizing
(aluminum) calorizing, the surface is
oxidized to form a protective layer of
Al2O3.
Calorizing permits the use, at high
temperature of a strong but easily
oxidized steel, such as carbon (with
1% Mo) steel.

Chemical Conversion
Coatings from chemical conversion
are produced by corroding the
metal surface to form an adherent
protective corrosion product.
Anodizing consists of anodic
oxidation in an acid bath to bluid up
an oxide layer. best known
anodized aluminum (Al2O3).

 The surface layer is porous and

provides good adherence for paints.
The anodized surface can be sealed
by exposing to boiling water.
Bonderizing and Parkerizing
(Phosphatizating in a phosphoric acid
bath)
Chromatizing (exposure to chromic
acid and dichromates) and oxide or
heat coating for steel.

 Glassed Steel or glass-lined steel.

drug industry, in wine, brewery and
food plants.
Concrete is utilized for many
corrosion applications. Examples are
encasing structural steel, (also for
fireproofing), concrete-lined pipe,
and concrete vessels.

ORGANIC COATINGS
These involve a relatively thin barrier
between substrate material and the
environment. Examples are paints,
varnishes, lacquers and similar
coatings.
As a general rule, these coatings
should not be used where the
environment would rapidly attack the
substrate material.

3 main factors to consider.

1. Surface preparation.
2. Selection of primer or priming coat.
3. Selection of top coat or coats

 Surface Preparation surface roughening,

removal of dirt rust, mill scale, oil,

grease, welding flux, crayon marks, wax
and other impurities. A clean, rough
surface is needed.

- grit blast or sandblast.

- pickling and other types of
chemical treatments.
- solvent degreasing, hot or cold
alkali treatments, phophatizing
chromate treatment, electrochemical
treatment such as anodizing and
cathodic cleaning.

 To economic considerations, the

selection of surface preparation
method depends upon the metal to
be painted, the shape, size and
accessibility of the structure; the
coating system, and the service
conditions

Primers can contain rust-inhibitive

pigments such as zinc chromate and
zinc dust. Wett ability is needed so that
crevices and other surface defects will
be filled rather than bridged. Short
drying times are advantageous to
preclude contamination before the top
coats are applied, particularly in field
applications.

Top coat selection is important.

An important point here is that good
appearance and good corrosion
protection.
Multiple coats are needed so a
pinhole in one coat is covered by a
complete film of another. Thickness is
important also because paint
deteriorates or weathers with time.

Various methods are available to

reduce maintenance painting costs.
- one is to institute a touch-up
program to cover bad spots early.
- apply the paint by a hot-spray
method.
- applying tape on edges.
- design the structures such that
minimum surface area and edges are
presented.

 To sum up, a good paint job consists

of proper surface preparation, proper
coating selection, and proper
application.
Asphalts and bituminous paints are
often used on pipelines.

 Alkyds, glyptols, concrete, red lead,

iron oxide, phenolics, lithopones,
titanium dioxide paints and chlorinated
rubber. Vinyl and epoxy paints have
been widely adopted for corrosion
applications.

ECONOMICS
Economic Considerations Control of
corrosion is primarily an economic
problem. Whether or not to apply a
control method is usually determinated
by the cost savings involved. The
method or methods utilized must be the
optimum economic choice.

 Alternative corrosion-control systems

vary in cost, and higher cost must be
justified.
With regard to costs of metals and
alloys, composition is the first
guideline.
Type 430 costs more than ordinary
steel because of the added 17% Cr,

 Type 304 costs more because of the

nickel content.
Type 316 costs even more because
Mo. is an expensive alloying element.
Copper costs more than iron.
However, other factors strongly
influence the price to the customer.

Ex. Weight bar of steel worth $5, sewing

machine needles $5000, balance
wheels for watches $200000.
- Tiny electric motor for a missile
costs $300, 1-hp. motors $50
- Titanium may be more economical
than steel for seawater.

 Corrosion is not a necessary evil.

Large savings can be obtained by
controlling corrosion. Complete cost
and maintenance data are helpful to
delineate the high cost items and to
determine return on investment.
Satisfactory performance and desired
life at a minimum total cost per year
are all important.