02 - Corrosion in Natural Environment

POLITECNICO di MILANO
DIPARTIMENTO di CHIMICA, MATERIALI e INGEGNERIA CHIMICA "G. NATTA"
PoliLaPP – Laboratorio di Corrosione dei Materiali “Pietro Pedeferri”
MATERIAL ENGINEERING AND NANOTECHNOLOGY
Corrosion Engineering
Prof. Marco Ormellese
CORROSION IN NATURAL ENVIRONMENT

Atmosphere
Soil
Waters
Sea water
Sede Leonardo Sede Mancinelli
Piazza L. Da Vinci, 32 – 20133 Cod. fisc. 80057930150 Via Mancinelli, 7 – 20131 Milano
Milano Partita IVA 04376620150 Tel. ++39-02 2399.3100
Tel. ++39-02 2399.3200 Sito web: www.chem.polimi.it Fax ++39-02 2399.3180
Fax ++39-02 2399.3209
POLITECNICO DI MILANO
DIPARTIMENTO DI CHIMICA, MATERIALI E INGEGNERIA CHIMICA "Giulio Natta"
Content
1 Atmospheric corrosion ........................................................................................................... 4

1.1 Carbon steel ............................................................................................................... 6
1.2 Weathering steels (Corten)......................................................................................... 7
1.3 Other metallic materials ............................................................................................. 8
2 Corrosion in soil ...................................................................................................................... 9

2.1 General corrosion ....................................................................................................... 9
2.2 Differential aeration ................................................................................................. 11
2.3 Galvanic corrosion ................................................................................................... 13
2.4 Microbiological Corrosion ....................................................................................... 14
2.5 Stray currents ........................................................................................................... 15
2.6 Corrosion prevention ............................................................................................... 17
2.7 Exercise_1 ................................................................................................................ 18
2.8 Exercise_2 ................................................................................................................ 19
2.9 Exercise_3 ................................................................................................................ 19
3 Corrosion in fresh and industrial waters ........................................................................... 20

3.1 Alkalinity ................................................................................................................. 20
3.2 Hardness and scaling power..................................................................................... 20
3.3 Corrosion rate........................................................................................................... 22
3.4 Materials for pipeline and tanks ............................................................................... 22
3.5 Steels and cast iron................................................................................................... 23
3.6 Galvanised steel ....................................................................................................... 24
3.7 Copper ...................................................................................................................... 24
3.8 Stainless steels ......................................................................................................... 24
3.9 Exercise_1 ................................................................................................................ 25
3.10 Exercise_2 ................................................................................................................ 25
3.11 Exercise_3 ................................................................................................................ 25
Corrosion Engineering – Natural Environment 2 of 34

4 Corrosion in SEA water ....................................................................................................... 27

4.1 Salinity and chlorinity .............................................................................................. 27
4.2 Oxygen ..................................................................................................................... 29
4.3 Fouling ..................................................................................................................... 30
4.4 Corrosion Zones ....................................................................................................... 30
4.5 Corrosion of Carbon and Low Alloy Steel .............................................................. 31
4.6 Exercise_1 ................................................................................................................ 33
4.7 Exercise_2 ................................................................................................................ 34

1 Atmospheric corrosion
Metallic structures exposed to atmosphere (buildings, bridges, statues, works of art, vehicles
Figure) are subjected to corrosion when on the metallic surface a thin wet film is created by the
humidity in the air.
The severity of the corrosion and the rate at which corrosion will take place are dependant
primarily upon the properties of the surface formed electrolytes, which in turn are dependant
upon factors such as the humidity and pollution levels in the atmosphere.
Figure 1 – Metallic structure exposed to atmospheric condition:
Atmospheric corrosion is an electrochemical process, requiring the presence of an electrolyte.

Thin film "invisible" electrolytes tend to form on metallic surfaces under atmospheric corrosion
conditions, when a certain critical humidity level is reached. For iron, this level is around 60%,
in unpolluted atmospheres. The critical humidity level is not a constant - it depends on the

corroding material, the hygroscopic nature of corrosion products and surface deposits and the
presence of atmospheric pollutants.
Meteorological factors
Macro
(rain, time of wetness,
environment
humidity, temperature)
Atmospheric contaminants Micro

(SO2, SO3, NOx, Cl–, dust) environment
Intrinsic factors (material

and corrosion products)
Figure 2 – Factors influencing atmospheric corrosion
The most common atmospheric contaminants are:
• Sulphur dioxide (SO2)
• Nitrogen oxides (NOx)
• Chlorides
• Solid particles
In the presence of sulphur oxides SO2 and SO3 (SOx) the water condensation increases and the
pH decreases (pH of acid rains is 3-4); the acidity deeply increases corrosion rate corrosion
products are more soluble and less protective. Nitrogen oxides (NOx) can act as catalysts and
transform SO2 in SO3 (more aggressive). Finally chlorides are very hygroscopic salt and form
corrosion product less protective. They accelerate corrosion process because the electrolyte is
more conductive and promote localised corrosion (Figure 3).

Hygroscopic
salt
Corrosion rate
R.H. (%)
0 50 100
Critical R.H.
Figure 3 – Effect of chlorides on critical relative humidity
The presence of solid particles favours the capillary condensation and provides a shielding effect
promoting crevice corrosion. Factors that affect atmospheric corrosion change from a region to
another. For this reason atmospheric environments are most commonly divided into four
categories: rural, urban, industrial and marine. The environments vary depending on the severity
from a corrosive point of view. Several metallic materials are used for the structure exposed to
the atmosphere. Some examples are reported in Figure 1.
1.1 Carbon steel
This material presents low corrosion resistance, forming rust as corrosion product that is not
protective. The protection is achieved by means of metallic coating (Zn) or painting. Different
coating can be applied on the steel surface both metallic (Zn, Cr, Sn, Al) and non metallic
(organic, inorganic and conversion coatings). Coating can act in different ways; protecting the
metal with a physical “barrier” mechanism (Figure 13.4), with an active protection (Figure 5).
O2 H2O
Steel
Figure 4 – Physical barrier effect of a painting cycle

