Corrosion and Deterioration of Material (MatE 6114)

Assignment on: Atmospheric Corrosion

 
Assignment Submission to: - Tesfaye Refera (Ph. D.)
Prepared by: - Solomon Mamuye
E-mail: [email protected]
ID: GSR/2676/12
 10.1 INTRODUCTION

 Atmospheric Corrosion is the degradation of materials

caused by air and pollutant contained in the air through
electrochemical process. Which may be
rain, dew, humidity or melting snow.
 Atmospheric corrosion takes place under
humid conditions, where the atmospheric relative
humidity exceeds the equilibrium relative humidity over the metal
surface.
 The corrosion rate is controlled by time of wetness, temperature and
the electrolyte composition.
 Classification of atmospheric corrosion
Atmospheric corrosion can be classified in the
following categories:
(a) Dry corrosion.
(b) Damp corrosion.
(c) Wet corrosion.

dry corrosion
Occures without presence of any liquid – direct reaction of gases in air with
metal.
many common metals develop films of oxide.
In the presence of traces of gaseous pollutants, copper,
silver and other non-ferrous metals undergo film
formation which is known as tarnishing.
Tarnishing is surface discoloration of metal or It is alteration in surface luster
 Damp Corrosion

 Damp corrosion would occur only when the relative humidity reaches at
70% which is the critical value for the onset of corrosion.
 This precise level of critical value of humidity varies with the type of
contaminants, such as dust and salt particles, and the composition of
metals.
 Damp environments promote the corrosion of most metals. Water
saturated with dissolved gases, such as CO2, H2S and SO2, cause
severe (dangerous) corrosion of iron and steels, copper, nickel, silver
and other non-metallic materials and alloys.
 In agricultural areas abundance of ammonia, during the rainy seasons,
subjects copper fittings to seasonal cracking and causes serious damage
to water distribution systems.
 Wet Corrosion

 The most frequently observed form of atmospheric corrosion.

 The metal surface remains constantly in contact with water.
 The rate of corrosion would depend on the solubility of the
corrosion product.
 Higher solubility means a higher rate of corrosion, because the
dissolved ions increase the electrolytic conductivity.
 Patina (thin green layer formation on copper, such as
brochantite, and corrosion of iron and steel structures are
common examples of corrosion caused by wet atmosphere.
Major Factors Affecting Atmospheric Corrosion
Time of Wetness
 It is the time during which the metal surface remains covered
with water before inducing corrosion.
 It depends on: Temperature, Porosity voids, degree of oxidation,
grain boundaries, nature of surface.
 relative humidity exceeds 80% and the temperature stays above
32°C, is taken as a limit for time of wetness.
Water Adsorption
 Water may be adsorbed in the molecular or dissociated form on a
metallic surface.

fig. water adsorption on a metal surface

 Effect of Atmospheric Factors on Atmospheric Corrosion
Relative Humide

 This is the primary driving force for atmospheric corrosion to occur.

 Atmospheric corrosion does not occur in dry air.

 The corrosion rates of metals increases sharply beyond a threshold level of relative
humidity called 'critical relative humidity.‘
 The level of the critical humidity varies with the nature of the
metal and the type of contaminant (such as KC1 and NaCl which reduces the
critical humidity).
 If the atmosphere is clear and uncontaminated, corrosion is
negligible at a relative humidity as high as 99%. However, in the presence of
contaminants, corrosion begins to increases around 80% RH.
 For example, steel can corrode even at 35% RH, in the marine environment.
 PH

 Decreased pH on a metallic substrate caused by dissolution of certain

contaminants like SO4-may lead to an acidification process and acceleration of
atmospheric corrosion.
DEW
 Dew is more corrosive than rain water because of a higher concentration of
atmospheric contaminants, hygroscopic salts and a lower pH value.
FOG
 Due to the low pH of fog water (1.8-3.5) in highly contaminated regions, like the
cities of Lahore and Karachi in Pakistan, fog is a corrosion promoter.
Dust and soot
 Impurities from emissions, such as CO2 and CO are adsorbed in dust particles and
create micro-corrosion cells. Dust particles being hygroscopic promote serious
corrosion by adsorption of salts promoting corrosion.
 Wind Velocity

Wind velocity affects the concentration profile of

salt particles in a particular area.
 It is responsible for the transport of pollutants which may be deposited on a metallic
substrate and dislodge a protective layer formed on a metal surface and promote
corrosion.
Corrosion Products
The corrosion products formed on a metallic surface (for example, Fe2O3, Fe3O4)
may induce or retard atmospheric corrosion.
Breakdown of the protective films by corrosion-inducing ions, such as chloride ions,
destroys passivity and accelerates the rate of atmospheric corrosion.

