Atmospheric Corrosion

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Atmospheric Corrosion
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Corrosion of mild steel
Corrosion of
aluminium
Exfoliation corrosion of
aluminium aerospace
alloy
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• Given the large surface areas of materials exposed to

the atmosphere, annual losses in the UK are of the order
of several hundred million pounds
• Compared with, for example, the effect of immersion sea

water on the corrosion of metals, atmospheric corrosion
is not as degrading. Additionally, not continuous in action
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Consider here corrosion processes in the

natural environment of the atmosphere.
Introduce following topics:
• The Atmospheric Environment
• Deposition Processes
• Atmospheric Corrosion
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The Atmospheric Environment; Composition
The atmosphere, also the sea, is one of the most common

natural environments to which materials are exposed.
Unlike most corrosion environments, the atmosphere does

not provide a constant exposure condition.
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For example, to determine the corrosion rate of a steel

specimen, may undertake following test:
• Laboratory measurement in 3.5% sodium chloride

solution at 20ºC
• Use defined mass transfer (i.e. constant stirring rate)
• Under such conditions, expect the corrosion rate to be

generally reproducible (± 50%)
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Similar specimen exposed in the atmosphere does not

experience a constant environment; hence, measured
corrosion rates are much less reproducible.
Main components of the atmosphere have an effectively

constant composition; however, minor components that
affect corrosion may vary significantly.
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AVERAGE COMPOSITION OF THE NATURAL ATMOSPHERE
Substance Concentration (vol% or ppm by vol)

Nitrogen (N2) 78.1%
Oxygen (O2) 20.9%
Water vapour (H2O) 0-5%
Argon (Ar) 0.93%
Carbon dioxide (CO2) 380 ppm
Other rare gases (Ne, He, etc.) 30 ppm
Hydrocarbons (mainly CH4) 2 ppm
Hydrogen (H2) 0.5 ppm
Nitrogen oxide (N2O) 0.3 ppm
Ammonia (NH3) < 0.1 ppm
Sulphur dioxide (SO2) 10-3 ppm
Oxides of nitrogen (NOx) 10-3 ppm
Hydrogen sulphide (H2S) 10-3 ppm
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Concentrations of water vapour vary naturally over large

range.
For example, on a hot, humid day there may be several

percent H2O vapour in the air.
Conversely, concentration drops to close to zero on a cold,

dry day.
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Natural air pollution
3 main primary sources of natural air gas pollution:

Volcanic action
Vegetation
Animal wastes.
Additionally, 2 primary sources of particulate pollution:

Sea-spray
Dust from the earth
Secondary sources of pollution arise from transformations in

the atmosphere, e.g. ozone and other photochemical action.
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Pollution is generally classified into “primary” species that

remain unchanged in the atmosphere after emission.
“Secondary” species result from transformation (change)

from some other primary species.
Pollutants also classified as either gaseous, particulate (

i.e. dust from ground), or aqueous (i.e. dissolved in rain).
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SOURCES OF NATURAL POLLUTANTS

Primary Primary
Volcanic action SO2, H2S, HCl, Cl2 – gaseous;
Volcanic ash - particulate
Biological respiration CO2 – gaseous
Animal waste NH3, organic sulphides – gaseous
Vegetation Hydrocarbons – gaseous
Soil microbes N2O – gaseous
Sea spray Cl-, SO42- – particulate aerosol
Soil (earth) from the ground Inorganic dusts - particulate
Natural (forest) fires CO2 – gaseous
Ash and smoke - particulates
Secondary Secondary
Oxidation of SO2 SO3 – gaseous
Reaction of NH3 + SO42- SO42- – particulate aerosol
Reaction of sea-spray with SO3 (NH4)2SO4 – particulate aerosol
HCl – gaseous
Oxidation of N2 during lightning NO/NO2 (NOx) – gaseous
Atmospheric photochemistry O3 (ozone) – gaseous
Plant hydrocarbons + O3 Hydrocarbon peroxides and radicals
(“Blue mountains of Virginia”) – gaseous
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Man-made atmospheric pollution
Main sources of man-made pollution from burning fossil

