Forms of Corrosion

Randhir Kumar Singh Asst Professor OPJIT

Eight Forms of Corrosion

1. 2. 3. 4. 5. 6. 7. 8. General Corrosion or Uniform Attack Galvanic or Two-Metal Corrosion Crevice Corrosion Pitting Intergranular Corrosion Selective Leaching Erosion Corrosion Stress Corrosion
2

Uniform Corrosion

Uniform corrosion or general corrosion, as sometimes called, is defined as a type of corrosion attack (deterioration) that is more or less uniformly distributed over the entire exposed surface of a metal Uniform corrosion also refers to the corrosion that proceeds at approximately the same rate over the exposed metal surface. Cast irons and steels corrode uniformly when exposed to open atmospheres, soils and natural waters, leading to the rusty appearance. In natural environment, oxygen is the primary cause of uniform corrosion of steels and other metals and alloys.

Cont
The photo on the right showed uniform corrosion (rusting) of a pair of steel nuts used to fasten a galvanized steel clamp on a street lamp post. In sharp contrast, the galvanized steel clamp did not show any signs of corrosion but its surface was discolored by the rust. It is also interesting to note that the surface of the top bolt looked like galvanized but the surface of the bolt below was completely rusted (just like the nut).

Uniform Corrosion

Mechanisms

What causes uniform corrosion? The anodic reaction in the corrosion process is always the oxidation reaction: M = M+ + e (1) In acidic environments, i.e., pH<7, the cathodic process is mainly the reduction of hydrogen ions: 2H+ + 2e = H2 (2) In alkaline or neutral environment, i.e., pH=7 or pH>7, reduction of dissolved oxygen is the predominant cathodic process that causes uniform corrosion: O2 + 2H2O + 4e = 4OH(3) With uniform distribution of cathodic reactants over the entire exposed metal surface, reactions (2) and/or (3) take place in a "uniform" manner and there is no preferential site or location for cathodic or anodic reaction. The cathodes and anodes are located randomly and alternating with time. The end result is a more or less uniform loss of dimension.

Prevention

How to prevent uniform corrosion? Uniform corrosion or general corrosion can be prevented through a number of methods: Use thicker materials for corrosion allowance Use paints or metallic coatings such as plating, galvanizing or anodizing Use Corrosion inhibitors or modifying the environment Cathodic protection (Sacrificial Anode or Impressed Current -ICCP) and Anodic Protection

Galvanic Corrosion, Bimetallic Corrosion or Dissimilar Metal Corrosion

What is galvanic corrosion? Galvanic corrosion or "Bimetallic Corrosion" or "Dissimilar Metal Corrosion", as sometimes called, is defined as the accelerated corrosion of a metal because of an electrical contact (including physical contact) with a more noble metal or nonmetallic conductor (the cathode) in a corrosive electrolyte. The less corrosion resistant or the "active" member of the couple experiences accelerated corrosion while the more corrosion resistant or the "noble" member of the couple experiences reduced corrosion due to the "cathodic protection" effect. The most severe attack occurs at the joint between the two dissimilar metals. Further away from the bi-metallic joint, the degree of accelerated attack is reduced.

Galvanic Corrosion
In this photo, a 5-mm thick aluminum alloy plate is physically (and hence, electrically) connected to a 10mm thick mild steel structural support. Galvanic corrosion occurred on the aluminium plate along the joint with the mild steel. Perforation of aluminum plate occurred within 2 years due to the huge acceleration factor in galvanic corrosion.

Galvanic Corrosion

10

Mechanisms

What causes galvanic corrosion? Different metals and alloys have different electrochemical potentials (or corrosion potentials) in the same electrolyte. When the corrosion potentials of various metals and alloys are measured in a common electrolyte (e.g. natural seawater) and are listed in an orderly manner (descending or ascending) in a tabular form, a Galvanic Series is created. It should be emphasized that the corrosion potentials must be measured for all metals and alloys in the same electrolyte under the same environmental conditions (temperature, pH, flow rate etc.), otherwise, the potentials are not comparable. The potential difference (i.e., the voltage) between two dissimilar metals is the driving force for the destructive attack on the active metal (anode). Current flows through the electrolyte to the more noble metal (cathode) and the less noble (anode) metal will corrode. The conductivity of electrolyte will also affect the degree of attack. The cathode to anode area ratio is directly proportional to the acceleration factor.
11