Fig. breakdown of oxide layer adsorption of

chloride ion.
 Pollutants
 Outdoor pollutants, like SO2, H2S, CO2, HNO3, NH3, HC1 and
HCOOH, are corrosion promoters. They accelerate corrosion with
humidity, temperature, wind and weather cycles.

Table. Outdoor ranges of

pollutants

Distance From The Source

Distance from the contamination source is an important factor in

atmospheric corrosion. Proximity to sea accelerates the corrosion rate
due to abundance of sea salts. At a distance inland of 10 km or more,
the corrosion rate is the same as observed further inland.
 pollutants chemistry and their impact on
atmospheric corrosion

Chlorine Containing Compounds

 These include CI2 and HC1. For instance, the atmospheric corrosion rate of
steel is accelerated at a critical humidity level of 70%.
 A hygroscopic salt absorbing water from the atmosphere can produce an
electrolyte which decreases the saturation relative humidity figure. Such salts
are called 'hygroscopics,' and are abundantly present in the environment.
 If the humidity exceeds this critical value, the saturated salt solution takes up
water until equilibrium is achieved and conversely the salt solution releases
water if the humidity level falls below the critical value.

Table. Selected hygroscopic salts

 Rain

•   plays a dual role, increasing the rate of atmospheric corrosion or

Rain
decreasing it under certain conditions.
1) Increase
(a) In the presence of atmospheric pollutants, like S02 in the air, it may
wash corrosion promoters, like and SO from the atmosphere and wet
deposit them in the presence of electrolyte layer, thus accelerating
corrosion.
(b) Degree of contamination.
(c) Orientation and design.
(d) Nature of substrate.
(2) Decrease
(a) Period of dry deposition.
(b) Structure and design.
(c) Droplets or crystals of chloride are formed in the atmosphere in a
marine environment.
 Cont…

 Chlorine dissociates to form a chlorine radical which reacts with organic

compounds to form hydrochloric acid.

 The adsorption of chloride and destruction of a protective layer is shown

in Fig. In the presence of chloride, iron and steel corrode at
significantly lower humidity levels.

Figure 10.4 Adsorption of Cl2 on a rust surface

 Oxides of Nitrogen
 Nitrogen and oxygen are present in the air and react significantly at
• combustion
  temperature.

 small amount of present in the atmosphere from the bacterial action on

nitrogen compound in soil.
 is a good absorber of light and undergoes the following reaction:

 The effect of oxides of nitrogen on atmospheric corrosion are not well

understood.
 Oxides of Carbon
 Sources of CO are mainly oxidation of methane in marshes
(>6%), oceans (3.9%) and from other natural resources (9.1%).
There are three distinct situations which produce CO.

 At high temperature C02 may dissociate to form CO and O2

 Carbon dioxide is soluble in water (1.45 g C0 2 per liter) which

makes it corrosive in the dissolved form.
 H + and CO3 ions are released which stimulate corrosion.

 The corrosion rate is increased with an increase in C0 2 pressure.

 Hydrogen Sulfide

• H2S
  is produced by the action of sulfate-reducing bacteria, fossil
fuels, combustion and petroleum refining.
 H2S in a dry atmosphere is only weakly corrosive. It dissociates
into and , the later being a corrosive species.
 Corrosion induced by H2S is a major risk in oil field equipment.

 The adsorption of H2S on a metallic surface is shown in the Fig.

 Oxides of Sulfur

• During
  the combustion of sulfur-containing materials, both SO2 and SO3
are formed.
 A significant proportion of SO2 is absorbed into aerosol particles where it
is oxidized to SO4.

 SO2 reacts with ions on the surfaces where it is absorbed and leads to the
formation of H2S04.

 The SO4 ion is released again when H2SO4 dissolves in water.

 SO2 is the main contributor to atmospheric corrosion.
 Mechanisms of Atmospheric corrosion
( Electrochemical Cycle)
 The rusting of steel or iron is accelerated by water (electrolyte) and
corrosion proceeds instantly after wetting.
 The primary cathodic reaction which occurs is

 At the anode redox potential are in the order of 0.3-0.5 VSHE.

 If pH is below 4, the oxyhydroxide may be reduced to Fe2+. Such a
situation may arise in rains or fogs.
 The reduction of oxygen becomes the rate controlling step.
 The charge balance is maintained by the generation of Fe2+ by the
anodic reaction.
 As soon as Fe2+ is generated, a variety of oxides and hydroxides, such
as Fe203, Fe304, Fe(OH)2, Fe(OH)3 and -FeOOH, may be formed.
 Con…
 The stable species of FeOOH exist in several different forms (,  and ).
•  
 The rust generally contains one inner layer of amorphous FeOOH and a crystalline
Fe304 outer layer.