O2
Electrolyte
Zinc coating i
Steel e
-
Cathodic reaction Anodic reaction
O2+4e-+2H2O=4OH- Zn=Zn+++2e-
Figure 5 – Active protection of a Zn-rich coating on carbon steel
The efficiency of the coating depends on the environment. In Figure 6 are reported the service
lives of a zinc coated structure as a function of the coating thickness for different environment al
conditions
80
70 rural
Service life (years)
60
marine
50
40 town
30
20 industrial
10
0
0 20 40 60 80 100 120 140
Zinc layer thickness (µm)
Figure 6 – Corrosion rate of zinc coating as a function of exposure
1.2 Weathering steels (Corten)
Weathering steel, best-known under the trademark COR-TEN steel, is a group of steel alloys
which were developed to obviate the need for painting, and form a stable rust-like appearance if
exposed to the weather for several years. “Weathering" means that due to their chemical
compositions, these steels exhibit increased resistance to atmospheric corrosion compared to
unalloyed steels (Figure 7). This is because the steel forms a protective layer on its surface under
the influence of the weather.

600
Thickness reduction (µm)

Carbon steel
400
Weathering steel
200
0
0 5 10
Exposition (years)
Figure 7 – Comparison between corrosion rate of carbon steel and weathering steel
The corrosion-retarding effect of the protective layer is produced by the particular distribution
and concentration of alloying elements in it. The layer protecting the surface develops and
regenerates continuously when subjected to the influence of the weather.
1.3 Other metallic materials
Stainless steels present very good resistance to atmospheric corrosion. Some application a
reported in Figure 13.8. Also aluminum and its alloys present very good behavior in low
contaminated environments; the aluminum oxide is stable for 4,5<pH<9 and without chlorides.
Anodic oxidation can improve further the corrosion. Due a protective noble patina copper and its
alloys present good resistance to atmospheric corrosion
Figure 8 - Stainless steel (Petronas towers); aluminum; copper

2 Corrosion in soil
Soil corrosion is a complex phenomenon, with a multitude of variables involved. Soil is a

complex aggregated constituted by solid particles, water with dissolved chemical species and air.
Water retention depends on granulometry; soils with sand and large aggregates facilitate water
drainage, while muds and clays increase water retention. Availability of oxygen in soil depends
not only on physical diffusion but also on chemical and biochemical reactions with chemicals
and micro-organisms present in the soil. Furthermore plant root respiration and microbial activity
absorb O2 and produce CO2 with a maximum concentration at a depth of 0.5-1 m.
Table 1 - Corrosion reaction that can occur in soil
Anodic reaction Fe = Fe2+ + 2e-

Cathodic reaction 1/ + H2O + 2e- = 2OH-
2O2
Oxidation of iron ions Fe2+ + 1/4O2 + 1/2H2O = Fe3+ + OH-

Corrosion products 2Fe3+ + 3H2O = Fe2O3 + 6H+
precipitation 2Fe3+ + Fe2+ + 4H2O = Fe3O4 + 8H+
Carbonates Ca(HCO3)2 = CaCO3 + H2O + CO2
precipitation
Different are the forms of corrosion in soils both general corrosion (aerated soils) and corrosion
tubercles (aerated soils + chlorides and sulphates), and localised corrosion (differential aeration,
galvanic coupling, stray current corrosion, microbial corrosion, stress corrosion cracking of
carbon steel).
2.1 General corrosion
General corrosion in neutral aerated soils (pH > 5) depends on oxygen availability but in general
is negligible. The penetration rate for new pipelines: is 10-30 µm/y and after 10 years reduces to
1-3 µm/y. In acidic soils (pH < 5) it is possible hydrogen evolution that can increase with
decreasing pH (Figure 10). In aerated condition the rate determining step is the cathodic process
(Figure 11).

Figure 9 – General corrosion on a bare pipeline embedded in soil
Figure 10 – Reduction of corrosion rate in aerated neutral soil
Ia Anodic Im
process
Ia = Iel = Ic = Im
Current = Current
flowing in ICORR in
the electrolyte the metal
Iel Cathodic Ic
process
Figure 11 – Corrosion controlling step: cathodic process
In aerated soils in the presence of chlorides and sulphates the typical corrosion form is the
corrosion is the formation of tubercles. In the presence of chlorides and sulphates concentration

higher than 200 ppm and 1000 ppm, respectively, the formation of soluble iron salts produces
non-protective deposit that promotes the formation of corrosion tubercles (Figure 12). Being the
deposit non protective and with defect the oxygen content does not decrease at the metallic
surface. Due to presence of high concentration of chlorides and sulphates the conductivity of the
soil is quite high. The penetration depth varies between 100 µm/y and hundreds of mm/y
depending both on cathodic/anodic areas ratio and the rate of O2 availability to the cathodic
areas.
Tubercules
Corrosion Fe2O3
products
Fe3+
Cl-
SO4-- H+
Fe2+
pit
Figure 12 – Tubercles formation in soil rich in chlorides and sulphates
2.2 Differential aeration
Local corrosion through differential aeration takes place when the soil surrounding the structure
is not homogeneous and shows variable oxygen permeability. A typical case study is the
presence of both a clayey layer and a sandy layer (Figure 13).
O2 O2
Clay islands
Fe2+
O2
Anodic reaction
Cathodic reaction zone corrose
Anodic
Cathodic reaction
reaction
Clayey soil Sandy soil

