Marine and Natural Waters: Corrosion under specialized conditions where applied or residual

stresses are present (Jones 1996, Fontana 1986). (See

The most abundant and widespread corrosive elec- Stress Corrosion Cracking; Hydrogen Embrittlement;
trolyte is water. The corrosiveness of fresh, brackish, Corrosion Fatigue; Erosion and CaŠitation Cor-
and sea waters to a variety of metals and alloys rosion.)
depends on many factors including water chemistry,
temperature, velocity of flow, and biological growths
(biofouling). Controlling corrosion on structures in
natural waters is becoming increasingly difficult as the 2. Influence of Water Chemistry and Temperature
search for mineral and fossil fuel resources is extended on Corrosivity
further offshore, and as more sophisticated technology The corrosivity of natural freshwater varies with
demands increasing performance from existing struc- hardness (CaCO content) and temperature, as well as
tural materials. In addition, the validity of many of the $
with the concentrations of dissolved oxygen, chloride,
most successful traditional methods of controlling and sulfur compounds. Hard waters with high dis-
corrosion is being questioned due to environmental solved mineral contents tend to be less corrosive to
concerns. steel and copper piping because carbonaceous scales
often deposit on the metal surface and protect it from
uniform corrosion. Pitting may develop, however, if
the scale does not provide complete coverage of the
1. Types of Corrosion surface.
Seawater is more corrosive than freshwater owing
All common types of corrosion (see Corrosion of
to its higher conductivity and chloride ion content
Metals: OŠerŠiew; Degradation, Taxonomy of) are
(Dexter 1987a). Seawater contains 3–3.5% dissolved
found on one material or another in natural waters.
salts, and its slightly alkaline pH varies from 7.5 to 8.5.
Uniform or general corrosion occurs on iron, steel,
For a given salt content (salinity), seawater corrosivity
low-alloy steels, copper, and many copper-based
is affected primarily by oxygen content and tem-
alloys, such as brasses, bronzes, and cupronickels. It is
perature. Brackish waters (mixtures of fresh and salt
relatively easy to detect and control, especially when it
waters found in tidal bays and estuaries) have corro-
is anticipated while a project is in the design stage. On
sivities intermediate between those of fresh and sea
iron and steel immersed in aerated, quiescent, fresh,
waters. The corrosion rate of structural steel in
brackish, and sea waters, the uniform corrosion rate
seawater depends directly on dissolved oxygen con-
varies from 50–125 µm perpendicular to the surface
centration and to a lesser extent on temperature.
per year of immersion (300–500 µm per year in the
Although decreasing the dissolved oxygen concen-
splash zone above the high-tide level). Schumacher
tration decreases the corrosion rate of steel, it has an
(1979) gives additional data on corrosion rates of a
uncertain effect on passive metals such as aluminum
variety of alloys under various water flow conditions
alloys and stainless steels.
and depths of immersion.
A decrease in temperature slows the rate of all
Galvanic corrosion can occur on all metals in
corrosion reactions and, consequently, corrosion rates
seawater. According to the galvanic series (see Corr-
in the deep ocean, where the water temperature is a
osion, GalŠanic) titanium, nickel alloys, copper alloys,
uniform 4 mC, tend to be lower than in the warmer
and stainless steels are the least likely to be damaged
surface waters. There are many exceptions to this
by galvanic corrosion, whereas iron, steel, and alum-
general rule, however. The corrosion rate of steel is so
inum are the most likely (Schumacher 1979, Jones
sensitive to dissolved oxygen that it increases in some
1996). The lateral extent of attack depends on the
deep, cold waters high in oxygen despite the decreasing
water conductivity. In highly conductive seawater,
temperature. Aluminum alloys also tend to corrode
galvanic effects are evident at distances up to 30 m
more rapidly in the deep ocean, but this is due to a
from the two-metal junction, whereas in freshwater
reduction in the pH of the water, rather than to oxygen
the effect may be confined to within 1 mm of the
concentration or temperature (Dexter 1987a).
junction.
Crevice corrosion and pitting are examples of highly
localized forms of attack, which are harder to detect
and more difficult to prevent than uniform corrosion
3. Influence of Water Flow Speed
(see Corrosion, CreŠice; Corrosion, Pitting). These loca-
lized forms of corrosion are experienced on passive An increase in velocity of flow to 2 m sV" increases the
(see PassiŠity and Breakdown) metals such as alum- corrosion rate of steel in seawater, but it may suppress
inum alloys and stainless steels, with yearly pene- the tendency for pitting to initiate on passive alloys
tration rates sometimes exceeding 0.1 m. Stress corr- (LaQue 1975). For most alloys, increasing the velocity
osion cracking, hydrogen embrittlement, corrosion of flow beyond about 2 m sV" results in an increase in
fatigue, and erosion-corrosion can also be detrimental corrosion rate. For iron, steel, and copper alloys, the

