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Workshop Basic Chemistry of

Corrosion and Corrosion Control

21 November 2007

By : Alfajri Ismail
Technical Manager 3M Indonesia
Internationally, 1 tone of steel turns into rust every
90 seconds.

The energy required to make 1 tone of steel is

approximately equal to the energy an average
family consumes over three months.

Of every tone of steel from the worlds production,

approximately 50% is required to replace rusted

Source: Zinc Today, newsletter of the American Zinc Association

(Spring 1997)
Kerugian Akibat Korosi

Sekitar 1 5 % dari Pendapatan Domestik

Nasional / Gross Domestic Product (GDP).

Amerika Serikat pada tahun 1998 kerugian

akibat korosi adalah sebesar US $ 276 Milyar
yang merupakan 3,15 % dari GDP
Data Kerugian Akibat Korosi
No Sektor Industri / Negara Kerugian (US $)

1 Industri pesawat terbang (USA) 13 M / tahun

2 Pesawat militer (USA) 3 M/ tahun

3 Pesawat (tidak bisa terbang) 100.000 / hari

4 Angkatan Udara dan Laut (Australia) 50 juta / tahun

5 Otomotif (Finlandia) 300 Juta / tahun

6 Otomotif (USA) 0,25 % GNP tahun 1998

7 Menara Eiffel (Perancis) 40 juta / 7 tahun

8 Minyak dan gas (AGIP) 0,40 / barrel produksi tahun 1999

9 Minyak dan Gas (Laut Utara) 60% biaya pemeliharaan tahun 1999

10 Swiss 3 5 % GNP
80 % kerusakan material pada industri minyak dan
gas diakibatkan oleh korosi (US $ Milyar)

7 3.7 Eksplorasi
Pipa transmisi
Distribusi gas
0.9 Transport
7 Penyimpanan
Rust Never Sleep

2003 Brooks/Cole, a division of Thomson Learning, Inc. Thomson Learning is a trademark used herein under license.
When Corrosion can happen?
Reaction of a metal with its environment
Aqueous corrosion
reaction with water (usually containing dissolved ions)
High temperature oxidation
reaction with oxygen at high temperature
High temperature corrosion
reaction with other gases
Definition of Corrosion
1. Definition of corrosion in the context of
Corrosion Science : the reaction of a
solid with its environment.

2. Definition of corrosion in the context of

Corrosion Engineering : the reaction of
an engineering constructional metal
(material) with its environment with a
consequent deterioration in properties of
the metal (material).
Examples of Corrosion
Rusting of steel
corrosion product (rust) is solid but not protective
Reaction of aluminium with water
corrosion product is insoluble in water, so may be
Burning of magnesium in air
high temperature oxidation
Three types of oxides
may form, depending
on the volume ratio
between the metal and
the oxide:

(a) magnesium produces a

porous oxide film,

(b) aluminum forms a

protective, adherent,
nonporous oxide film,

(c) iron forms an oxide film

that spills off the
surface and provides
poor protection.
Three important factor of corrosion

1. Metalcomposition, detailed atomic structure, microscopic

and macroscopic heterogeneities, stress (tensile, compressive,
cyclic), etc.

2. Environmentchemical nature, concentrations of reactive

species and destructive impurities, pressure, temperature, etc.

3. Metal/environment interfacekinetics of metal oxidation

and dissolution, kinetics of reduction of species in solution; nature
and location of corrosion products; film growth and film dissolution,

Environments in
Effect of Composition
With regard to the effect of composition, ferrous metals fall into three
broad categories:
1. The ordinary cast irons, wrought irons and steels, to
which no alloying elements are added, and which are vulnerable to

2. Low-alloy steels, which contain about ,2-3% of alloying

elements, commonly copper, chromium and nickel. These steels still
rust, but under certain conditions in the atmosphere, the rust formed
becomes adherent and protective so that the corrosion rate becomes
several times less rapid than with the ordinary steels mentioned above.