Sandy soil
Figure 13 – Differential aeration corrosion

The metal surface in contact with clay, which is not permeable to oxygen, becomes anodic and
metal dissolution takes place (Fe = Fe2+ + 2e-). On the other hand, metal in contact with sand,
which is highly permeable to oxygen, becomes cathodic and oxygen reduction takes place (O2 +
H2O + 4e- = 4OH-). Therefore a macrocell is established with the separation of the cathodic from
the anodic areas. The corrosion rate is given by the cathodic process rate, equal to the oxygen
diffusion limiting current density multiplied by the cathodic/anodic surface area ratio, when
cathodic surfaces are much larger than anodic ones. So when an extensive surface is available for
the cathodic process, the corrosion rate could be very high. For example, if the cathodic process
rate is 100 mA/m2 (possible in well aerated zones) and the cathodic/anodic area ratio is a 10:1,
the corrosion rate can be as high as about 1 mm/y. Typical cathodic/anodic area ratio is 5.
When considering the macrocell mechanism, as in differential aeration corrosion, the corrosion
rate depends on macrocell circuit resistance and therefore on environment resistivity. This
explains why corrosion manuals include the empirical rule that the corrosion rate depends on soil
resistivity (Table 2), although this rule is nowadays considered insufficient. Soil resistivity
depends on various factors, particularly geological structure, particle size, porosity, permeability,
and water content and its composition. For example, the relationship between resistivity and
water content is schematically illustrated in Figure 14. A clayey soil with 5% humidity may have
a resistivity of 104 Ωm, which decreases to only 10 Ωm if humidity rises to 20%. Soil resistivity
may have considerable seasonal variations, particularly in the upper layers due to precipitation
and agricultural and industrial activities.
Table 2 - Empirical correlation between soil corrosiveness and soil resistivity
Resistivity
Corrosivity
(Ω x m)
<5 Very severe
5 - 10 Severe
10 - 30 Moderate
30 - 100 Low
100 - 250 Very low
> 250 Negligible

1000
Sandy
Resistivity (Ωm) 100

Rural
10
Clay
1
0 5 10 15 2 0 25 30 35 40
Humidity (%)
Figure 14 – Variation of resistivity with water content
After extensive experimentation carried out in the United States, the National Bureau of
Standards through a statistical approach derived an equation that correlates the corrosion rate of
different metals to the period of exposure and soil resistivity:
Vcorr = K t n-1
where t is exposure period in years, and K and n are two constants that depend on metal and soil
resistivity.
2.3 Galvanic corrosion
The presence of two metals having different nobilities may lead to galvanic corrosion. The less
noble metal, which has a lower potential in the natural environment, assumes anodic behaviour,
and the more noble metal assumes cathodic behaviour. Galvanic corrosion is favoured in low
resistivity environments: the lower the resistivity the greater the corrosion effects, both as
corrosion rate and extension of involved zones. Although soil is an environment with medium to
high resistivity, especially if compared to seawater, where bimetallic corrosion is dreaded, the
effects of galvanic corrosion are not negligible because of soil’s extensive electric field
geometry. For example it is possible to have corrosion of steel structure if they are coupled with
the copper of the grounding system (Figure 15).

tank
corrosion
I
I
Grounding Grounding
(Copper) (Copper)
Figure 15 – Galvanic corrosion of a carbon steel tank bottom due to coupling with a
copper grounding system
2.4 Microbiological Corrosion
It is estimated that about half of the corrosion attacks on buried pipelines can be attributed to
bacterial and microbiological corrosion. It has been observed that this takes place mainly in
neutral or alkaline soils rich in organic content and is absent in acidic or neutral soils with a high
salt content.
The most damaging family of these micro-organisms is made up of sulphate-reducing bacteria

(SRB) that develop and live in anaerobic environments. The properties of clayey soils, which are
neutral and oxygen-free, appear ideal for excluding corrosion from an electrochemical
perspective, yet they actually provide conditions that most favour the growth of these bacteria
and thus provide the worst outcome from a corrosion point of view: literature data agree on a
corrosion rate even above 1 mm/y. SRB are highly adaptable and are generally able to resist even
a temperature of 60°C. Certain families of bacteria resist even up to 80°C and a pressure of 400
bars, which are conditions encountered in oil and gas formation. Although they are not active in
aerobic conditions, they survive and are ready to resume growth as soon as anaerobic micro and
macro environments are created.

The SRB corrosion mechanism is quite complex and not yet completely understood. The first
mechanism was proposed in 1934: through a hydrogenase enzyme, bacteria make use of
hydrogen produced at the cathode to reduce sulphate ions through the following reactions:
4Fe = 4Fe2+ + 8e
8H+ + 8e = 8H
SO42- + 8H = S2- + 4H2O
Fe2+ + S2- = FeS
3Fe2+ + 6OH- = 3Fe(OH)2
The modern theory takes into consideration other mechanisms, where the controlling factors
involved are:
• use of hydrogen by both SRB (to reduce sulphates and sulphides) and by other non-
sulphate reducing bacteria
• cathodic depolarisation through ferrous sulphide precipitation
• anodic stimulation by sulphide ion
• prevention of formation of a protective sulphate film when there is an excess of ferrous

ions
• formation of concentration cells.
2.5 Stray currents
If a metal structure is located in a stationary or variable electric field, it may be interfered with,
leading to a corrosion attack. For example, a structure located between a pipeline and its CP
groundbed becomes a conductor competing with soil to transport the CP current. Zones close to
the groundbed (positive potential field zone) capture the current, becoming cathodically
protected, while those areas close to the pipeline (negative potential field) release that captured
current and suffer corrosion. Non-stationary interference produced by DC transit systems on
structures close to the rails produces the same effects, even if it is discontinuous.