fuels, and other combustible materials in processes such
as waste incineration.
Additional atmospheric pollution arises from chemical

processing, sewage treatment and farming.
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SOURCES OF MAN-MADE POLLUTION
Primary Primary
General combustion (all fuels) CO, CO2 – gaseous
“Fly-ash”, carbon (smoke) – particulate
Fossil fuel combustion (oil, coal, gas) SO2, NOx – gaseous
Incineration (waste, plastics, coal) HCl, Cl2 – gaseous
Transport (vehicle exhaust) NOx, CO, hydrocarbons – gaseous
carbon (smoke) – particulate
Chemical processing Hydrocarbons, sulphides, NH3 – gaseous
Sewage treatment Sulphides, NH3 – gaseous
Farming (domesticated animals) CH4, NH3, sulphides – gaseous
Farming (growing crops) Hydrocarbons (CH4) – gaseous
Secondary Secondary
Oxidation of SO2 by O3 SO3 – gaseous
SO42- – particulate aerosol
Reaction of NH3 + SO42- (NH4)2SO4 – particulate aerosol
H2SO4 – “acid rain”
Oxidation of NOx by O3 NO3- - particulate aerosol
HNO3 – “acid rain”
Hydrocarbons + O3 Hydrocarbon peroxides and radicals
(“Photochemical smog”) – gaseous
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Climate effects; weather at a specific location.
Weather changes from place-to-place, from country-to-

country and from season-to-season.
General weather pattern for a region of a country usually

termed macroclimate.
Significant local variations (microclimate effects) with height

or distance from the sea; through human activity (e.g. cities
usually slightly warmer and more humid than the countryside);
very locally (e.g. depending on arrangement of buildings).
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• High smokestacks may transport pollutant emissions

over many hundreds of kilometres
• Medium height sources may transport to 50 kilometres
• Low emitter, i.e. domestic chimney, transports up to 250

metres
• Exhaust system, about 10-20 metres
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Pollutant deposition
Pollutants in the atmosphere consist of:

• “dry” species: gases, dry salt particles, dusts and smoke,
• “wet” species; gases, ionic salts dissolved in water droplets.
While suspended in the atmosphere, contribute to general

atmospheric pollution- reduction in atmospheric quality.
No influence on atmospheric corrosion or ground quality until

deposit onto a surface or the ground .
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Dry deposition
Gases or particulates (particles) transport to a surface by 3

main mechanisms:
• advection due to the airflow (wind)
• convection due to thermal air currents
• diffusion due to concentration gradient of the species

between the surface and atmosphere
Dry deposition generally accounts for most pollution

transport to a surface: ~ 70% of deposition on land.
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Wet deposition
Although most atmospheric pollution transport to surfaces

in the dry state, significant quantity dissolves in water
droplets in clouds and eventually falls as precipitation (i.e.
rain, snow, or fog).
Depending on the local climate, amounts to about 30%

pollutant deposition.
Note: gaseous pollutants dissolving in moisture film on

surface is counted as dry deposition.
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CONCENTRATION RANGES FOR ATMOSPHERIC POLLUTANTS
Pollutant Industrial (μg m-3) Urban (μg m-3) Rural (μg m-3)
SO2 100 – 200 30 – 80 5 – 20
NOx 100 – 200 20 – 40 < 10
HCl 10 – 20 1–5 <1
Smoke and ash 100 – 1000 20 – 50 < 20
Inland Coastal
Sea-salt aerosol (air) 30 μg m-3 1000 μg m-3
(rain) 5 mg dm-3 50 mg dm-3
Other dusts 0.1 – 50 μg m-3
Note that 1 μg m-3 = 1 ppb (part per billion – 109)