Prevention

How to prevent galvanic corrosion? Galvanic corrosion can be prevented through a number of methods: Select metals/alloys as close together as possible in the galvanic series. Avoid unfavorable area effect of a small anode and large cathode. Insulate dissimilar metals wherever practical Apply coatings with caution. Paint the cathode (or both) and keep the coatings in good repair on the anode. Avoid threaded joints for materials far apart in the galvanic series.
12

Crevice Corrosion

Crevice Corrosion refers to the localized attack on a metal surface at, or immediately adjacent to, the gap or crevice between two joining surfaces. The gap or crevice can be formed between two metals or a metal and non-metallic material. Outside the gap or without the gap, both metals are resistant to corrosion. The damage caused by crevice corrosion is normally confined to one metal at localized area within or close to the joining surfaces.
13

Crevice Corrosion

14

Cont

In this photo, a type 316 stainless steel tube and tube sheet from a heat exchanger in a seawater reverse osmosis (SWRO) desalination plant suffered crevice corrosion due to the presence of crevice (gap) between the tube and tube sheet.
15

Mechanisms

Crevice corrosion is initiated by a difference in concentration of some chemical constituents, usually oxygen, which set up an electrochemical concentration cell (differential aeration cell in the case of oxygen). Outside of the crevice (the cathode), the oxygen content and the pH are higher - but chlorides are lower. Chlorides concentrate inside the crevice (the anode), worsening the situation. Ferrous ions form ferric chloride and attack the stainless steel rapidly. The pH and the oxygen content are lower in the crevice than in the bulk water solution, just as they are inside a pit. The pH inside the crevice may be as low as 2 in a neutral solution. Once a crevice has formed, the propagation mechanism for crevice corrosion is the same as for pitting corrosion.

16

Cont
The major factors influencing crevice corrosion are: crevice type: metal-to-metal, metal-to-non-metal crevice geometry: gap size, depth, surface roughness material: alloy composition (e.g. Cr, Mo), structure environment: pH, temperature, halide ions, oxygen
17

Cont
A material's resistance to crevice corrosion is usually evaluated and ranked using the critical crevice temperature (CCT) in accordance with the ASTM Standard G48-03: Standard Test Methods for Pitting and Crevice Corrosion of Stainless Steels and Alloys by Use of FeCl3. The critical crevice temperature is the minimum temperature (C) to produce crevice attack and CCT is usually lower than the critical pitting temperature (CPT).

18

Prevention
Crevice corrosion can be designed out of the system Use welded butt joints instead of riveted or bolted joints in new equipment Eliminate crevices in existing lap joints by continuous welding or soldering Avoid creating stagnant conditions and ensure complete drainage in vessels Use solid, non-absorbent gaskets such as Teflon. Use higher alloys (ASTM G48) for increased resistance to crevice corrosion

19

Pitting Corrosion

Pitting Corrosion is the localized corrosion of a metal surface confined to a point or small area, that takes the form of cavities. Pitting corrosion is one of the most damaging forms of corrosion. Pitting factor is the ratio of the depth of the deepest pit resulting from corrosion divided by the average penetration as calculated from weight loss. Pitting corrosion is usually found on passive metals and alloys such aluminium alloys, stainless steels and stainless alloys when the ultra-thin passive film (oxide film) is chemically or mechanically damaged and does not immediately re-passivate. The resulting pits can become wide and shallow or narrow and deep which can rapidly perforate the wall thickness of a metal.
20

Cont

The following photo shows pitting corrosion of a SAF2304 duplex stainless steel after exposure to 3.5% NaCl solution.
21

Pitting

22

Cont

The shape of pitting corrosion can only be identified through metallography where a pitted sample is cross-sectioned and the pit shape, the pit size, and the pit depth of penetration can be determined.

ASTM-G46 has a standard visual chart for rating of pitting corrosion.