Another type of localised corrosion that can take place is soil is that due to the due the presence
of to stray current produced both of traction system (e.g., trains) or of cathodic protection
system.
Stray current can interferes metallic structure altering their electrical state, promoting localised
corrosion.
Not-stationary interference problems stem from the fundamental design of electrified rail transit
systems, whereby current is returned to substations via the running rails. The ground surrounding
the rails can be viewed as a parallel conductor to the rails. The magnitude of stray current flow in
the ground conductor will increase as its resistivity decreases. Any metallic structure buried in
ground of this nature will tend to “attract” stray current, as it represents a very low resistance
current path. The highest rate of metal dissolution occurs where the current leaves the structure
and undesirable overprotection effects can occur at the points of current pick-up.
rail
tram substation
+
I Rr
substation i R1 i R2
– Cathodic zone
pipeline
Anodic zone
I Rt
iRr
Cathodic zone Anodic zone i=
R1 + R t + R 2
Figure 16 – Non-stationary stray current; electrical scheme

In the presence of non-stationary interference, corrosion decreases if Rr is low (welded rails), soil
resistance (R1 + R2) and pipeline resistance R2 are high (insulated joints, protective coatings).
Stationary interference occurs if a buried metallic structure is immerged in an electrical field

generated by an anodic dispersor of a cathodic protection system. In order to have interference
the structure must be close to the dispersor. Two are the possibilities: the pipeline crosses a
cathodically protected pipeline or the two pipelines are parallel.
Figure 17 – Example of stationary stray current induced by an anodic system on a non

protected pipe
2.6 Corrosion prevention
An extensive use of coatings together with CP is employed worldwide to prevent corrosion of

buried steel structures. As already discussed, a protective coating alone is not enough to
guarantee total protection because coating ages and defects or damages are inevitably caused
during transportation, installation and operating. Damages are due to soil-related stresses,
coating brittleness or softening respectively at low and high temperatures, and a lack of coating
adherence due to inadequate preparation of the surface. Especially with wrapped tapes, folds
may form acting as water traps which CP cannot enter. This situation is particularly insidious
because CP cannot be effective, hence SRB corrosion starts as soon as oxygen is depleted and
CP monitoring techniques are unable to find them out.
As schematically shown in Figure 18, a good coating should have optimum chemical properties
(such as resistance to corrosive agents and cathodic reactions) and good mechanical properties; it
should not be expensive (the material itself and its application) and should be easy to apply and
repair. Three types of coatings are used: bituminous or tar types, polyethylene or polypropylene
thermoplastic coatings and epoxy resins (thermosetting type).
Mechanical
Good characteristics Chemical
adherence resistance
Ease of Ideal Temperature

repair coating stability
Short time Cathodic

Economic protection
application
resistance
Figure 18 - Ideal properties of a pipeline coating
2.7 Exercise_1
In free corrosion, carbon steel corrosion rate decreases with time. But, in the case of carbon steel
corrosion due to galvanic coupling (for example with a grounding copper net), corrosion rate of
carbon steel does not decrease with time. Which are the causes of this behavior?
Solution EX_1
In the case of free corrosion of carbon steel in soil, the formation of corrosion products creates in
time a sort of scale on carbon steel surface. This scale reduces oxygen diffusion at the metal
surface, and so the reduces corrosion rate. This is true is chlorides and sulphates content is lower
than 200 ppm and 1000 ppm, respectively. In the presence of a galvanic coupling with a more
noble metal (copper, for example), corrosion localises on carbon steel while cathodic process
(oxygen reduction) localises on the more noble metal. Corrosion rate does not decrease because
the cathodic process of oxygen reduction is not reduced by the corrosion product scale
formation, since oxygen reduces at copper surface.

2.8 Exercise_2
Consider a galvanic coupling between carbon steel and copper. Which is the corrosion rate in the
case of dry soil or clayey soil? Let 10 ppm the amount of oxygen in dry soil, and 1 ppm the
amount of oxygen in wet soil.
Solution EX_2
In the presence of carbon steel – copper galvanic coupling, corrosion localises on carbon steel
(which is the less noble metal) while cathodic process (oxygen reduction) localises on copper
(the more noble metal). Corrosion rate depends on the following parameters: driving force (i.e.,
the difference of practical potentials of the two metals), the ratio between cathodic and anodic
surfaces; the conductivity of soil; the availability of oxygen. In the case of soil, the ratio between
cathodic and anodic areas is around 5. Considering a dry soil, carbon steel free corrosion rate is
around 10 times the amount of oxygen: being oxygen content equal to 10 ppm, corrosion rate is
100 µm/y. In the case of galvanic coupling, corrosion rate increases to 500 µm/y due to the ratio
between cathodic and anodic surfaces. In a wet soil, oxygen content is reduced to 1 ppm, and so
in the case of galvanic coupling, corrosion rate is 50 µm/y.
2.9 Exercise_3
A carbon steel pipeline laid parallel to a railway system. Calculate the penetration rate in the case
of an electrical interference of 1 mA flowing in a defect with an equivalent diameter of 1 cm.
How to avoid the electrical interference.
Solution EX_3
If the anodic interference current of 1 mA flow from the metal to soil thought a 1 cm diameter
defect, the corrosion rate is:
vcorr = I/S = I/(πD2/4) = 1 mA/(π 1cm2/4) = 1.27 mA/cm2 = 12.7 mA/m2
Being in the case of carbon steel a corrosion rate of 1 mA/m2 equal to a penetration rate of 1
µm/y, the penetration rate is 1.27 cm/y. So it is a very high corrosion rate. The corrosion occurs
only during the train circulation, so the amount of corroded metal has to be evaluated
considering the total charge (I x t) exchanged in one year, for example.