3. Stainless steels, which contain high percentages of alloying

elements, e.g. 18% chromium, 8% nickel and 3% molybdenum. Steels
of this type are practically non-corrodible in appropriate circumstances.
Why does metal corrode?
Energy is released as material
proceeds towards natural state i.e.
the thermodynamically stable state.
Valency and Ions
When atoms lose or gain electrons, they become
Cations are positive and are formed by elements
on the left side of the periodic chart.

Anions are negative and are formed by elements

on the right side of the periodic chart.

Valence describes the possible number of electrons

an ion will pick up or donate. The valence state a
particular compound is also called its oxidation state.
In general, for metal M corroding:

M Mz+ + z e- (oxidation)

z e- + Z/4 O2 Z/ O2-
2 (reduction)

M + Z/4 O2 MOZ/2

For example, the corrosion of zinc in hydrochloric acid is

the net result of two electrochemical reactions:

Zn Zn2+ + 2 e- Anodic
2 HCl + 2e- H2 + 2Cl- (2 H+ + 2 e- H2) Cathodic

Zn + 2HCl H2 + ZnCl2 (Zn+ + 2Cl-)


It follows, that during metallic corrosion

Anodic Reactions
Zn Zn2+ + 2e- zinc corrosion
Fe Fe2+ + 2e- iron corrosion
Al Al3+ + 3e- aluminium corrosion
Fe2+ Fe3+ + e- ferrous ion oxidation
H2 2H+ + 2e- hydrogen oxidation
2H2O O2 + 4H+ + 4e- oxygen evolution
Oxidation reactions
Produce electrons
and there are several possible CATHODIC reactions:

hydrogen evolution (acids) 2 H+ + 2 e- H2

oxygen reduction (acids) O2 + 4H+ + 4 e- 2 H2O
oxygen reduction (neutral or base) O2 + 2 H2O + 4 e- 4 OH-
metal ion reduction M3+ + e- M2+
metal deposition M+ + e- M

Reduction reactions
Consume electrons

Note: More than one oxidation and more than one

reduction reaction can occur during corrosion.
Thus, metals tend to dissolve more readily in aerated acids
than in pure, de-aerated acid:
In aerated acids, oxygen reduction AND hydrogen
evolution can occur simultaneously:
2 H+ + 2 e- H2

O2 + 4H+ + 4 e- 2 H2O

Also, an oxidizer, such as ferric ion, as an impurity in

commercial acids makes them much more corrosive than
pure acids because of the extra cathodic reaction that
may occur:
Fe3+ + e- Fe2+
Effect of pH on reaction rate
Consider hydrogen evolution reaction :
2H+ + 2e- H2
The concentration of hydrogen ions will influence
the rate of the reaction
As the hydrogen ion concentration is increased (i.e.
the solution made more acid), so the rate of the
reaction increases
Similarly the potential will influence the reaction -
the more negative the potential the faster the
Effect of pH and potential on rate of
hydrogen evolution




Effect of pH on reaction rate
H2 2H+ + 2e-

This reaction will go faster in alkaline solution

(since H+ will be removed by H+ + OH- H2O)

This reaction will go faster at more positive

potentials (because electrons will be removed
from metal)
Effect of pH and potential on rate of
hydrogen oxidation
Faster Reduction

Slower Reduction Rates equal
Faster Electrochemical
The Nernst equation
2H+ + 2e- = H2
The Nernst equation gives
RT H ]
[ +
E = E0 ln
nF [ H2 ]
For 1 atm. hydrogen gas
E = E0 ln [ H + ]
Limitations of Pourbaix Diagrams
Tell us what can happen, not necessarily what
will happen

No information on rate of reaction

Can only be plotted for pure metals and simple

solutions, not for alloys
Five basic types of corrosion
Uniform or General corrosion: a regular loss of metal from the
surface cases a uniform thinning.

Localized corrosion: the majority of metal loss is experienced in

discrete areas.

Metallurgically Induced corrosion

Mechanically Assisted corrosion: physical environmental

factors play a significant role in metal loss.

Stress corrosion: generally cracking that is induced by

environmental factors.
8 Type of Corrosion
1. Uniform attack (general corrosion);
2. Galvanic corrosion;
3. Crevice corrosion;
4. Pitting;
5. Intergraular attack (IGA);
6. Selective leaching;
7. Erosion Corrosion;
8. Stress corrosion cracking (SCC)

This is the most common

form of corrosion.

