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Various Corrosive Environments And Their Role In Corrosion

Prepared By Sajan Brahmbhatt Roll No. 936 B.E. IV-Metallurgy

There are various environments in which deterioration of material takes place some of the prominent environments are listed and discussed below:

Atmospheric Corrosion Corrosion in Fresh Water and Other Waters Corrosion in Seawater Corrosion in Soils Corrosion in Concrete

Atmospheric Corrosion
Environmental Factors and Their Effects:
Atmospheric corrosion is electrochemical corrosion in a system that consists of a metallic material, corrosion products and possibly other deposits, a surface layer of water (often more or less polluted), and the atmosphere. The general cathodic reaction is reduction of oxygen, which diffuses through the surface layer of water and deposits.

The three main factors, i.e. time of wetness, composition of electrolyte, and temperature, depend for one thing on the type of atmosphere: 1. Rural (inland): dry environment with little or no pollution 2. Marine: on and by the sea, with high humidity and chlorides 3. Urban: polluted by exhaust, smoke and soot 4. Industrial: highly polluted by industry smoke and precipitate

Climatic conditions are also important. For instance, the corrosion conditions may be severe in the tropical zone due to high temperature and particularly at the coast high humidity. If the metal surfaces are completely clean and smooth, and there is no pollution of the atmosphere, significant corrosion does not occur at a relative humidity below 100%. In reality, however, materials like steel, copper, zinc and nickel corrode when the relative humidity exceeds 5070%. This is partly due to corrosion products. If the surface in addition is contaminated by chloride, soot or dust particles, which are hygroscopic, the corrosion rate is considerable at lower relative humidity than when it exceeds 60%. Industrial and urban atmospheres contain more or less solid particles consisting of carbon, soot, sand, oxides, and salts, e.g. chloride and sulphate. Many of these substances attract moisture from the air; some of them also attract polluting and corrosive gases. The salts cause high conductivity, and carbon particles can lead to a large number of small galvanic elements because the particles act as efficient cathodes after deposition on the surface.

Rain affects the corrosion rate in different and opposite ways. Some effects stimulate corrosion, but rain may also wash away pollutants and thus reduce the corrosion rate. The most significant pollutant in the form of a gas is SO 2, originating from combustion of oil, gas or coal containing some sulphur. Together with water, SO2 forms sulphuric acid, H2SO4. Therefore, metallic materials that corrode strongly in acids are not suitable without a coating in industrial atmospheres with high contents of SO2. In marine atmospheres measured corrosion rates are related to the rates of chloride deposition. Automobile corrosion worries a huge number of people and is of large economic significance. Internal cavities in doors and nearly closed sections are critical places. This is due to varying temperature and bad ventilation, leading to formation and conservation of condensate, i.e. long time of wetness.

Atmospheric Corrosion on Different Materials

o The corrosion rate of steel depends strongly on the type of atmosphere. o Some alloying elements also have a large effect on the corrosion rate. o For instance, small amounts of Cu, Cr and Ni cause the rust layer formed during service to be denser, so that the corrosion rate becomes relatively low after some time. Steels alloyed in this way are the so-called weathering steels, of which Cor-Ten steel is a well-known product. The rust layer is often decorative with nice colors, and such steels are used in front panels for buildings.

o Several aluminum alloys show very good corrosion resistance in various atmospheres. o Extensive galvanic corrosion may occur on Aluminum in contact with copper, mild steel (in marine atmosphere) and graphite, less in contact with stainless steel, while aluminum is compatible with Zinc. o Stainless steel behaves mainly in accordance with its name under atmospheric conditions. o For comparison, corrosion rates in different waters are also shown in the table. The low rates of corrosion on zinc are due to protecting surface films of basic zinc chloride and carbonate. o Copper and copper alloys are highly resistant to atmospheric corrosion because of surface films mainly composed of basic copper salts. o Tin as well as nickel and nickel alloys also corrode at similar rates. o Lead possesses excellent corrosion resistance in atmospheres due to surface protecting films (insoluble sulphate, sulphide, carbonate and oxide).