3 Corrosion in fresh and industrial waters
Fresh waters can be divided into three different groups on the basis of their origin: meteoric
water, surface waters and underground waters. Fresh water are often corrosive for metallic
materials used in pipelines, tank, and generally for the structure they are in contact with.
Corrosion morphology and corrosion rate depend both on the material, the chemical-physical
characteristics and the operating condition. On iron and carbon steel is frequent general
corrosion that occurs in narrow areas; copper is less sensitive to corrosion, but can suffer
localised attacks (pits). Corrosion rate is expressed as the maximum localised depth loss (usually
mm/y). Recent standard proposals propose the evaluation of the corrosivity of fresh waters in
terms of corrosion probability, in different classes: negligible, low, moderate, severe, very
severe.
With respect to carbon steels, fresh waters are corrosive only in they contain oxygen or other
oxidising species.
In the absence of oxygen it is possible to have corrosive attack due to anaerobic bacteria, in
particular sulphate reducing bacteria.
In waters that contain oxygen, the entity of the corrosive attack depends on several factors: the
ability in forming a calcareous deposit on the metallic surface, the temperature and the electrical
conductivity (related to the salts content), pH, chlorides and sulphates content, the alkalinity, the
hardness and the presence of bacteria.
3.1 Alkalinity
Alkalinity of water defines its ability in neutralising acid solutions and gives information on its
buffering power,
3.2 Hardness and scaling power
Water hardness express the content of Ca and Mg ions those that stimulate the formation of the
calcareous deposit. Hardness is measured as mg/L of CaCO3 (equivalent to Ca and Mg
content).For example, if the sum of Ca2+ and Mg2+ equivalents in 1 L of water is 1,5 the water
hardness is: 1,5*50 = 75 mg/L, where 50 is the CaCO3 equivalent weight (PM/z=100/2). Natural

waters present hardness values ranging from few mg/L up to several hundreds of g/L. Hardness
is often expressed in French degrees (°F) 1°F corresponds to 10 mg/L of CaCO3 Waters can be
classified as a function of the hardness.
Table 3 – Classification of water on the base of hardness
The ability in forming a calcareous deposit depends on water pH and alkalinity as reported in
Figure 19. It is worth noting that an increase in alkalinity or in the pH lowers the water
aggressiveness increasing the ability of forming deposits. In aerated waters oxygen reduction
reaction (the cathodic process) on the metallic surfaces locally increases the pH favouring the
carbonate precipitation.
pH
10
9
Scaling:
Acqua protective
incrostante
8
7
Acqua aggressiva
Aggressive
6
0 50 100 150 200 250 300 350
Alkalinity (ppm come
Alcalinità (ppm CaCOCaCO3)
3)
Figure 19 – Ranges of pH and alkalinity for the calcareous deposit formation
The evaluation of the ability in forming a calcareous deposit require the knowledge of the
saturation chemical equilibriums carbonates that depends in a complex way on the physical-

chemical parameters: pH, pCO2, temperature, alkalinity, salt content. Usually the ability of
forming a deposit is evaluated using indexes; among them the two most common indexes are the
saturation index o Langelier index and the Ryznar index that allow a semiquantitative
determination of the ability in the formation on the metallic material of calcareous deposit
potentially protective
Waters that favours the formation of a calcareous deposit are generally not very aggressive. On
the contrary in the absence of calcareous deposit the corrosion rate, controller by the oxygen
supply rate on the steel surface increases increasing the oxygen content and the turbulence
3.3 Corrosion rate
The corrosion rate is determined by the maximum amount of oxygen that may reach the steel
surface, equal to the limiting oxygen current density, obtained by the combination of Fick’s law
and faraday law:
4 FD[O2 ]
iL =
d
Where F is the Faraday constant, D the diffusion coefficient, d the double layer and [O2] the
oxygen content. If deposition of calcium carbonate occur, corrosion rate is decreased
3.4 Materials for pipeline and tanks
Materials used for fresh water pipeline are cast iron, concrete, carbon steel galvanised steel, PE
and PVC. The material choice depends both on economical consideration, and on several other
factors, in particular on the diameter and the pressure. For example, prestressed concrete is used
in large diameter pipes with little pressure, grey cast iron if the pressure does not exceed 15-20
bar and little pressure variation carbon and galvanised steel in those pipeline subjected to high
pressure with strong variations. In civil installations several materials are used often coupled
together. The most common materials are: copper and copper alloys (brass); galvanised steel;
plastics (PVC/PE).

3.5 Steels and cast iron
Ferrous materials in contact with aerated water are susceptible to general corrosion, with both
morphology uniform and localised. Corrosion does not occur in the absence of oxygen and
without free acidity; The threshold value for the oxygen content under which corrosivity is
negligible is 0,1 mg/L and 0,02 mg/L for cold and hot water respectively. The most frequent
form of attack is the non uniform one with the formation of shallow pits when the superficial
deposits only partially protective. This appends in particular in correspondence of the welds in
waters with high Cl- and SO42- ions content and low total alkalinity. In Table 4 are reported an
estimation of the corrosion probability on the basis of water characteristics.
Table 4 - Negligible corrosion conditions for carbon steel and galvanised steels
Index Carbon steel Galvanised

steel
pH >7 >7
Alk M (meq/L) >2 >2
Acid P (meq/L) < 0,05 < 0,7
Ca (mg/L) > 20 > 20
O2 (mg/L) < 0,02 < 0,1
HCO3-/(SO42-+Cl-) (meq/L) > 1,5 >1
(2SO42-+Cl-)/AlkM (meq/L) <5 <1
Carbon steel is used also for industrial water as cooling waters or water derived from the
condensation of process vapours that contain small quantities of substances as H2S, HCl or
organic acids. In both cases, pH must be controller adding corrosion inhibitors. These treatments
decrease the aggressiveness of the liquid phase and permit the use of carbon steel with sufficient
reliability.