Fig. Formation of rust layers

 The intermediate corrosion products also contain both Fe and Fe species.

2+ 3+

 The oxidation of Fe2+ to Fe3+ may be generated by hydrogen peroxide (H2O2),

hydroxyl radical (HOE), hydroperoxyl radical (2) or super oxide radical ion (2).
 The following are the reactions:

and also
 Cont…
 Another cathodic process takes on the oxide covered surface:

 This cathodic reaction has the slowest rate, hence, it is the rate
controlling cathodic reaction.
 It is followed by reduction of the rust formed to magnetite.

 It normally takes place under wet conditions.

 Upon oxyhydrolysis, Fe304 reverts to rust (FeOOH) in the
presence of oxygen and water.

 The freshly formed rust is not protective.

 The role of sulfur dioxide
 The oxidation of sulfur dioxide:
 

  The absorption of S02 in an aqueous layer leads to its acidification due to the
formation of 4 ion.

Fig. Oxidation of S02 in presence of moist particles and formation of H 2S04

 A reservoir of soluble sulfate nests surrounded by a hydroxide layer are formed
at the anodic site on the rusted surface.
 The sulfate nest acts as a storehouse for the supply of SO.
 In sulfate-containing solution, the following reactions occur:
 Con…
 Corrosion would only stop when SO is removed or unless fresh FeS04 is not
•  formed, such as in dry weather.
 The formation of SO in the rust leads to the formation of corrosion cells at the rust
-

FeS04 (sulfate nests) interface.

 Corrosion would continue to take place as long as the supply of SOis abundant. the
contribution of an electrochemical cycle to atmospheric corrosion is shown in Fig.

 To maintain corrosion, the corrosion cell requires an electronically conducting path

which is provided by ferrous sulfate.
 Con…
 The formation of FeS04 nests is illustrated in the following Fig.
 The Acidic Regeneration Theory
 The sulfuric acid formed by oxidation of S02 absorbed in the rust layer attacks
steel in the presence of oxygen to form ferrous sulfate (FeS04).

 The sulfuric acid is reformed by oxidative hydrolysis.

 The production of FeS04 provides the electrolyte necessary to carry the electrical
current and leadsto the dissolution of the protective Fe203 or Fe304 film on iron
and steel surface.
 One S02 ion can cause dissolution of 100 atoms of iron.
 The acidification process leads to more and more corrosion of iron and generation
of FeS0 . The acid regeneration process is illustrated in Fig.
4
 Potential-PH Diagram ( Fe - H2 0)
 The following Fig. show Potential-pH diagram for the Fe-H20 system at 25° C,
for a concentration of iron ionic species of 0.1 M. The approximate regimes for
fog and rain are indicated.

 The PH potential diagram can, however, be used only under equilibrium

conditions.
 Atmospheric Corrosion of Copper and its Alloy
 Copper and copper alloys are well-known for their excellent resistance to
corrosion in corroding environments.
 Several statues of bronze and brass stood for hundreds of years before being
destroyed by environmental pollutants.
Environmental Exposure
 On exposure to the atmosphere, copper and copper alloys are known to form a thin
layer of greenish blue or brownish green corrosion product, called patina.
 The following are the major copper alloys of interest in corrosion engineering:
(a) Brasses. These are basically copper-zinc alloys containing up to 43% zinc.
The brasses have high ductility and they can be cold worked. Cartridge brass
(70/30 brass) is the most commonly used brass and is used where high ductility is
required.
(b) Bronzes:- Copper-tin alloys are known as tin bronze. Alpha brasses contains
up to 9% tin at room temperature and they can be cold worked.
 The primary components of patina are copper oxide and salts of copper, such as:
 Con…
 The basic ingredients of corrosion products are oxides CU2O and CuO which
are highly protective. They react with the environmental pollutants to form salts.

 The most common ingredient of patinas in urban areas is the basic sulfate salt
Cu4(S04)(OH)6 called brochantite.