The most important methods for preventing atmospheric corrosion are


1) To select a corrosion-resistant structural material, 2) To use a corrosion-resistant coating (metallic, inorganic, organic or composite), 3) To close internal cavities in order to avoid access of humid air, or conversely, 4) To make sure that there is ample ventilation and drainage,
5)

To supply oil, grease, or special substances

Corrosion in Fresh Water and Other Waters


This group of environments comprises primarily fresh water in lakes, rivers and brooks, rain and ground water. In addition there are waters contaminated in someway, or with some matter added. A common condition for corrosion in natural waters is the presence of oxygen. o The rate-determining step is often diffusion of oxygen to the metal surface. This is particularly the case for corrosion of unalloyed or low-alloy steels. At least partly it applies also to zinc when pH < 89, where reduction of hydrogen may play an additional role. On the other hand, materials like aluminumand stainless steels (and Zn at higher pH values) are under anodic control (passivation).

o Contrary to atmospheric corrosion, corrosion in natural waters is hardly dependent on the grade of iron, unalloyed and low alloy steel, because composition and treatment of the steel in this case have little effect on the barrier properties of surface layers of corrosion products. o In the pH ranges < 4 and > 10, however, the composition of the steel or iron is significant because the corrosion process involves hydrogen evolution and passivation, respectively. o At low pH values, the corrosion rate increases with increasing contents of C, N, P and S, with cold working. o The reason is depolarization, partly of the hydrogen reduction and partly of the anodic dissolution reaction. The effects of some other elements, such as As, Mn, Cu, Cr and Ni, depend on the concentration. o The properties of steel and other metallic materials in acidic environments are of interest when applied to ground water with sulphate-reducing bacteria and water contaminated by H2S. o Oxygen concentration, temperature and flow velocity have large effects on oxygen transport to the metal surface and consequently on the corrosion rate in natural waters. In addition, variation in corrosion rate is also caused by the composition of the water, since this may strongly affect the barrier properties of surface layers. o Natural waters contain different amounts of Ca and Mg salts. If the salt content is high, the water is called hard, in the opposite case it is soft. o At pH < 4, iron corrodes faster because of hydrogen reduction, while the lower corrosion rate at pH > 10 may partly be due to diffusion-limiting deposition (see below) and partly to passivation. o Hard waters are known to be less corrosive than soft ones. o The reason for this is that, when the salt content becomes high enough, deposits particularly CaCO3 are formed, which hinder the oxygen diffusion to the metal surface. o When the measured pH is higher than pHs, i.e. the saturation index SI is positive (the water is supersaturated with CaCO3), CaCO3 is deposited. o Good correlation has been found between SI and corrosively of the water. o Acid salts, i.e. salts that hydrolyze and give acid solutions, lead to corrosion under combined hydrogen evolution and oxygen reduction to the extent that may be expected at the actual pH. The oxygen reduction reaction may be more efficient than usual. Examples of such salts are AlCl3 and FeCl3. o Ammonium salts (e.g. NH4Cl) are also acidic, and they give higher corrosion rates than other salts at the same pH. This applies particularly to ammonium nitrate, which in the presence of NH3 may give extreme corrosion rates. o Alkaline salts (e.g. Na3PO4, Na2SiO3, and Na2CO3), which hydrolyze and give alkaline solutions, act as corrosion inhibitors by passivation of iron and steels under access by oxygen. Oxide is formed, but in some cases one get a more or less passivizing salt layer in addition (phosphate, silicate).

o Oxidizing salts may either lead to rapid corrosion by providing an extra cathodic reaction (as do FeCl3, and CuCl2), or to inhibition and passivation. Organic matter in the water may affect corrosion in different ways. Substances that exist suspended or dissolved may be deposited and form more or less voluminous layers in regions with low flow velocity. This may give a reduced average corrosion rate, but increased and sometimes heavy localized corrosion, i.e. deposit corrosion. In hot tubes, such layers may also result in local overheating and crack formation. In pipes with smaller diameters, such deposits may reduce the effective crosssection strongly and sometimes block the pipe completely. Deposit corrosion takes place underneath the tubercles. Several cases of corrosion attacks in which bacteria have played a significant role have been experienced, e.g. in cooling water systems and heat exchangers. Corrosion in public water piping systems is responsible for large economic loss. In pipes of cast iron, steel and other metallic materials, Corrosion may be prevented by use of coatings or by water treatment (addition of calcium compounds, alkalization or carbonation).