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“Acid rain”
Describes all forms of deposition, including wet and dry,

that eventually result in acidification of surface water.
Important to recall that, in the absence of any acidic

pollutants such as SO2, NOx and HCl, natural rainwater is
slightly acidic due to the presence of atmospheric CO2.
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The natural pH of rainwater readily calculated from following equilibrium:
CO2 + H2O  H+ + HCO3-
K= [ H  ].[ HCO3 ]
[CO2 ]
K = 1 x 10-7.6
[H+] = [HCO3-]
[H+]2 = 1 x 10-7.6 x pCO2
Volume concentration of CO2 in the atmosphere in 2018 was ~400 ppm:

hence, [H+]2 ~ 10-11 => [H+] = 10-5.5 = pH 5.5
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Atmospheric classifications
ISO9223, international standard:

provides a classification scheme for ranking pollution in a
particular climatic location. Scheme based on deposition
rates of SO2 and Cl-.
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SULPHUR DIOXIDE CHLORIDE
Deposition rate Concentration Chloride Deposition rate

SO2 class
mg/m2/day mg/m3 class mg/m2/day
P0 <10 <12 S0 <3
P1 10 - 35 12 - 40 S1 3 - 60
P2 36 - 80 41 - 90 S2 61 - 300
P3 81 - 200 91 - 250 S3 >300
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Humidity and time of wetness
Atmospheric corrosion, like all metallic corrosion, only

proceeds when sufficient water present to solvate ions
generated during anodic and cathodic reactions.
Atmospheric humidity clearly important in determining when

atmospheric corrosion proceeds.
Atmospheric humidity is a measure of amount of water

vapour in air.
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Humidity defined in two ways:
Absolute humidity = Concentration (pressure) of water

vapour in the air
Relative humidity = Actual water vapour pressure/

Saturated (maximum) water vapour pressure
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Relative humidity
Defines the thermodynamic water vapour activity at any

temperature. Important when considering condensation of
water on a surface.
• From the definition, at RH = 100%, liquid water is a stable

phase and condensation occurs.
• For RH < 100%, water vapour is the stable phase and,

normally, condensation does not occur.
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The saturated or maximum concentration of water vapour in

air varies as a function of temperature:
• At 100ºC water boils, so the maximum vapour pressure of

water is 1 atmosphere.
• Below 100ºC, the water vapour pressure is less than 1

atmosphere
For a given humidity, temperature below which water vapour

condenses termed the dewpoint.
Metal corrosion can not occur unless sufficient liquid water
on surface. Time during which the RH exceeds a critical
value is defined as the Time-of-Wetness of the surface.
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From 0 to 40oC water content of saturated air roughly

doubles for every 11oC rise in temperature:
• If air at 50% humidity is cooled by 11oC, it becomes

saturated with water vapour, increasing the atmospheric
corrosion rate of metals
• If air saturated with water vapour at given temperature

heated by 11oC, relative humidity falls to 50%
Fundamental to atmospheric corrosion
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ISO9223: classification scheme for ranking a particular

climate in terms of its time-of-wetness.
Time-of-wetness (TOW) calculated as the total time when

the RH is greater than 80% at temperatures above 0ºC.
Note, when raining, RH by definition is equal to100%.
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WETNESS TIME OF WETNESS

EXAMPLES OF OCCURRENCE
CLASS (hours/year) (%)
T1 <10 <0.1 Indoor

T2 10-250 0.1 - 3 Indoor, unheated
Outdoor, dry/cold climate, ventilated
T3 250-2600 3 - 30
buildings.
T4 2600-5200 30 - 60 Outdoor temperate climate.
T5 >5200 >60 Tropical outdoor or surf.
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Corrosion rates of steel with

time of exposure at different
locations worldwide
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Surface condition
In atmospheric corrosion, electrochemical (anodic and

cathodic) reactions occur in very thin layer of water
condensed on the corroding surface.
Physical and chemical nature of the surface (e.g.

roughness and contamination), as well as amount of water
condensed on the surface, control rate of corrosion.
Typical thicknesses of water layers on a clean (freshly

polished) metal surface are given in following Table:
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CONDITIONS WATER LAYER THICKNESS
Wet during rainfall > 500 μm
Covered by dew or condensation 50 –200 μm
100% relative humidity 1 – 5 μm
< 100% RH < 1 μm
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General atmospheric corrosion of metals
ISO9223 also provides a classification scheme for the

corrosivity of an environment based on the expected
corrosion rates of materials exposed outdoors for 1 year.
Thus, from a knowledge of the pollution classifications and

the TOW (time of wetness) classification, the corrosivity
classification can be derived.
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CORROSION RATES OF METALS