A chemical reaction (or

electrochemical reaction)
occurs over entire exposed
surface (or large areas)
more or less uniformly.

Dry, damp or wet conditions have

profound effect on corrosion.

Dry atmospheres:
at ambient temperatures, most
metals corrode very slowly;
atmospheric oxygen promotes a
protective oxide film ... such films
are defect-free (sort of!), non-
porous (more or less!) and self-
Wet atmospheres:

Corrosion increases with

moisture content;

At critical moisture level (~ 70%

RH), an invisible, thin film of
moisture forms on (metal)
surface, provides electrolyte
for current.

Critical RH depends on surface

condition: cleanliness, presence of
oxide or scale, presence of salts or
other contaminants that may be
Wet atmospheres:
Promote puddles, pockets, visible water layers
(from dew, sea spray, rain, etc.);

Crevices, condensation traps, etc., create water

pools, and lead to wet atmospheric corrosion
even when rest of surface dry;

Soluble corrosion products increase wet corrosion

(dissolved ions increase conductivity, sustain
higher electrical currents);

Insoluble corrosion products may retain moisture

during alternate wet and dry conditions, lead to
continuous wet corrosion.
Wet atmospheric corrosion is often governed by
level of contaminants. e.g., marine salts vary
drastically with distance from the sea: steel at 25 m
from the sea will corrode 12x faster than same
steel 250 m away.

Industrial atmospheres are generally more

corrosive than rural, mainly because of sulfur
compounds produced by burning fuels.

SO2 selectively adsorbs on metals under humid

conditions metal oxide corrosion products catalyze
oxidation to SO3:

SO2 + 1/2 O2 SO3 (with a catalyst)

H2O + SO3 H2SO4
Nitrogen compounds promote atmospheric
corrosion from fuel burning (NOx as well as SOx),
as well as by thunderstorms.
N2 + x O2 2 NOx;
Nitrogen-based fertilizers (from NH3) increase
nitrogen pollutants in atmosphere.

H2S promotes atmospheric corrosion (e.g., Ag, Cu)

from industry (oil & gas, pulp and paper , etc.);
from decomposition of organic S compounds;
from sulfate-reducing bacteria (SRB) in polluted
rivers etc.
SRB + SO42- H2S
Surface temperature very
important - as T rises, corrosion rate
rises - though damp and wet corrosion
stop when moisture driven off;

Metal surfaces that retain moisture

generally corrode faster than rain-
washed surfaces; rain flushes impurities
off surfaces, removes particles, etc. that
promote differential aeration, etc.;

Note: dust, particles, etc. on surfaces

create crevices that can condense
moisture at various RHs.

Salt or soluble corrosion

products will form electrolytes in
condensed moisture - lower critical RH,
also increase corrosion.
Relative humidity very important: for clean Fe,
critical RH 60%

Above this, rust begins to form slowly from

deposited water film. At 75 - 80% RH,
corrosion rate increases rapidly (probably
because of capillary condensation within the
rust layer).

If corrosion product rust is micro porous,

moisture will condense at different RHs
depending on pore size:
1.5 nm - diameter pore (capillary) condenses
water at 50% RH;
36 nm - diameter pore at 98% RH.

Uniform attack minimized by:

Specifying proper materials;
Correctly applying coatings;
Using corrosion inhibition;
Protecting cathodically.
Galvanic corrosion MAY arise when
dissimilar metals are in contact in
aqueous solution.

The potential difference between

them will initiate attack, the corrosion
rate depends on the surface reactions
of (usually) both metals

Galvanic potentials are made use of in

batteries, e.g. the Daniel cell.
In the Daniel cell, the zinc
electrode is 1.1V negative
with respect to the copper

This has the accepted sign convention; however, some workers use opposite sign convention. These
potentials are listed in accordance with the Stockholm Convention. See J. OM. Bockris and A. K. N.
Reddy, Modern Electrochemistry, Plenum Press, New York, 2002

The cathodic reaction in

galvanic corrosion is usually
oxygen reduction or
hydrogen evolution, not
metal deposition.