23

Mechanisms

For a defect-free "perfect" material, pitting corrosion is caused by the ENVIRONMENT (chemistry) that may contain aggressive chemical species such as chloride. Chloride is particularly damaging to the passive film (oxide) so pitting can initiate at oxide breaks. The environment may also set up a differential aeration cell (a water droplet on the surface of a steel, for example) and pitting can initiate at the anodic site (centre of the water droplet). For a homogeneous environment, pitting IS caused by the MATERIAL that may contain inclusions (MnS is the major culprit for the initiation of pitting in steels) or defects. In most cases, both the environment and the material contribute to pit initiation. The ENVIRONMENT (chemistry) and the MATERIAL (metallurgy) factors determine whether an existing pit can be repassivated or not. Sufficient aeration (supply of oxygen to the reaction site) may enhance the formation of oxide at the pitting site and thus repassivate or heal the damaged passive film (oxide) - the pit is repassivated and no pitting occurs. An existing pit can also be repassivated if the material contains sufficient amount of alloying elements such as Cr, Mo, Ti, W, N, etc.. These elements, particularly Mo, can significantly enhance the enrichment of Cr in the oxide and thus heals or repassivates the pit.
24

Prevention
Pitting corrosion can be prevented through: Proper selection of materials with known resistance to the service environment Control pH, chloride concentration and temperature Cathodic protection and/or Anodic Protection Use higher alloys (ASTM G48) for increased resistance to pitting corrosion
25

Erosion Corrosion
Erosion Corrosion refers to the combined action involving erosion and corrosion in the presence of a moving corrosive fluid or a metal component moving through the fluid, leading to accelerated loss of metal.

26

Mechanisms

The mechanical effect of flow or velocity of a fluid combined with the corrosive action of the fluid causes accelerated loss of metal. The initial stage involves the mechanical removal of a metal's protective film and then corrosion of bare metal by a flowing corrosive occurs. The process is cyclic until perforation of the component occurs. Erosion-corrosion is usually found at high flow rates around tube blockages, tube inlet ends, or in pump impellers. Cavitation-corrosion is a special form of erosioncorrosion. It is caused by water bubbles produced by a high-speed impeller, which then collapse and cause pits on the metal surface.
27

Cont

The photo shows erosion corrosion of a cast aluminum pump casing due to excessively high flow rate of the coolant.
28

Cont

29

Prevention
Erosion corrosion can be prevented through: streamline the piping to reduce turbulence control fluid velocity using more resistant materials using corrosion inhibitors or cathodic protection to minimize erosion corrosion

30

Intergranular Corrosion

Intergranular corrosion is sometimes also called "intercrystalline corrosion" or "interdendritic corrosion". In the presence of tensile stress, cracking may occur along grain boundaries and this type of corrosion is frequently called "intergranular stress corrosion cracking (IGSCC)" or simply "intergranular corrosion cracking". "Intergranular" or 'intercrystalline" means between grains or crystals. As the name suggests, this is a form of corrosive attack that progresses preferentially along interdendritic paths (the grain boundaries). Positive identification of this type of corrosion usually requires microstructure examination under a microscopy although sometimes it is visually recognizable as in the case of weld decay.
31

Intergranular Corrosion

The photos above show the microstructure of a type 304 stainless steel. The figure on the left is the normalized microstructure and the one on the right is the "sensitized" structure and is susceptible to intergranular corrosion or intergranular stress corrosion cracking.
32

Intergranular Corrosion

33

Mechanisms
This type of attack results from local differences in composition, such as coring commonly encountered in alloy castings. Grain boundary precipitation, notably chromium carbides in stainless steels, is a well recognized and accepted mechanism of intergranular corrosion. The precipitation of chromium carbides consumed the alloying element - chromium from a narrow band along the grain boundary and this makes the zone anodic to the unaffected grains. The chromium depleted zone becomes the preferential path for corrosion attack or crack propagation if under tensile stress. Intermetallics segregation at grain boundaries in aluminum alloys also causes intergranular corrosion but with a different name - "exfoliation".
34