CORROSIVITY
CATEGORY
Units Carbon steel Zinc Copper Aluminium
g m-2 y-1 0 - 10 0 - 0.7 0 - 0.9

C1 (very low) negligible
µm y-1 0 - 1.3 0 - 0.1 0 - 0.1
g m-2 y-1 10 - 200 0.7 - 5 0.9 - 5

C2 (low) 0 - 0.6
µm y-1 1.3 - 25 0.1 -0.7 0.1 - 0.6
g m-2 y-1 200 - 400 5 - 15 5 - 12

C3 (medium) 0.6 - 2
µm y-1 25 - 50 0.7 - 2.1 0.6 - 1.3
g m-2 y-1 400 - 650 15 - 30 12 - 25

C4 (high) 2-5
µm y-1 50 - 80 2.1 - 4.2 1.3 - 2.8
g m-2 y-1 650 - 1500 30 - 60 25 - 50

C5 (very high) 5 - 10
µm y-1 80 - 200 4.2 - 8.4 2.8 - 5.6
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Factors affecting critical relative humidity
Water condensation can occur on metals at relative

humidity less than 100% from two mechanisms:
• Firstly, small diameter cracks and pores on the surface,

i.e. in corrosion product layer, can significantly reduce the
equilibrium humidity for condensation.
A long thin crack can stabilise water at ibase even though
external humidity relatively low. Process termed capillary
condensation and is the reason why a polished metal
surface corrodes initially more slowly than rusty surfaces.
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• Second mechanism for reduction in critical RH is

important and relates to chemical contamination (e.g. by
pollutants) on the surface.
Dried salt on a surface will have a tendency to dissolve in

condensed water to give, initially, a saturated solution of
the salt on the metal surface.
The dissolved salt reduces thermodynamic activity of

water and, hence, equilibrium RH in air immediately above
surface.
Following Table shows the RH at which water condenses
on a surface, contaminated with the salt.
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RH OF CONDENSATION ON A POLLUTED SURFACE AT 20ºC
Polluting salt RH of condensation

Na2SO4 93%
(NH4)2SO4 81%
NaCl 78%
MgCl2 ; CaCl2 35%
Calcium and magnesium chloride Surface polluted with sea salt is
are components of sea salt. wet at all RH > 35%
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Influence of humidity
on the corrosion rate
of zinc
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Atmospheric
corrosion of
selected metals
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Measurements show that the corrosion rate during drying is

many times higher than when a surface is just wet.
Hence, wetting and drying are critical components of the

mechanism of corrosion. Thus an artificial (accelerated)
test should use wet-dry cycles in order to be realistic.
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Corrosion rate of iron during wetting and drying
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Brown rust layer formed in the atmosphere generally consists of a

crystalline iron oxide-hydroxide, lepidocrocite, FeO(OH); magnetite,
Fe3O4, may also form.
The anodic reactions in atmospheric corrosion of iron are:
• Formation of ferrous hydroxide:

Fe + 2H2O  Fe(OH)2 + 2H+ + 2e-
• Oxidation of Fe(OH)2 to lepidocrocite:
Fe(OH)2  FeO(OH) + H+ + e-
• Oxidation of Fe(OH)2 to magnetite:

3Fe(OH)2  Fe3O4 + 2H2O + 2H+ + 2e-
The last two reactions are reversible, hence both magnetite and
lepidocrocite can be reduced to ferrous hydroxide.
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Zinc is considerably more active than iron, but corrodes in

the atmosphere at a rate that is about 10-20 times less.
The corrosion product layer that forms is highly protective.
Like iron, the corrosion rate of zinc follows a power law

relationship, but the value of the exponent is close to one,
i.e. zinc tends to have linear corrosion kinetics.
Linear kinetics make it easy to predict the lifetime of a

galvanized coating on steel.
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During atmospheric corrosion of zinc, a thin, non-porous

zinc hydroxide layer initially forms.
Subsequently transforms, at its interface with the

atmosphere, to a basic zinc salt that is slightly soluble.
Corrosion product layer thickness stays approximately

constant, being determined by the solubility of the basic
salt. In turn, this is determined by the concentration of
pollutants in the atmosphere
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• Formation of zinc hydroxide:

Zn + 2H2O  Zn(OH)2 + 2H+ + 2e-
• Reaction with CO2:

4Zn(OH)2 + CO2  3Zn(OH)2.ZnCO3 + H2O
basic zinc carbonate
• Reaction with SO3:
5Zn(OH)2 + SO3  4Zn(OH)2.ZnSO4 + H2O
basic zinc sulphate
• Reaction with HCl:
5Zn(OH)2 + 2HCl  4Zn(OH)2.ZnCl2 + 2H2O
basic zinc chloride
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Few metals are exposed in the atmosphere without some

kind of additional protection – usually painting.
Zinc and steel are the most common but copper (and
copper alloys) and lead are also used uncoated.
Both materials have similar corrosion mechanisms to zinc,

but considerably lower corrosion rates.
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Problems can arise with buildings clad with passive metals,

such as aluminium or stainless steel, which are then presumed
to be “maintenance free”.
However, although the general corrosion rates may be low,

airborne particulate deposition can initiate local pitting
corrosion.
Is is important to keep such surfaces clean by regular washing

in order to remove the build-up of salts and other deposits
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Atmospheric Corrosion

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• Given the large surface areas of materials exposed to

• Compared with, for example, the effect of immersion sea

Consider here corrosion processes in the

Introduce following topics:

• The Atmospheric Environment

The Atmospheric Environment; Composition

The atmosphere, also the sea, is one of the most common

Unlike most corrosion environments, the atmosphere does

For example, to determine the corrosion rate of a steel

• Laboratory measurement in 3.5% sodium chloride

• Use defined mass transfer (i.e. constant stirring rate)

• Under such conditions, expect the corrosion rate to be

Similar specimen exposed in the atmosphere does not

Main components of the atmosphere have an effectively

Substance Concentration (vol% or ppm by vol)

Concentrations of water vapour vary naturally over large

For example, on a hot, humid day there may be several

Conversely, concentration drops to close to zero on a cold,

Natural air pollution

3 main primary sources of natural air gas pollution:

Additionally, 2 primary sources of particulate pollution:

Secondary sources of pollution arise from transformations in

Pollution is generally classified into “primary” species that

“Secondary” species result from transformation (change)

Pollutants also classified as either gaseous, particulate (

SOURCES OF NATURAL POLLUTANTS

Man-made atmospheric pollution

Main sources of man-made pollution from burning fossil

Additional atmospheric pollution arises from chemical

SOURCES OF MAN-MADE POLLUTION

Climate effects; weather at a specific location.

Weather changes from place-to-place, from country-to-

General weather pattern for a region of a country usually

Significant local variations (microclimate effects) with height

• High smokestacks may transport pollutant emissions

• Medium height sources may transport to 50 kilometres

• Low emitter, i.e. domestic chimney, transports up to 250

• Exhaust system, about 10-20 metres

Pollutants in the atmosphere consist of:

• “wet” species; gases, ionic salts dissolved in water droplets.

While suspended in the atmosphere, contribute to general

No influence on atmospheric corrosion or ground quality until

Gases or particulates (particles) transport to a surface by 3

• advection due to the airflow (wind)

• convection due to thermal air currents

• diffusion due to concentration gradient of the species

Dry deposition generally accounts for most pollution

Although most atmospheric pollution transport to surfaces

Depending on the local climate, amounts to about 30%

Note: gaseous pollutants dissolving in moisture film on

CONCENTRATION RANGES FOR ATMOSPHERIC POLLUTANTS

Smoke and ash 100 – 1000 20 – 50 < 20

Note that 1 μg m-3 = 1 ppb (part per billion – 109)

Describes all forms of deposition, including wet and dry,

Important to recall that, in the absence of any acidic

The natural pH of rainwater readily calculated from following equilibrium:

CO2 + H2O  H+ + HCO3-

[H+]2 = 1 x 10-7.6 x pCO2

Volume concentration of CO2 in the atmosphere in 2018 was ~400 ppm:

ISO9223, international standard:

rates of SO2 and Cl-.

SULPHUR DIOXIDE CHLORIDE