Marcus P. Corrosion mechanisms in theory and practice

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approach depends on many factors, such as the nature of the environment in which

MIC occurred (e.g., soil, cooling water, seawater), the type of microorganisms

involved, and the nature of the material. In practice, several approaches are often

used in order to increase their efficiency. Many reviews on this subject are available

in the literature [37,78,111,122,123]. Thus, the different approaches are discussed

here only briefly. In any case, it is important to note that in the case of MIC the

affected structure should not be cleaned prior to analysis in order to be able to

trace the origin of the problem.

Changing or Modifying the Material

The choice of a material that is not susceptible or less susceptible to bacterial

degradation may be one solution. However, this is often not possible for economic

reasons.

Modifying the Environment or Process Parameters

The environment can be modified through, for instance, avoidance of anaerobic

zones or modification of the pH in order to prevent acid accumulation. A good

example of this is in the use of sand, gravel, or chalk as a nonaggressive backfill

around buried steel pipes. This provides drainage and consequently better aeration

of the soil. Chalk also provides an alkaline environment that may prevent acid

accumulation. Similarly, stagnant conditions should be avoided in water systems.

The process parameters may also be changed. For example, an increase in water

velocity in heat exchanger tubes leads to partial detachment of biofilm. However,

it is not always possible to change the process parameters. Besides, one must be

careful not to induce other corrosion problems. For instance, a high water velocity

may cause erosion-corrosion on some metals and alloys.

Organic Coatings

Organic coatings are widely used for the protection of steel in environments such

as buried pipes, exteriors of buildings, and marine structures. However, all paint

coatings are more or less biodegradable (see plastic materials). Besides, care must

be taken with the surface preparation before painting and application of organic

coatings in order to avoid voids or pores, where microorganisms may grow with

highly localized corrosion as a result.

Cathodic Protection

Cathodic protection is widely used in the case of buried steel pipes and marine

structures. As a rule, in order to control the anaerobic corrosion of iron by SRB,

the potential of the structure is depressed to at least –1 V versus Cu/CuSO

instead of –0.85 V versus Cu/CuSO

, which is usually recommended in the

absence of SRB [125]. Cathodic protection is often used in combination with

organic coatings because the presence of the organic coating diminishes the need

for protection current by several decades compared with that of the unpainted

metals. In addition, the cathodic protection will be efficient at defects in the

organic coating.

Microbially Influenced Corrosion 593

Biocides

Biocides are commonly used for many industrial applications such as industrial

water systems. Biocides may be divided into two categories: (a) oxidizing

agents such as chlorine, ozone, and chlorine dioxide and (b) nonoxidizing agents

such as bisthiocyanate, isothiazolines, acrolein, dodecylguanidine hydrochloride,

formaldehyde, glutaraldehyde, chlorophenols, and quaternary ammonium salts.

However, bacteria may adapt to biocides in different ways, such as the

production of enzymes, changes in the internal structure of the cell, or changes in the

composition of the cell wall. In order to minimize this problem, several biocides are

generally used alternatively in practice. Furthermore, although all biocides are

efficient on the planktonic population (i.e., microorganisms in the water phase), few

are efficient in the case of microorganisms in a biofilm, so that an increase in the

dosage up to 100 times is needed [129]. Besides, the use of biocides is more and more

limited by environmental legislation due to their toxicity to higher organisms.

Microbiological Methods

As already mentioned, bacterial life depends on many factors. A variation in, for

instance, pH, oxygen concentration, temperature, or light conditions may be used to

control microbial growth. However, care must be taken to ensure that changes in

these parameters do not induce changes in the bacterial population that result in the

growth of other microorganisms that may cause MIC. Besides, a change in these

parameters may increase the electrochemical corrosion of metals and alloys. A

decrease or increase in pH, for instance, may cause corrosion on copper and

aluminum alloys.

Physical Methods

Physical methods such as filtration of the water, mechanical removal of the

biofilm, or the use of ultraviolet (UV) radiation can be used for some specific

applications. For instance, UV light sterilization has been used in potable water

systems and cooling water systems instead of chlorination, which is otherwise

commonly used. However, in general, these methods are less efficient and more

costly than the use of chemicals [120,121].

Simulation of the Biogenic Attack

Besides the previously mentioned countermeasures, a technique that has gained in

importance reproduces the biogenic attack under conditions that are optimized for

the deterioration-causing agents, the microorganisms. By simulation of the biogenic

attack on materials, a quick-motion effect can be produced that allows materials to

be tested for their suitability for given applications. The simulation may even be used

for the development of resistant materials [97]. This has been shown in the case of

biogenic sulfuric acid attack on cement-bound concrete, mortar, and bricks; on

resin- or sulfur-bound concrete; on pipeline linings made of synthetics; and in the

case of biogenic nitric acid attack on cement-bound concrete and natural stone. It

must be emphasized that simulation of biogenic attack on materials requires profound

594 Thierry and Sand

knowledge of all the processes and participating microorganisms. If these are known,

the situation may be remodeled under conditions optimized for the microorganisms

resulting in a reduced time span for the corrosion to become detectable. The problem

of biogenic sulfuric acid corrosion in sewage pipelines has been described extensively

[6,7,38,80]. A countermeasure was a simulation that allowed remodeling of the

microbially caused process within a period of 1 instead of 8 years. Corrosion is

caused in this system by sulfuric acid–excreting thiobacilli, which thrive because

of hydrogen sulfide emissions from the sewage. H

S was increased if sewage

became anaerobic and was stripped later on. Thiobacilli need water, grow optimally

at 30°C (instead of 16°C in the Hamburg sewage system), and need oxygen. These

conditions were created in a simulation apparatus constructed for materials testing.