Corrosion in Seawater
The importance of seawater as a corrosive environment has increased during the last few decades because of offshore exploration of oil and gas. There is also an increasing application of seawater for production of fresh water in parts of the world where this is in short supply. Corrosion is a major problem in desalination plants. Seawater has a chloride content that gives maximum corrosion rate. Mechanism:

o The corrosion rate is usually not particularly large because the water contains Ca and Mg salts. The bulk pH in seawater is commonly 88.3, but due to cathodic production of OH, the pH value at the surface increases sufficiently for deposition of CaCO3 and possibly to a smaller extent some Mg(OH)2together with iron hydroxide. o The deposits form a surface layer that reduces oxygen diffusion so much that the average corrosion rate on steel in seawater (0.10.15 mm/year) is less than in soft fresh water. Because the corrosion rate depends on the supply of oxygen, it will be highest in the splash zone where a thin water film exists a major proportion of the time, and where parts of the corrosion product layer frequently are washed away. On offshore structures the splash zone is the most difficult zone to protect satisfactorily, because it is not possible to make use of cathodic protection. Thick organic coatings (e.g. Neoprene) orMonel sheathing have been used in many cases. Metals in seawater are exposed to marine growth (fouling). The fouling tendency is very different for different metals and increases in the following order: 1. Copper and 9010 coppernickel. 2. Brass and bronze. 3. 7030 coppernickel, Aluminum, Bronze and Zinc. 4. Nickelcopper. 5. Carbon steel, low-alloy steels, stainless steels, nickel alloys and titanium.

Some Important methods for preventing sea water corrosion


o Chlorination is frequently carried out, primarily by adding sodium hypochlorite. In stainless steel systems, amounts corresponding to 12 ppm Cl2 are often added continuously. o By this, slime formation is prevented, but at the same time the potential is raised, and the risk for initiation of crevice corrosion is increased. o Recent research shows that the resistance to crevice corrosion initiation on high-alloy stainless steel increases with the time in chlorinated seawater. o If moderate chlorination is applied in the beginning, with increasing addition of sodium hypochlorite after some time, the risk for initiation of corrosion will be lower than if full chlorination was applied from the start. o Corrosion in seawater may also occur on metallic materials that originally are protected by thinner or thicker organic coatings. o The reason for this is that water, oxygen and chlorides diffuse through the coating. Undermining corrosion starts and the coating will slowly be broken down. o One example of this is corrosion on sea cables. The outer layers of a sea cable consist of a metallic reinforcement usually steel wires with hot-dip zinc coating and an external layer of jute and asphalt or polypropylene and asphalt.

Corrosion in Soils
Soils can be classified on the basis of particle size.

o Gravel contains the coarsest Particles (> 2 mm) and clay the finest ones (< 0.002 mm), with sand and silt in between. o Soils containing the finest particles, with ample distribution of small particle sizes are very dense and prevent supply of oxygen (but not of water), while gravel allows oxygen to be transported easily. Most metallic materials that are used in soils corrode under cathodic control, i.e. under control of oxygen transport. Thus, the density of the soil is important. The relationship is, however, somewhat complicated: the corrosion rate is often lower in porous than in more compact soil, because preventive deposits may be formed more easily in the former case. Where the density varies along the metal surface, differential aeration cells may be established with concentrated corrosion at areas with a dense soil. There are also other important environmental factors: other conditions affecting water and oxygen supply, resistivity, dissolved salts, pH, microbiological activity and stray electric currents. Generally, aggressive soils have low resistivity. In corrosive sediments it may be up to 20004000 ohm cm, in little or non corrosive 40006000 ohm cm or more.