Table. Constituents found on corroded surface of copper

 Requirements For Patina Formation
 (1) Copper ions (Cu++): These are produced by oxidation of copper by SO2
•   in the atmosphere.
 (2) Aqueous layer: Water monolayers ranging from 5 nm to 10 nm thickness
may be formed on clean copper exposed to 60-90% RH.
 (3) Sulfur: Oxidized sulfur species are present in copper minerals.
 (4) Oxidizer: An atmospheric gas or a product of precipitates.
Role of Sulfur in Atmospheric corrosion of Copper
 Sulfur dioxide stimulates oxidation. It is the major driving force for corrosion
in metropolitan areas.
 H2S, SO2 and COS(carbonyl sulfide) in all these participate directly in the
corrosion process.
 SO2 may hydrolyze to form a bisulfate ion.

 which is converted to SO- ion by either ozone or transition metal ions which
may be present on the films on copper
 Con…
 Once SO is formed and enters the aqueous layers, Cu4(S04)(OH)6 (brochantite) is
•  formed, which is the major component of patina.
 Other products formed on patinas may be posnjakite [Cu4(S04)(OH) 6H20] and
malachite [Cu2(C03)(OH)2].
Cracking of Copper Alloys
 Ammonia and ammonium compounds are the major species associated with stress
corrosion cracking (SCC) of copper alloys.
 Water layers on metals dissolve significant quantities of ammonia from the air.
 The formation of cupric ammonium complex and the copper alloy surface is
essential for the onset of stress corrosion cracking.

 Adsorbed layers on the copper alloy surface dissolves significant quantities of

ammonia and stimulates the corrosion process by formation of complex Cu(NH3)
ions which are adsorbed on the surface.
 The cupric ammonia complex is the major contributor to seasonal cracking.
 Seasonal Cracking of Alpha Brass
 Alpha brass (70/30) when subjected to a stress in the presence of oxygen and
ammonia, cracks occur along the grain boundaries either in an intergranular form
or in a transgranular form. Either type of cracks are known as seasonal
cracking.
 Four steps are basically involved in the process:
(1) Segregation on the grain boundaries and formation of complexes with
ammonia.
(2) Creation of anodic and cathodic areas induced by electrochemical
processes.
(3) Plastic deformation and by accelerating crack growth by applied stress.
(4) Propagation of the crack resulting in failure.
 The SCC may be minimized by annealing brasses and preventing them from
exposure to ammonia containing environment. The seasonal cracking of brass is
shown in Fig.
 Aluminum and its Alloys
 Aluminum resists corrosion from the atmosphere if there is an absence of
narrow crevices.
 The corrosion resistance of aluminum is due to its tendency to form a compact
oxide layer over the surface.
 The oxide formed offers a high resistance to corrosion.
Corrosion Behavior of Aluminum in Atmosphere
 Aluminum corrosion rates of 0.03 to 4 µm/year have been reported.
 Table. shows the corrosion rates of aluminum and selected aluminum alloys in
different environments.
 Con…
 Casting aluminum alloys containing Si and Mg show a good resistance to
corrosion in all atmospheres, whereas alloys containing copper show a
poor resistance in industrial and marine environments.
 Aluminum alloys of Series 5xxx (Al-Mg), and 6xxx (Al-Mg-Si) show a
good resistance to atmospheric corrosion.
 Alloys of Al 6061, 6013, 5052 and 5054 can be used in the atmosphere
without any serious risk of corrosion. Table.Nominal compositions of
selected aluminum alloys
 Con…
 Alloys of series 2xxx and 7000, such as Al 2024 and Al 7075 are susceptible to
intergranular exfoliation and stress corrosion cracking in marine environments.
 The ranking of aluminum alloys in different atmospheres is shown in Table.
 Potential-PH Diagram ( Al - H20)
 A potential-pH diagram is shown in Fig. The Pourbaix diagram for aluminum and
water illustrates the stable phase for the different potentials and pHs. The numbers
—2, —4, etc. mean ion concentration of 10 ,10 , etc. in gram ions per liter.
 Con…
 The diagram, however, provides no information on the rate of corrosion
of aluminum and does not guarantee that corrosion would not occur in the
neutral pH range as flaws on metals, crevices and pits can cause corrosion by
developing a different pH within these regions.
 The protective oxides films formed prevent the outdoor atmosphere corrosion.
 Films, such as boehmite (-AIOOH), bayerite [-Al(OH)3] and hydragillite
[ -Al(OH)3] contain varying amounts of water.
 These films are amorphous. The crystalline films found on corroded aluminum
surfaces are shown in Table.
 Con…
 A variety of basic salts may be formed by deposition of S0 or on the protective
•  film formed on aluminum and stimulate corrosion.
 The protective film would dissolve in the region of low pH.
 The passivity of the film is destroyed by alkalization which stimulates the
cathodic reduction reaction leading to the dissolution of the protective layer on
the onset of corrosion.
Factors Contributing to The Corrosion of Aluminum
(a) Absorbed water layer:- The aqueous layers provide the conductive medium
for mobilization of aluminum cations and adsorbed anions.
 (b) Chloride levels:- the formation of AICI3 or Al(OH)2Cl, which are soluble in
weak acidic solution and do not offer resistance to aluminum dissolution.
(C) Sulfides and sulfates:- In aqueous layers, S02 dissolves and ionizes to
produce ion.