3.6 Galvanised steel
Hot galvanised steel pipeline are used in particular in civil installations. Zinc film presents higher
corrosion resistance than carbon steel, since zinc forms on the surface a film of corrosion
products that are protective. Depending on the thickness the zinc can last the whole service life.
In order to promote the formation of protective corrosion products water must be rich enough in
bicarbonate ions. Corrosion velocity depends among other factors on the presence in the solution
of inhibiting species as phosphates, silicates aluminium ions and organic molecules. Above 60-
70°C it is possible to have an inversion of the potential of the zinc and the steel; thus zinc
became cathodic respect to steel stimulating its attack. In installation together with copper and
copper alloy it is possible to have an inversion in the behaviour of the zinc due to the copper
deposition. In mixed systems, in particular with copper, copper alloys and stainless steel in
correspondence of the contact zones between different materials the zinc film corrodes due to the
galvanic contact: the corrosion penetration inside the pipe increase with the water conductivity.
In Table the water characteristic that minimise corrosion probability are reported.
3.7 Copper
Copper is the most widely used material in civil implant tank to its corrosion resistance. Uniform
corrosion is rare and does not cause serious damages only the not desirable release of copper
ions in the solution. In fact the presence of protective corrosion products as Cu2(OH)2CO3 avoid
the corrosion process. Copper solubility increases as pH decreases and as the total inorganic
carbon concentration increases. Negligible uniform corrosion conditions requires the following
conditions: AcidP < 1.5 meq/L and Alk > 1 meq/L. The most frequent corrosion morphology is
pitting that occurs if anomalous conditions at the pipeline surface occurs, in particular in the
presence of carbon deposit formed by the deformation processes oils cracking.
3.8 Stainless steels
These materials are used in the transport and distribution of fresh waters and in the food industry
where the contamination must be avoided. Most common stainless steels are the austenitic (AISI
304 and 316) and austeno-ferritic ones (22Cr5Ni3Mo). Austenitic stainless steels are used in
most applications. The choice between AISI 304 and AISI 316 depends mainly on the fact that

the steels must be welded or not, on the chlorides content and on the fluidodinamic regime of the
water (stagnant or flowing) and finally in the presence of cracks or deposits. In flowing water in
the absence of cracks and wells AISI 304 is used if the chloride concentration is up to 200 ppm,
AISI 316 up to 1.000 ppm. In the presence of crack or the other conditions mentioned before
AISI 304 and AISI 316 are used only if the chlorides concentration is lower than 50 and 250
ppm respectively. If bacteria are present (in particular the oxidising ones as gallinella) it is
possible the occurring of attacks even if the concentrations are lower that those reported. Since
welds are week points it happens that sometimes AISI 304.
3.9 Exercise_1
In your opinion, is the galvanized steel for hot tap water a good material selection?
Solution EX_1
In the presence of hot tap water, with temperature higher than 60°C, the use of galvanised steel is
not correct. In fact, at high temperature the practical potential of zinc becomes more noble that
the practical potential of carbon steel. So in the case of possible defect of the zinc layer, the
carbon steel will behave as anodic material.
3.10 Exercise_2
Why the corrosion rate of the carbon steel radiator is negligible?
Solution EX_2
Carbon steel corrosion in waters depends on oxygen dissolve in water and on fluido-dynamic
conditions. In the case of radiators, being the system a closed circuit, there is no oxygen renewal.
Let be 10 ppm the oxygen dissolved in water at the first filling. All this oxygen is consumed for
corrosion of carbon steel. When oxygen is consumed, there no cathodic reactant for the corrosion
of carbon steel. That’s the reason why corrosion rate is negligible.
3.11 Exercise_3
A carbon steel fire-system plant suffered localized corrosion after 4 years from installation. The
thickness of the pipe is 4 mm. Water composition is as follow: hardness 2°F, oxygen 1 ppm,

chlorides 50 ppm, sulfates 80 ppm, pH 7.5, T 15-20°C, conductibility 500 mS/cm. Which is the
cause of corrosion?
Solution EX_3
Considering pipeline thickness and service life, corrosion rate is around 1 mm/y. This is an high
corrosion rate, not compatible with corrosion in aerated environment (the amount of oxygen is 1
ppm, so in stagnant condition maximum corrosion rate is 10 µm/y, in turbulent condition is
around 50 µm/y). Due to the presence of sulphates, being the fire-system is a closed circuit plant,
the possible corrosion cause is the presence of bacteria, in particular the SRB.

4 Corrosion in sea water
Composition and chemical–physical properties of sea water are almost constant through out the
world, except for small but significant local variations. For example, the pH is usually between
8.1 and 8.3, but it may decrease to about 7 in closed bays. The amount of dissolved oxygen,
temperature and local turbulence are very important factors influencing corrosion, as well as
activities of micro-organisms, that contribute to marine fouling, together with the
carbonate/bicarbonate chemical equilibrium are to be taken into account.
All these factors change according to the geographical location, the water depth and seasons.
Most significant variations are observed along the coast due to the mixing with fresh water or
because of high evaporation in closed bays, together with human activities and pollution.
Sea water is generally stratified: the thickness of surface layers varies from few metres up to
even tens of metres since wave action and atmospheric turbulence create a uniform chemical
composition, temperature and density profiles. The properties of the subsequent deeper strata
change gradually.
4.1 Salinity and chlorinity
From a chemical-physical standpoint, sea water is a solution of chemical species, dissolved

gasses and dispersed solids that hosts biological processes. Table lists main chemical species
present in seawater out of the numerous ones, practically all elements. The ratio between
concentrations of principal ions in sea water is quite constant.
The total amount of dissolved solids in sea water determines its salinity. This is expressed as the
amount of salt, grams in one kilogram of water, or more often in g/L or in parts per million
(ppm). Typical values are 34-36 g/L, but may vary from 39 g/L in the Mediterranean Sea to 44
g/L in the Persian Gulf and 7.8 g/L in the Baltic Sea.
Anomalous cases such as a decrease in salinity in surface layers may be verified close to coasts
near river deltas.

Table 5 - Content of eleven most abundant species in sea water, with salinity 35 g/L and
density 1.023 t/m3 at 25°C
Salinity is often derived from chlorinity, which represents the total amount of halogens (chlorine,
iodine, bromine) present, obtained through titration with silver nitrate and expressed as
equivalent chloride content (g/L or ppm). Salinity may be calculated from chlorinity through the
following empirical equation.
salinity (g/L) = 0.3 + 1.8 x chlorinity (g/L)
The high conductivity of sea water (κ), about 100-200 times greater than that of fresh water, is
related to the amount of ionic species dissolved in it. However, it is not possible to assign an
average value, since varies with salinity and temperature. The effect of these two factors may be
described through empirical equations:
κ = 1/ρ = (0.15 + 0.005 x T) chlorinity
κ = 1/ρ = 0.55 (0.15 + 0.005 x T) (salinity − 0.3)
where T is the temperature of sea water in °C, κ is expressed in S m-1 and resistivity ρ in Ωm.
Figure 20 reports the relationship of equation.