The results of the experiments confirmed that thiobacilli were the corrosion-causing

agents [96]. However, differences were noted between the results of chemical testing

(resistance of the same materials against pure sulfuric acid) and the results of these

biotests. The chemical test was not able to detect significant differences in the

resistance of the materials toward the acid attack (all materials corroded more or

less similarly), whereas the biotest revealed severe differences. Some concretes

were only slightly attacked (1 % loss of substance after 1 year of simulation)

whereas others lost 10% of their substance [97]. This finding demonstrates that

microbial interactions between material and microorganism are of the utmost

importance in the determination of resistance to a biogenic attack. The biotest can-

not be replaced by chemical and/or physical tests. Because of these test results, the

simulation apparatus is now used (internationally) for the development of new

materials with increased resistance to biogenic attack.

DIAGNOSTIC OF MIC

The diagnosis of MIC is a severe problem. In most cases, damage seems to be

explainable by the well-known and from the practical work familiar mechanisms

involving chemistry, physics, and materials sciences. This is a result of the fact that

engineers and technicians were never introduced, while studying, to the possibility

of microorganisms being a causative agent in corrosion. Thus, the often-observed

sediments, deposits, slimy layers, etc. tend to be neglected, although they indicate

at least the presence of microorganisms. Whereas it is well known that under natural

conditions microorganisms are ubiquitous, this fact seems to be neglected in the

case of technical environments.

However, life may also be possible in the latter case if several requirements are

fulfilled. Microorganisms, like all living beings need water. However, they are more

versatile than other organisms, because their growth limit is the water activity

value of a

= 0.6 (–680 bar osmotic pressure). Active microorganisms have been

detected in the temperature range from –10°C to 114°C; in the pH range from 0 to

12; at pressures above 1000 bar (deap sea vents); with and without oxygen, hydrogen

sulfide, carcinogenic and mutagenic compounds; and even under conditions of

high radiation (storage basins of nuclear power plants). Thus, if these requirements

are met, participation of microbes in cases of corrosion should be anticipated.

Especially when the following additional markers are found, MIC damage

becomes likely:

Microbially Influenced Corrosion 595

1. The occurrence of a slimy layer on the surface of a material. This can be

tested with the finger. Besides, removal of some slime and burning with a

lighter might cause the smell of burned hair = proteins.

2. The smell of mud or even rotten eggs (H

S) indicates MIC.

3. Coloration or discoloration of a material is suspicious.

4. A high water content besides a soft nature of deposits is often indicative of MIC.

5. Finally, crevice or pitting corrosion is often the result of microbial activity.

In general, almost all materials are susceptible to MIC problems: metals such

as mild and stainless steels, alloys, aluminum, copper; mineral materials such as

concrete, stone, brick, marble, sandstone, ceramics, glass; natural organic materials

such as wood, paper, leather, textiles, starch, polymers (lipids); synthetic organic

materials such as plastics, paints, coatings, glues, polymers; and hydrocarbons

such as mineral oils, waxes, tar, lubricants, cutting emulsions, fats, and greases.

Only in the groups of plastics are there several compounds that are not biodegradable.

Microorganisms do not have the enzymes necessary for a depolymerization.

Besides, some nondegradable compounds resulting from chemical synthesis

called xenobiotics exist (often pesticides, etc.).

Consequently, MIC may play an important role in many cases of

(bio)deterioration/corrosion. For a thorough diagnosis it is crucial that the preced-

ing points are checked and that experts are consulted. The site of corrosion should

be left untouched and under the same conditions as before the detection of the fail-

ure. Cleaning should be avoided in any case. Good documentation is needed,

meaning photographs, video, data from probes, materials, history, etc. If the diag-

nosis is not done properly, a good chance exists that there will soon be another

failure at the same (or a neighboring) site.

CONCLUDING REMARKS

Microbially induced corrosion is a ubiquitous phenomenon, but the participation of

microorganisms and their importance are not fully realized. This is often the result of

a lack of knowledge, because courses of study in the technical disciplines do not

impart this knowledge to students [53]. Another reason may be the fact that, in

contrast to a case of corrosion in which no biological factors are involved, in a case

of MIC only an interdisciplinary approach will give the knowledge necessary to

understand the mechanisms, However, this is inevitable because the microbiology

and the physicochemical processes causing MIC are usually too complicated to be

solved by simple test methods [23,85,86,140]. Most processes involved belong to

naturally occurring terrestrial cycles of matter. These cycles are the reason why life

can persist. Thus, we shall only be able to modify and slow down these processes,

never to inhibit them totally. Profound knowledge of all participating processes

will make it possible to enhance the life span of materials considerably [135].

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