To predict galvanic corrosion

of couples in seawater, we
use the table of Galvanic
Series of some commercial
metals and alloys in
seawater that.
Galvanic corrosion is under cathodic control if
we reduce the area of the Cathode (by coating,
etc.) we reduce the corrosion; if we reduce the
area of the Anode, corrosion will continue at the
same rate but over a smaller area, so perforation
etc. will occur sooner.

1. Select metals as close together as possible in galvanic series;

2. Avoid small-anode/large-cathode combinations . . . choose
fasteners of more noble materials;
3. Insulate dissimilar metals (e.g., sleeve bolts in flange joints, as
well as use insulating washers);
4. Apply coatings carefully, keep in good condition (esp. those on
5. Add inhibitors, if possible, to environment;
6. Avoid threaded joints where possible;
7. Design for anodic member (make thicker, easily replaceable,
8. Install a third metal that is anodic to BOTH in the couple.
Crevice corrosion is an intensive,
localized form of corrosion. It
generally occurs in cracks, holes,
crevices, lap joints, under gaskets,
rivet and bolt heads, and anywhere
else that small amounts of solution
can lay stagnate.

Crevice corrosion begins with the

typical corrosion cell, an oxygen
concentration cell. As the oxygen is
depleted the growth of the corrosion
cell is driven by the accumulation of
acidic hydrolyzed salts in the crevice
Initial Stages
Consider riveted metal section,
immersed in aerated seawater (pH 7)
e.g. stainless steel

Although O2 within crevice is rapidly

used up, corrosion continues,
Later Stages
controlled by overall cathodic reaction
outside the crevice.

Oxidation: M M+ + e-
O2 + 2 H2O + 4 e- 4 OH-

Most metal ions (except alkali metals)

M+ + H2O MOH + H+
Both Cl- and H+ accelerate metal
dissolution (Cl- breaks down oxide, also H+
partly responsible).
Minimizing Crevice Corrosion
Methods and procedures for combating or minimizing crevice corrosion are as follows:

1. Use welded butt joints instead of riveted or bolted joints in new equipment.
Sound welds and complete penetration are necessary to avoid porosity and
crevices on the inside (if welded only from one side).

2. Close crevices in existing lap joints by continuous welding, caulking, or


3. Design vessels for complete drainage; avoid sharp corners and stagnant areas.
Complete draining facilitates washing and cleaning and tends to prevent solids
from settling on the bottom of the vessel.

4. Inspect equipment and remove deposits frequently.

5. Remove solids in suspension early in the process, if possible.

6. Remove wet packing materials during long shutdowns.

Pitting Corrosion
Extremely localized form of attack
that often causes rapid
penetration of the wall thickness.

Difficult to detect (pits may be small on

surface, but extensive below surface
from undercutting; may be covered
with deposit);

Can cause equipment to fail (by

perforation) with very little weight loss; Pitting of 18-8 stainless steel by acid-
chloride solution.
Difficult to measure as pit depth and
distribution vary widely under
(nominally) identical conditions;

Incubation period may be months or Pitting of stainless steel

years. condenser tube.
Pitting Corrosion
pit growth
Pits usually occur on upward-facing
horizontal surfaces,

and less frequently on vertical surfaces;

pit growth Gravity is involved.

rarely on downward-facing surfaces;

pit growth
Has some features in common with CREVICE CORROSION....
consider metal M being pitted by aerated NaCl solution...
inside pit - anodic, rapid dissolution;
outside pit - cathodic, O2 reduction;
most M+ will hydrolyse, form H+;
positive charges attract Cl- ions;
H+ and Cl- accelerate metal dissolution;

high ionic concentrations in pit make O2

solubility very low;
high density of solution within pits
means pits are more stable when
Autocatalytic processes
occurring in a corrosion pit. growing downwards;
static environment accelerates process.

At high pH (i.e., high OH-

concentration), precipitation of
iron hydroxides and oxidation to
Fe3+ oxides can lead to
corrosion product caps or tubes
around pits on steels.