Various biological factors affect corrosion in soils.

o Organic acids originating from humus are relatively corrosive versus steel, zinc, lead and copper. o In certain soil types, particularly acidic clay, very high corrosion rates have been experienced under anaerobic conditions. This is commonly caused by sulphate-reducing bacteria, which is indicated by ferrous sulphide found as part of the corrosion products. o On the critical surface area of the pipeline, the current runs from metal to environment by anodic dissolution of the metal, giving high corrosion rates under unfavorable conditions. o Stray currents may originate from railways, electrolysis plants, electric cables and large electric plants. Generally, direct current causes the greatest problem. Alternating Stray current has usually little effect on steel, but it may attack lead to a great extent. Stray current originating from a cathodic protection system may cause localized corrosion on steel pipelines. Composition of carbon steel and low-alloy steel is of little significance for corrosion in soils, as is the case for corrosion in seawater and other waters. A problem of particularly large economic significance is corrosion on buried pipelines, and there are special reasons to worry about the external corrosion.

o Examples from some communities show that a major part of the water in the public fresh water pipeline system gets lost due to leakage, mainly because of corrosion. o The leakages cause damage to other property, the capacity demand of the waste water system increases, costly repair is needed, and such work may conflict with other activities and traffic. To prevent this, one of the external coating systems that have been recommended for water pipelines in soil is 25 m zinc + asphalt or Bitumen. o Generally, the most important measures for corrosion prevention in soils are use of organic coatings (coal tar, plastics or rubber (6 mm), wound tape), inorganic coatings (cement mortar or enamel, but these are brittle and may easily be damaged mechanically), fiberreinforced cement mortar, metallic coatings (hot-dip or thermal spray zinc), filling by limestone or other calcium-containing matter, and cathodic protection. o The combination of reinforced coal tar coating and cathodic protection has been used extensively to protect pipelines and tanks.

Corrosion in Concrete
The development and building of large concrete structures for offshore oil and gas production in the 1970s called for increased attention to corrosion of steel reinforcement, and of seawaterexposed steel parts in metallic contact with the reinforcement. Concrete constitutes an alkaline environment for the embedded steel reinforcement, which leads to passivation of the steel. As passivized steel is liable to localized corrosion in environments with sufficient concentration of an aggressive substance like chloride.

o A crucial corrosion mechanism is therefore the transport of chloride and oxygen through the outer layer of concrete, which covers the reinforcement. o At an early stage of the actual research it was assumed and shown by laboratory experiments that intensive corrosion might occur on i) reinforcement steel bars at cracks in theconcrete cover, ii) On seawater-exposed steel parts that were metallically connected to the reinforcement, because these cases most often implied a large area ratio between the reinforcement (cathode) and the exposed steel (anode). Sites without cracks but with extensive penetration of chloride through the concrete cover were also assumed to be strongly liable to corrosion due to local breakdown of the passive oxide layer on the steel bars. There is still some uncertainty as regards risk for galvanic corrosion on exposed steel parts. This problem may exist, particularly due to efficient aeration of the concrete in the splash zone. In harbor structures, bridge structures and buildings, many cases of extensive damage due to corrosion of reinforcement have occurred during recent years. For structures exposed to the atmosphere there is, in addition to possible localized breakdown due to chloride, a second important mechanism: carbonation of the concrete, which reduces the pH of the solution in pores and leads to general breakdown of passivity. Besides localized or general surface corrosion of the reinforcing bars, stress corrosion cracking or corrosion fatigue may take place, which emphasizes the severity of the attacks. A major cause of corrosion in these structures is that they have not been subject to the same strict rules as offshore structures with respect with concrete quality and cover. One of the problems is connected with concrete decks on road bridges, where salt containing a high proportion of chlorides may originate from de-icing or from the sea. In addition to mechanical repair (replacement of old concrete and application of surface coatings), electrochemical methods are used for rehabilitation of concrete structures nowadays. Electrochemical methods comprise chloride removal, re-alkalization and cathodic protection. Advancement is that improved concrete with low permeability has been developed in recent years. In addition to the mentioned protection methods, i.e. use of high-quality concrete, sufficient cover, external organic coating or sealing, and cathodic protection, possible methods for prevention of reinforcement corrosion in new concrete structures include also the application of a protection measure directly on to the reinforcement: i) hot-dip zinc coating, with varying experience as to the effectiveness, ii) Powder epoxy coating, e.g. for bridge decks, iii) Reinforcing bars iv) Corrosion inhibitors, primarily in high quality concrete with a thick cover.

Reference
o Internet

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