 Once is released, it is readily available to form poorly soluble basic aluminum

hydroxy sulfate Alx(S04)y(OH)2.
 Con…

(d) Nature of oxide layer:- Boehmite [-AlOOH or Al(OH)3-H20] and

Bayerite [Al(OH)3-3H20] are the major protective films found on an
aluminum surface.
 Bayerite (Al203.3H20) is very stable at a wide range of pH as shown by pH
potential diagrams and is responsible for the outstanding corrosion
resistance of aluminum.

Fig.a Corrosion of zinc in industrial atmosphere fig.b A simplified representation

of mechanics of atmospheric corrosion of aluminum
 Atmospheric Corrosion of Zinc
 Zinc is one of the most important tools used by engineers to control the
corrosion of steel in the atmosphere.
 Zinc coated steels are used in general building, constructions in
automobile bodies, in hardware, containers, tubes, pipe fittings, wires,
ropes and hundreds of other applications.
 Zinc is little susceptible to corrosion even at high humidity. At 99%
relative humidity the atmospheric corrosion of zinc amounts to 0.007
g/m2/day.
Factors Influencing The Corrosion of Zinc
 (a) The duration and frequency of moisture content:- Corrosion is heavy
due to a prolonged covering with condensed water and a
contamination of the atmosphere.
 (b) The rate of drying of surface:- In sheltered area, the drying time is low
and the corrosion rate of zinc is accelerated.
 (c) The magnitude of industrial pollution:- In highly industrial environment,
a 610 g/m2 zinc coating would rust after 4 years and may be 80%
rusted in 10 years
 Con…
 Fig. shows corrosion of zinc by atmospheric pollutants.

 The corrosion rate of zinc in different Typical values of dust contents

environments is shown in the following Table. in different environments are
shown in Table.
 Influence of Atmospheric Variable on The Corrosion of Zinc
 Zinc oxide is the initial film which is formed in the presence of moisture or water.
 It is transformed into zinc hydroxide in an outdoor environment.

 If the pH of the moisture is sufficiently high, the zinc hydroxide formed reacts
with the pollutants present to form the corresponding basic zinc salts.

 In the carbonate type layer, ZnCO3 is most abundant.

 The most common carbonate films are: ZnCO3 and Zn5(C03)2(OH)6.
 Con…
 Hydrozincate [Zn5(C03)2(OH6)] compound is abundantly found in
protective rust layers of zinc.
 It is formed by a combination of Zn(OH)2 and zinc carbonate.

 The zinc hydroxide and the basic zinc salts form patina which protects the
zinc surface from further attacks.
 The increase in the corrosion rate is attributed to the formation of ZnS04.

 The formation of basic zinc sulfate leads to increased corrosion.

 ZnS0 dissolves the protective hydroxide layers and protective salts. The
4

formation ofZnS04 is shown below:

Corrosion Rate of Zinc in Different Atmosphere
(a) Urban atmosphere:- The average corrosion rate of zinc
corresponds to a material loss of 2-7 μm/year.
(b) Industrial atmosphere:- The average corrosion rate is about
3-20 μm/year.
 Major corrosion products formed in industrial atmospheres are:
ZnOH(C03)o.5, Zn(OH)1.5 (SO4)0.25 and ZnS04.
 Figure. shows the corrosion of zinc by atmospheric pollution.
 Con…
(c) Marine atmosphere:- In marine environments, mixed salts of
Zn5(OH)gCl2 are deposited on the zinc surface and not protective.
 In a highly polluted atmosphere [Zn5Cl2(OH)8.H20] called 'Simonkollite'
is formed.
 The corrosion of zinc coated steel in a marine atmosphere is shown in Fig.
 Con…
 The average rate of corrosion of zinc is 1-7 μm/year in coastal areas.
 Assuming a zinc coating thickness of 80-100 |xm, the corrosion
protection would amount to:

10-12 years in industrial atmosphere

20-22 years in marine climates
50 years in rural areas.
 A zinc coating of 700-800 g/m2 is expected to have a service life of
more than 30 years if the structure is located at a distance of 200 m
from the coast.
Thank You!