Corrosion tube growth mechanism.

Pitting Environments
Usually, solutions containing chloride or chlorine-
containing ions (e.g., hypochlorites [bleaches]) have
strong pitting tendencies.

Bromides are also aggressive, but fluorides and

iodides are not.

Cupric, ferric and mercuric ions promote pitting . . .

easily reduced cathodically and do not require
dissolved O2; CuCl2 and FeCl3 are extremely

Thiosulphate ion (S2O32-) may also promote pitting.

Erosion corrosion is a degradation of material surface due to
mechanical action, often by impinging liquid, abrasion by a slurry,
particles suspended in fast flowing liquid or gas, bubles or droplets,
cavitation, etc
The mechanism can be described
as follows:

Mechanical erosion of the

material, or protective (or
passive) oxide layer on its

Enhanced corrosion of the

material, if the corrosion rate of
the material depends on the
thickness of the oxide layer.
Most metals/alloys are susceptible
to erosion-corrosion.

Metals that rely on protective surface film for

corrosion protection are particularly vulnerable,
e.g.: Al, Pb, SS, CS.

Attack occurs when film cannot form because

of erosion caused by suspended particles (for
example), or when rate of film formation is
less than rate of dissolution and transfer to
bulk fluid.

Magnetite film dissolves reductively

High mass transfer rates remove soluble Fe II species;
Oxide particles eroded from weakened film by fluid shear stress;

Fe3O4 + (3n-4) H2O + 2e 3Fe(OH)n(2-n) + (3n-8)H+

Velocity Effects

Schematic showing the effect of flow velocity on

erosion-corrosion rate.

N.B. Turbulent flow regime for V < Vc is sometimes called

Flow-Assisted Corrosion regime.
Prevention of Erosion-Corrosion
Design (avoid impingement geometries, high
velocity, etc.);

Materials (use Cr-containing steels);

Use hard, corrosion-resistant coatings.

Cathodic Protection
Cathodic protection can, in principle, be applied to any metallic
structure in contact with a bulk electrolyte. In practice its main
use is to protect steel structures buried in soil or immersed in
water. It cannot be used to prevent atmospheric corrosion.
Structures that are commonly protected by cathodic protection are the exterior
surfaces of:
Ships hulls
Storage tank bases
Jetties and harbour structures
Steel sheet, tubular and foundation pilings
Offshore platforms, floating and sub sea structures

Cathodic protection is also used to protect the internal surfaces of:

Large diameter pipelines
Ships tanks (product and ballast)
Storage tanks (oil and water)
Water-circulating systems.
Principle of Cathodic Protection
Fe Fe2+ + 2e (1)

2H+ + 2e H2 (2)

2H2O + 2e H2 + 2OH- (3)

O2 + 2H2O + 4e 4OH- (4)

The principle of cathodic protection is in connecting an external

anode to the metal to be protected and the passing of an electrical
dc current so that all areas of the metal surface become cathodic
and therefore do not corrode.

(a) by impressing an electric current

from an external power source.

(b) by connecting the component to a

Sacrificial coatings
Zinc, cadmium and aluminium can protect steel by
sacrificial action: being anodic with respect to iron, they
hold the potential of the latter at a value at which it will not
corrode. Since the corrosion product is usually highly
protective, these metals build up a surface layer which
limits corrosion and prolongs the life of the coating. These
coatings can be used alone, or as a foundation for a paint
system, and their effect can be enhanced by chemical
conversion coatings.
Steel sheeting is coated with zinc by hot-dipping in the
molten metal, by heating with zinc dust (Sherardizing),
The Zn coating acts as a sacrificial anode... at the
inevitable imperfections, holes, etc., zinc dissolves
preferentially, deposits loose, flocculant Zn(OH)2 from
aqueous solution.

Protection continues as long as

enough Zn is left ... if large enough
areas of steel are exposed steel
corrosion will occur usually at the
middle of the exposed area.
If the temperature >60C, the Zn (OH)2 changes
from a loose to a hard, compact form.