Prevention
Intergranular corrosion can be prevented through: Use low carbon (e.g. 304L, 316L) grade of stainless steels Use stabilized grades alloyed with titanium (for example type 321) or niobium (for example type 347). Titanium and niobium are strong carbideformers. They react with the carbon to form the corresponding carbides thereby preventing chromium depletion. Use post-weld heat treatment.
35

Stress Corrosion Cracking (SCC)

Stress-corrosion cracking (SCC) is a cracking process that requires the simultaneous action of a corrodent and sustained tensile stress. This excludes corrosion-reduced sections that fail by fast fracture. It also excludes intercrystalline or transcrystalline corrosion, which can disintegrate an alloy without applied or residual stress. Stress-corrosion cracking may occur in combination with hydrogen embrittlement.
36

Cont
The image of stress corrosion I see

Is that of a huge unwanted tree Against whose trunk we chop and chop,
But which outgrows the chips that drop; And from each gash made in its bark

A new branch grows to make more dark

The shade of ignorance around its base, Where scientists toil with puzzled face.

(by S P Rideout 1967)

37

Mechanisms

Stress corrosion cracking results from the conjoint action of three components: (1) a susceptible material; (2) a specific chemical species (environment) and (3) tensile stress. For example, copper and its alloys are susceptible to ammonia compounds, mild steels are susceptible to alkalis and stainless steels are susceptible to chlorides. There is no unified mechanism for stress corrosion cracking in the literature. Various models have been proposed which include the following: Adsorption model: specific chemical species adsorbs on the crack surface and lowers the fracture stress. Film rupture model: stress ruptures the passive film locally and sets up an active-passive cell. Newly formed passive film is ruptured again under stress and the cycle continues until failure. Pre-existing active path model: Pre-existing path such as grain boundaries where intermetallics and compounds are formed. Embrittlement model: Hydrogen embrittlement is a major mechanism of SCC for steels and other alloys such as titanium. Hydrogen atoms diffuse to the crack tip and embrittle the metal.
38

SCC

39

Prevention
Stress corrosion cracking can be prevented through: Avoid the chemical species that causes SCC. Control of hardness and stress level (residual or load). Introduce compressive stress by shot-peening for example. Use of materials known not to crack in the specified environment. Control operating temperature and/or the electrochemical potential of the alloy.

40

Hydrogen-Induced Cracking

Hydrogen-Induced Cracking (HIC) is the stepwise internal cracks that connect adjacent hydrogen blisters on different planes in the metal, or to the metal surface. It is also known as stepwise cracking. HIC is especially prevalent in iron alloys because of the restricted slip capabilities in the predominantly body-centered cubic (BCC) structure. HIC is generally limited to steels having a hardness of 22 or greater on the Rockwell C scale.

41

Mechanisms
Hydrogen-induced cracking results from atomic hydrogen being absorbed by solid metals. This can occur during elevatedtemperature thermal treatments and in service during electroplating, contact with maintenance chemicals, wet H2S, corrosion reactions, cathodic protection, and operating in high-pressure hydrogen-containing environments.

42

Prevention
Hydrogen-induced cracking can be prevented through: Control of stress level (residual or load) and hardness. Avoid the hydrogen source. Baking to remove hydrogen.

43

Hydrogen Embrittlement (HE)

Hydrogen embrittlement (HE) is a process resulting in a decrease of the toughness or ductility of a metal due to the presence of atomic hydrogen. Hydrogen embrittlement has been recognized classically as being of two types. The first, known as internal hydrogen embrittlement, occurs when the hydrogen enters molten metal which becomes supersaturated with hydrogen immediately after solidification. The second type, environmental hydrogen embrittlement, results from hydrogen being absorbed by solid metals. This can occur during elevated-temperature thermal treatments and in service during electroplating, contact with maintenance chemicals, corrosion reactions, cathodic protection, and operating in high-pressure hydrogen.

