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.