Figure 20 - Graph for calculation of sea water resistivity as a function of salinity and
temperature (dotted lines indicate the most common range of sea water compositions)
4.2 Oxygen
Like nitrogen and carbon dioxide, oxygen dissolved in sea water comes from the atmosphere. It
is even produced through photosynthesis and consumed in respiration and putrefaction
processes.
In sea water with a salinity of about 35 g/L, dissolved oxygen in equilibrium with the atmosphere
varies from 9 ppm at 0°C to 6 ppm at 30°C, and gradually decreases to about 3 ppm at 60°C.
These concentrations also decrease with an increase in salinity. Oxygen solubility is practically
zero when salinity is greater than 150 g/L.
Oxygen concentration profiles with water depth are determined by biological activities,
temperatures and marine currents, which mix water of different layers. Furthermore,
photosynthetic processes occurring on surface layers could determine oxygen oversaturation
with concentrations twice as high as solubility. On the other hand, oxygen consumption under
anaerobic conditions such as stagnant water, sea mud or beneath fouling, favours growth of
sulphate-reducing bacteria.

4.3 Fouling
Fouling is made up of the growth of macro and micro organisms that develop in submerged
zones. It may cause localised corrosion by promoting anaerobic conditions that facilitate the
growth of sulphate-reducing bacteria or by setting up differential aeration conditions. It may
even be responsible for the destruction and degradation of protective coatings. In certain cases, it
may even protect steel by calcareous scale formation, thus impeding oxygen supply.
4.4 Corrosion Zones
Of all the natural environments, sea water is the most aggressive to carbon steel, because of its
high conductivity and high oxygen availability. The materials most resistant to general corrosion,
especially those with active-passive behaviour, are on the other hand susceptible to localised
corrosion. The presence of living organisms may lead to localised microbiological corrosion
attacks by sulphate-reducing bacteria due to the anaerobic conditions that occur.
It is possible to distinguish four zones of corrosion dependant on hydrodynamic conditions and

oxygen supply: atmospheric, splash and tidal zone, submerged, and sea mud zone. Each zone has
a distinct mechanism, morphology, corrosion rate and preventative measures.
Atmospheric Zone. This zone lies above the highest level where the structure is no longer
continuously wet by spray. The corrosion mechanism is often referred to as atmospheric
corrosion, whose rate depends on the geographical characteristics of the exposed site, especially
on the relative humidity and chemical pollutants collecting on the surface. Other factors
influencing atmospheric corrosion are wind velocity and direction, temperature, exposure to the
sun, type of precipitation, pollution and dust. Protection of carbon steel and low alloy steel is
provided mainly through organic coatings.
Splash zone. The splash zone extends from low tide level up to the beginning of the atmospheric
zone and is determined by geographical characteristics, primarily wave action and tide. In
closed, calm bays, where environmental conditions are controlled compared to open sea, the
splash zone is restricted to limited areas of the structure.

Submerged zone. This deals with submerged surfaces continuously in contact with sea water.
The corrosion rate depends greatly on environmental conditions that, as already seen, are
extremely variable from one site to another. In this zone, corrosion is prevented by CP.
Mud zone. Oxygen content in sea mud is very low, hence the corrosion rate due to oxygen is
reduced considerably. On the other hand, microbiologically induced corrosion is promoted by
sulphate-reducing bacteria, which are always present. CP is also applied in this zone.
4.5 Corrosion of Carbon and Low Alloy Steel
The cathodic process associated with corrosion of carbon steel is oxygen reduction:
O2 + 2H2O + 4e− = 4OH−
The corrosion rate is therefore determined by the maximum amount of oxygen that may reach
the steel surface, hence is equal to the limiting oxygen current density. This depends on: the
amount of oxygen dissolved in water, temperature, turbulence, and the presence of scales,
calcareous deposits, coatings and fouling through which oxygen must penetrate in order to reach
the metal surface.
An important consequence of corrosion is the deposit of a corrosion product and calcium

carbonate (calcareous deposit) over the steel surface, which slows down the corrosion rate. Field
experience has shown that the corrosion rate of carbon steel exposed to the sea is almost
independent from geographical location, and following the formation of scales it gradually slows
down (Figure 21). During early exposure, the average corrosion rate is between 0.08 – 0.12
mm/y, while for exposure over 20 years the corrosion rate decreases to 0.02 mm/y.
As a rule of thumb, the corrosion rate of bare steel in stagnant sea water, expressed as mA/m2, is
about 10 times the amount of dissolved oxygen expressed as parts per million. In flowing sea
water, the corrosion rate depends, other than on oxygen content, on water velocity and type of
flow regime, laminar or turbulent.

Penetration
(µm/year)
Effect of calcareous
100 deposit formation
50
25
5 10 Time (year)
Figure 21 - Typical trend of uniform corrosion rate of steel in sea water
Assuming a maximum oxygen content close to saturation at actual sea temperature, the oxygen-
limiting current density is given in a laminar regime by:
iL ≅ V 0.5
and in a turbulent regime by:
iL ≅ V
where V is water velocity.
In the presence of galvanic coupling between metals of different nobility, corrosion prediction
should be based on the electrochemical series prepared for sea water (Table 6). The corrosion
rate of less noble material (generally carbon steel) is determined by three factors that are not
always easily quantified: anode-cathode surface area ratio, availability of a cathodic reagent
(oxygen), and polarisation of the metal.
Localised corrosion, usually in the form of pitting, has been observed on steel structures either
without CP or with partial CP because of microbiological induced corrosion by sulphate-
reducing bacteria. Field experience related to offshore structures indicates that the corrosion rate
is almost independent of geographical location and water depth, and is generally greater than 1
mm/y.