44

Mechanisms

In the absence of residual stress or external loading, environmental hydrogen embrittlement is manifested in various forms, such as blistering, internal cracking, hydride formation, and reduced ductility. With a tensile stress or stress-intensity factor exceeding a specific threshold, the atomic hydrogen interacts with the metal to induce subcritical crack growth leading to fracture. In the absence of a corrosion reaction (polarized cathodically), the usual term used is hydrogen-assisted cracking (HAC) or hydrogen stress cracking (HSC). In the presence of active corrosion, usually as pits or crevices (polarized anodically), the cracking is generally called stress-corrosion cracking (SCC), but should more properly be called hydrogen-assisted stress-corrosion cracking (HSCC). Thus, HSC and electrochemically anodic SCC can operate separately or in combination (HSCC). In some metals, such as highsstrength steels, the mechanism is believed to be all, or nearly all, HSC. The participating mechanism of HSC is not always recognized and may be evaluated under the generic heading of SCC.
45

Prevention
Hydrogen embrittlement can be prevented through: Control of stress level (residual or load) and hardness. Avoid the hydrogen source. Baking to remove hydrogen.

46

Hydrogen Blistering
Hydrogen Blistering(HB) refers to the formation of subsurface planar cavities, called hydrogen blisters, in a metal resulting from excessive internal hydrogen pressure. Growth of near-surface blisters in low-strength metals usually results in surface bulges

47

Hydrogen Damage

48

Mechanisms

Hydrogen ions are reduced to hydrogen atoms that adsorb on the steel surface. Some of the hydrogen atoms will diffuse through the steel and accumulate at hydrogen traps, typically voids around inclusions. When hydrogen atoms meet in a trap and combine, they form hydrogen gas (H2) molecules in the trap. The accumulation hydrogen gas inside the extremely small cavity will lead to the buildup of excessive internal hydrogen pressure. At certain times, this internal hydrogen pressure will become sufficient to cause the steel to blister. Blisters occur usually in low strength steels (<80ksi yield strength) and are formed preferentially along elongated nonmetallic inclusions or laminations in line pipe steels
49

Prevention
Hydrogen Blistering can be prevented through: Control of impurity of steel. Avoid the hydrogen source. Baking to remove hydrogen.

50

Corrosion Fatigue
Corrosion Fatigue refers to the process in which a metal fractures prematurely under conditions of simultaneous corrosion and repeated cyclic loading at lower stress levels or fewer cycles than would be required to cause fatigue of that metal in the absence of the corrosive environment.

51

Corrosion Fatigue

52

Mechanisms

Corrosion Fatigue is caused by crack development under the simultaneous action of corrosion and cyclic stress. The usual case involves rapidly fluctuating stresses that may be well below the tensile strength. As stress is increased, the number of cycles required to cause fracture decreases. As in the case of stress corrosion cracking, corrosion fatigue is dependent on the interactions among loading, environmental, and metallurgical factors.
53

Cont

For a given material, the fatigue strength (or fatigue life at a given maximum stress value) generally decreases in the presence of an aggressive environment. For the majority of engineering alloys, the fatigue limit refers to the stress level below which failure does not occur within a specified number of cycles, usually 107 or 108 cycles, as shown in the S-N plot.
54

Prevention
Corrosion Fatigue can be prevented through: reducing the fatigue by minimizing vibration and pressure fluctuation. reducing the corrosion by using highperformance alloys resistant to corrosion fatigue reducing the corrosion by using coatings and inhibitors to delay the initiation of corrosion fatigue cracks
55

Cavitation and Impingement

Cavitation

Cavitation occurs when a fluid's operational pressure drops below it's vapor pressure causing gas pockets and bubbles to form and collapse. This can occur in what can be a rather explosive and dramatic fashion.

56

Cavitation Erosion

57

Mechanisms

In fact, this can actually produce steam at the suction of a pump in a matter of minutes. When a process fluid is supposed to be water in the 20-35C range, this is entirely unacceptable. Additionally, this condition can form an airlock, which prevents any incoming fluid from offering cooling effects, further exacerbating the problem. The locations where this is most likely to occur, such as:

At the suction of a pump, especially if operating near the net positive suction head required (NPSHR) At the discharge of a valve or regulator, especially when operating in a nearclosed position At other geometry-affected flow areas such as pipe elbows and expansions Also, by processes incurring sudden expansion, which can lead to dramatic pressure drops

This form of corrosion will eat out the volutes and impellers of centrifugal pumps with ultrapure water as the fluid. It will eat valve seats. It will contribute to other forms of erosion corrosion, such as found in elbows and tees
58

Prevention

Cavitation should be designed out by reducing hydrodynamic pressure gradients and designing to avoid pressure drops below the vapor pressure of the liquid and air ingress. The use of resilient coatings and cathodic protection can also be considered as supplementary control methods.