1
Marine and Natural Waters: Corrosion

corrosion rate becomes excessive above a critical 5. Corrosion Prevention and Control Methods
velocity (Schumacher 1979). Only the nickel- and
Prominent among corrosion control techniques in
cobalt-based superalloys, titanium, and some stainless
marine and fresh water systems is the use of coatings
steels retain a high degree of corrosion resistance at
(see Marine Coatings) together with cathodic pro-
hydrofoil velocities (
30 m sV").
tection (see Corrosion Protection Methods). These are
particularly effective on structures fully immersed in
seawater. Cathodic protection cannot be used above
the waterline, and it is difficult to use effectively in
fresh waters of low conductivity. In closed systems of
4. Influence of Biofouling all salinities, deaeration of the water and addition of
chemical inhibitors are often useful. Soft fresh waters
The general term biofouling includes both macro-
are sometimes treated with lime or soda ash to make
scopic organisms, such as barnacles and mussels, and
them less corrosive.
microscopic organisms, such as bacteria and micro-
The environmental risks associated with the use of
algae. The attachment of macroscopic marine fouling
corrosion and fouling control chemicals in open
organisms can have various effects on the corrosion of
natural water systems are becoming increasingly
a structure. A continuous fouling layer comprised of
recognized. Paints and chemicals containing mercury,
many species of organisms will often reduce the
lead, and chromates are no longer in use. As of the late
corrosion rate of structural steel by creating a barrier
1990s, formulations containing tributyl tin fluorides
to keep oxygen away from the surface. On the other
and oxides were still in use, but only within strict
hand, if the fouling layer does not provide complete
regulatory limitations. Even the most commonly used
coverage, it can encourage the initiation of pitting and
fouling control chemicals, chlorine, hypochlorite, and
crevice corrosion on susceptible materials (Edyvean
copper, were coming under increasing regulatory
1995). The only structural metals available with a
pressure. Thus, there was and still is a considerable
natural toxicity to fouling organisms are those with
urgency for the development of new, environmentally
more than 70% copper. The copper–nickel alloys with
friendly methods of corrosion and fouling control for
70–90% copper combine moderate strength with low,
natural water systems.
uniform corrosion rates (20–40 µm per year) and a
In summary, all known types of corrosion are
natural resistance to fouling (LaQue 1975).
experienced on one material or another used in natural
Films of microscopic organisms, such as bacterial
water systems. The corrosion rate for a given alloy
and microalgae, form on all solid surfaces immersed in
immersed with a given geometry and flow rate tends to
natural waters of all salinities. Such microbial biofilms
be controlled by the bulk water chemistry as modified
range in thickness from less than 10 µm to nearly
at the metal surface by the action of the organisms in
5 mm, and the nominal thickness increases with time
biofilms. Corrosion control in open systems is usually
of immersion. The films tend to become highly
achieved by a combination of coatings and cathodic
heterogeneous in both thickness and chemistry from
protection with increasing attention being given to
point to point along the metal surface (Lewandowski
environmental concerns.
et al. 1995, Xu et al. 1998). The heterogeneous nature
of the film causes corrosion of the underlying metal to
become more localized than it would be in the absence
of the film (Dexter 1995).
The effects of microbial biofilms on corrosion have
been documented for a number of environments and Bibliography
industries (see Bioactive Environments : Corrosion
and references therein). In many industrial environ- Dexter S 1987a Marine corrosion: seawater. In: Metals Hand-
ments, initiation of corrosion can be traced to the book, 9th edn., Vol. 13, Corrosion. ASM International, Metals
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reducing bacteria (SRB) or the iron and manganese Dexter S 1987b General biological corrosion. In: Metals
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Encyclopedia of Materials : Science and Technology
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