Table 6 - Galvanic series of metallic materials in sea water
• Gold, Platinum
• Graphite
• Titanium (passive)
• Silver
• Ni alloys (62Ni, 18Cr, 18Mo) Hastelloy C (62Ni, 17Cr, 15Mo) when
passive
• Nickel and Ni alloys, Stainless steels (AISI 304 and AISI 316) when
passive
• Silver for soldering
• Cu, Brass, Bronze, Cu-Ni (60-90Cu, 40-10Ni) Monel (70Ni,
30Cu)
• Hastelloy B 60Ni, 32Mo, 6Fe, 1Mn) when active
• Ni alloys (66Ni, 32Mo, 1Fe when active
• Nickel and Ni alloys (Inconel) when active
• Tin
• Pb
• Pb-Sn alloys for soldering
• Stainless steels (AISI 304 and AISI 316) when active
• Carbon steel and Cast iron
• Aluminium alloys (4.5 Cu, 1.5 Mg, 0.6 Mn)
• Cadmium
• Aluminium (commercial purity)
• Zinc
• Magnesium and magnesium alloys
4.6 Exercise_1
Estimate the corrosion rate of carbon steel in seawater in the following conditions: oxygen 6
ppm, stagnant condition, laminar regime (V = 0.3 m/s), turbulent regime (V = 4 m/s).
Solution EX_1
In the case of stagnant condition, corrosion rate is 60 µm/y, i.e. 10 times the amount of dissolved
oxygen.
In the case of laminar condition the corrosion rate is estimated as follow:
Vcorr = Vcorr,0 x (1 + V) = 60 x (1 + 0.3) = 78 µm/y
In the case of turbulent condition the corrosion rate is estimated as follow:
Vcorr = Vcorr,0 x (1 + V0.5) = 60 x (1 + 2) = 180 µm/y

4.7 Exercise_2
Corrosion damage in the splash zone is more aggressive that corrosion in immersed zone. Why?
Solution EX_2
In immersed condition the amount of oxygen is lower than 10 ppm, so the corrosion rate may be
estimated with the formula as per exercise n.1. In splash zone, the action of seawater current, of
tidal, of splash contribute to destroy the forming corrosion product, so the bare metal is always
exposed to the aggressivity of seawater.

02 - Corrosion in Natural Environment

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02 - Corrosion in Natural Environment

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POLITECNICO di MILANO

DIPARTIMENTO di CHIMICA, MATERIALI e INGEGNERIA CHIMICA "G. NATTA"

PoliLaPP – Laboratorio di Corrosione dei Materiali “Pietro Pedeferri”

MATERIAL ENGINEERING AND NANOTECHNOLOGY

CORROSION IN NATURAL ENVIRONMENT

Sede Leonardo Sede Mancinelli

1 Atmospheric corrosion ........................................................................................................... 4

2 Corrosion in soil ...................................................................................................................... 9

3 Corrosion in fresh and industrial waters ........................................................................... 20

Corrosion Engineering – Natural Environment 2 of 34

4 Corrosion in SEA water ....................................................................................................... 27

Corrosion Engineering – Natural Environment 3 of 34

Figure 1 – Metallic structure exposed to atmospheric condition:

Atmospheric corrosion is an electrochemical process, requiring the presence of an electrolyte.

Corrosion Engineering – Natural Environment 4 of 34

Atmospheric contaminants Micro

Intrinsic factors (material

Figure 2 – Factors influencing atmospheric corrosion

The most common atmospheric contaminants are:

• Sulphur dioxide (SO2)

• Nitrogen oxides (NOx)

Corrosion Engineering – Natural Environment 5 of 34

Figure 3 – Effect of chlorides on critical relative humidity

1.1 Carbon steel

Figure 4 – Physical barrier effect of a painting cycle

Corrosion Engineering – Natural Environment 6 of 34

Figure 5 – Active protection of a Zn-rich coating on carbon steel

Figure 6 – Corrosion rate of zinc coating as a function of exposure

1.2 Weathering steels (Corten)

Corrosion Engineering – Natural Environment 7 of 34

Thickness reduction (µm)

1.3 Other metallic materials

Figure 8 - Stainless steel (Petronas towers); aluminum; copper

Corrosion Engineering – Natural Environment 8 of 34

Soil corrosion is a complex phenomenon, with a multitude of variables involved. Soil is a

Table 1 - Corrosion reaction that can occur in soil

Anodic reaction Fe = Fe2+ + 2e-

Oxidation of iron ions Fe2+ + 1/4O2 + 1/2H2O = Fe3+ + OH-

2.1 General corrosion

Corrosion Engineering – Natural Environment 9 of 34

Figure 9 – General corrosion on a bare pipeline embedded in soil

Figure 10 – Reduction of corrosion rate in aerated neutral soil

Figure 11 – Corrosion controlling step: cathodic process

Corrosion Engineering – Natural Environment 10 of 34

Figure 12 – Tubercles formation in soil rich in chlorides and sulphates

2.2 Differential aeration

Clayey soil Sandy soil

Figure 13 – Differential aeration corrosion

Corrosion Engineering – Natural Environment 11 of 34

Table 2 - Empirical correlation between soil corrosiveness and soil resistivity

Corrosion Engineering – Natural Environment 12 of 34

Resistivity (Ωm) 100

Figure 14 – Variation of resistivity with water content

2.3 Galvanic corrosion

Corrosion Engineering – Natural Environment 13 of 34

2.4 Microbiological Corrosion

The most damaging family of these micro-organisms is made up of sulphate-reducing bacteria

Corrosion Engineering – Natural Environment 14 of 34

SO42- + 8H = S2- + 4H2O

Fe2+ + S2- = FeS

3Fe2+ + 6OH- = 3Fe(OH)2

• cathodic depolarisation through ferrous sulphide precipitation

• anodic stimulation by sulphide ion

• prevention of formation of a protective sulphate film when there is an excess of ferrous