This MAY change the polarity of the steel/Zn

couple by making the Zn more noble than the
steel; this CAN lead to rapid failure of the steel.

NOTE: Galvanized steel should only be used in pH

range 6 - 12.5.. ready dissolution of Zn in acids and
alkalis quickly removes protection outside the range.
CADMIUM PLATING similar action on steels to
zinc plating:
galvanic E less than for Zn;
more protective than Zn in marine environments
(chloride less soluble than ZnCl2- gives more
protective coat);
better than zinc in humid conditions indoors;
used less and less because Cd is toxic

TIN PLATING different action from Zn or Cd;

Sn is CATHODIC to steel; pinhole corrosion
can occur at imperfections in tin plate.
If the metal has a poor resistance to corrosion in the environment
under consideration make provision in the design for applying an
appropriate protective coating such as

(a) Metal reaction products, e.g. anodic oxide films on Al,

phosphate coatings on steel (for subsequent painting or
impregnation with grease), chromate films on light metals and
alloys (Zn, Al, Cd, Mg).

(b) Metallic coatings that form protective barriers (Ni, Cr) and also
protect the substrate by sacrificial action (Zn, Al or Cd on steel).

(c) Inorganic coatings, e.g. enamels, glasses, ceramics.

(d) Organic coatings, e.g. paints, plastics, greases.

Temporary protective
Apart from wrapping papers, which may be greased or
waxed, temporary protective materials can be applied to
metal surfaces to exclude moisture and dust.

They may take the form of greases or slushes, pastes,

thin films applied with solvents, or thick films of soft
thermoplastic materials which give mechanical protection.

All these types of protective may contain corrosion

inhibitors (see temporary protection guide).
Make environment less aggressive by removing
constituents that facilitate corrosion; decrease
temperature, decrease velocity*; where possible prevent
access of water and moisture.

For atmospheric corrosion dehumidify the air, remove

solid particles, add volatile corrosion inhibitors (for

For aqueous corrosion remove dissolved O2, increase

the pH (for steels), add inhibitors.
Control of RH
Most atmospheric corrosion can be prevented by
maintaining RH below 60%.

Desiccators and dehumidified stores can therefore be

used for storage.

In storerooms and warehouses it is important to maintain

the air temperature at a reasonable level and to avoid
large variations in temperature; a fall in temperature
overnight or at the weekend may lead to heavy
condensation of moisture.
Packages may employ desiccants: the two most common
agents are silica gel and activated alumina, both of
which are non-corrosive and an be regenerated by

Desiccated packages need careful design to take account

of the permeability of the wrapping material to water
vapour, the water content of the interior of the package,
and the absorptive capacity of the desiccant.
Selection of materials
Select metal or alloy (or non-metallic material) for the
particular environmental conditions prevailing
(composition, temperature, velocity, etc.) taking into
account mechanical and physical properties,
availability, method of fabrication and overall cost of

Decide whether or not an expensive corrosion-

resistant alloy is more economical than a cheaper metal
that requires protection and periodic maintenance.
If the metal has to be protected make provision in the design for
applying metallic or nonmetallic coatings or applying anodic or
cathodic protection. Avoid geometrical configurations that facilitate
corrosive conditions such as

(a) Features that trap dust, moisture and water.

(b) Crevices (or else fill them in) and situations where deposits can
form on the metal surface.
(c) Designs that lead to erosion-corrosion or to cavitations damage.
(d) Designs that result in inaccessible areas that cannot be re-
protected, e.g. by maintenance painting.
(e) Designs that lead to heterogeneities in the metal (differences in
thermal treatment) or in the environment (differences in
temperature, velocity).
Corrosion testing and monitoring
When there is no information on the behavior of a metal
or alloy or a fabrication under specific environmental
conditions (a newly formulated alloy and/or a new
environment) it is essential to carry out corrosion

Monitor composition of environment, corrosion rate of

metal, interfacial potential, etc. to ensure that control is
Supervision and inspection
Ensure that the application of a protective coating
(applied in situ or in a factory) is adequately
supervised and inspected in accordance with the
specification or code of practice.
Thank You