59

Impingement Corrosion
Impingement attack is related to cavitation damage, and has been defined as localized erosioncorrosion caused by turbulence or impinging flow. Entrained air bubbles tend to accelerate this action, as do suspended solids. This type of corrosion occurs in pumps, valves, orifices, on `heatexchanger tubes, and at elbows and tees in pipelines.

60

Cont

Impingement corrosion usually produces a pattern of localized attack with directional features. The pits or grooves tend to be undercut on the side away from the source of flow, in the same way that a sandy river bank at a bend in the river is undercut by the oncoming water. When a liquid is flowing over a surface (e.g. in a pipe), there is usually a critical velocity below which impingement does not occur and above which it increases rapidly. Impingement attack first received attention due to the poor behavior of some copper alloys in seawater. In practice, impingement and cavitation may occur together, and the resulting damage can be the result of both. Impingement may damage a protective oxide film and cause corrosion, or it may mechanically wear away the surface film to produce a deep groove.

61

Fretting Corrosion

Fretting corrosion refers to the deterioration at the interface between contacting surfaces as the result of corrosion and slight oscillatory slip between the two surfaces. Fretting corrosion are expected in many tightfitting parts that are designed not to slip against each other, but in the presence of vibration and pressure fluctuation, these parts do slip against each other such as bolted or riveted parts that vibrate.
62

Fretting Corrosion

63

Mechanisms
Fretting corrosion is a severe corrosive wear that occurs to heavily loaded surfaces that move only slightly but repeatedly against each other. Fretting corrosion is different from ordinary wear in that it occurs rapidly with little movement.

64

Prevention
Fretting Corrosion can be prevented through: Lubricate the surfaces Regularly inspect and maintain the lubrication

65

Dealloying, Selective Leaching & Graphitic Corrosion

Dealloying is the selective corrosion of one or more components of a solid solution alloy. It is also called parting, selective leaching or selective attack. Common dealloying examples are decarburization, decobaltification, denickelification, dezincification, and graphitic corrosion. Decarburization is the selective loss of carbon from the surface layer of a carbon-containing alloy due to reaction with one or more chemical substances in a medium that contacts the surface. Decobaltification is selective leaching of cobalt from cobalt-base alloys, such as Stellite, or from cemented carbides. Denickelification is the selective leaching of nickel from nickel-containing alloys. Most commonly observed in copper-nickel alloys after extended service in fresh water. Dezincification is the selective leaching of zinc from zinc-containing alloys. Most commonly found in copper-zinc alloys containing less than 85% copper after extended service in water containing dissolved oxygen.
66

Graphitic corrosion
Graphitic corrosion is the deterioration of gray cast iron in which the metallic constituents are selectively leached or converted to corrosion products leaving the graphite intact. Graphitic corrosion should not be confused with another term graphitization, which is used to describe the formation of graphite in iron or steel, usually from decomposition of iron carbide at elevated temperatures.

Graphitic corrosion of a gray cast iron valve

67

Mechanisms

Different metals and alloys have different electrochemical potentials (or corrosion potentials) in the same electrolyte. Modern alloys contain a number of different alloying elements that exhibit different corrosion potentials. The potential difference between the alloying elements is the driving force for the preferential attack on the more "active" element in the alloy. In the case of dezincification of brass, zinc is preferentially leached out of the copper-zinc alloy, leaving behind a copper-rich surface layer that is porous and brittle.

68

Selective Corrosion

69

Prevention
Dealloying, selective leaching and graphitic corrosion can be prevented through the following methods: Select metals/alloys that are more resistant to dealloying. For example, inhibited brass is more resistant to dezincification than alpha brass, ductile iron is more resistant to graphitic corrosion than gray cast iron. Control the environment to minimize the selective leaching Use sacrificial anode cathodic protection or impressed current cathodic protection
70

THANK YOU

71