Dr.

Hani Aziz Ameen

Types of Corrosion

Types of Corrosion
Asst. Prof. Dr. Hani Aziz Ameen Technical College - Baghdad Dies and Tools Engineering Department E-mail: haniazizameen@yahoo.com

1. Atmospheric Corrosion Atmospheric corrosion is defined as the corrosion or degradation of material exposed to the air and its pollutants rather than immersed in a liquid. This has been identified as one of the oldest forms of corrosion and has been reported to account for more failures in terms of cost and tonnage than any other single environment. Many researchers classify atmospheric corrosion under categories of dry, damp, and wet, thus emphasizing the different mechanisms of attack under increasing humidity or moisture. Corrosively of the atmosphere to metals varies greatly from one geographic location to another, depending on such weather factors as wind direction, precipitation and temperature changes, amount and type of urban and industrial pollutants and proximity to natural bodies of water. Service life may also be affected by the design of the structure if weather conditions cause repeated moisture condensation in unsealed crevices or in channels with no provision for drainage. [1] 2- Uniform Corrosion Uniform corrosion is the most common form of corrosion. It is normally characterized by a chemical or electrochemical reaction which proceeds uniformly over the entire exposed surface or over a large area. The metal becomes thinner and eventually fails.[2]

Dr. Hani Aziz Ameen Types of Corrosion With aluminum, this type of corrosion is observed especially in highly acidic or alkaline media, in which the solubility of the natural oxide film is high . The dissolution rate of the film is greater than its rate of formation; however, the ratio of both rates can change over time.[3] General corrosion or uniform corrosion occurs in the solutions where pH is either very high or very low or at high potentials in electrolytes with high chloride concentrations. In acidic (low pH) or alkaline (high pH) solutions, the aluminum oxide is unstable and thus non protective. [1]

3- Galvanic Corrosion Economically, galvanic corrosion creates the largest number of corrosion problems for aluminum alloys. Galvanic corrosion, is also known as a dissimilar metal corrosion, occurs when aluminum is electrically connected to a more noble metal, and both are in contact with the same electrolyte.[4]

Fig.(1) Galvanic Reaction [5] When two dissimilar metals are in contact, the corrosion rate of the more active metal(more negative Ecorr) is accelerated, while the corrosion rate of the noble metal(less negative Ecorr) is reduced. The higher the difference in Ecorr, the more severe is galvanic corrosion. 2

Dr. Hani Aziz Ameen Types of Corrosion Galvanic Series: a list of measured corrosion potentials (Ecorr) of a number of metals and alloys in a given electrolyte. Prevention of Galvanic Corrosion eliminate electrical contact b/w dissimilar metals (use gaskets, washers, o-rings, ext) If electrical contact can not be avoided it is preferable to: select dissimilar metals that are close in the galvanic series design for a small Ac/Aaarea ratio give thickness allowance for the more active metal coat the cathode to reduce Ac/Aa [2]

4- Crevice Corrosion Crevice corrosion requires the presence of a crevice a salt water environment oxygen (Fig.( 2)). The crevice can result from the over lap of two parts or a gap between a bolt and a structure . When aluminum is wetted with the salt water and water enters the crevice, little happens initially. Over time inside the crevice oxygen is consumed due the dissolution and precipitation of aluminum.

Fig. (2): Crevice Corrosion[1] Crevice corrosion can occur in a saltwater environment if the crevice become deaerated and the oxygen reduction reaction outside of the crevice 3

Dr. Hani Aziz Ameen Types of Corrosion mouth under these conditions. The crevice becomes more acidic and corrosion occurs at an increasing rate.[1] Crevice corrosion initiated by changes in local chemistry within the crevice: a. depletion of inhibitor in the crevice is b. depletion of oxygen in the crevice c. a shift to acid conditions in the crevice d. build-up of aggressive ion species (e.g. chloride) in the crevice[6] 5- Intergranular corrosion Intergranular (intercystalline) corrosion is selective of grain boundaries or closely adjacent reaction without appreciable attack of the grains themselves. Intergranular corrosion is a generic term that includes several variations associated with different metallic structures and thermomechanical treatment intergranular corrosion is caused by potential differences between the grain boundary region and the adjacent grain bodies. Salt water exposure can cause intergranular corrosion (IGC) in some aluminum alloys. Dix explained IGC of Al-copper (Cu) alloys in 1940. During aging at elevated temperatures (200C), precipitation of discrete particles occurs, with more advanced precipitation at the grain boundaries than in the grain matrix. The grain boundaries are surrounded by narrow zones of Al that etch smoothly. These zones become more pure, with a more active corrosion potential (solution potential) in aerated salt water [4].

Dr. Hani Aziz Ameen

Types of Corrosion

Fig. (3) Intergranular Corrosion In A Recrystallized Wrought Structure.[7]

In some alloy systems, IGC is a result of galvanic corrosion between anodic grain- boundary precipitates and the depleted zones, rather than between the matrix and the depleted zone. In 2xxx series alloys, it is a narrow band on either side of the boundary that is depleted in copper, in 5xxx series alloys; it is the anodic constituent Mg2Al3 when that constituent forms a continuous path along a grain boundary in copper free 7xxx series alloys. It is generally considered to be anodic zinc and magnesium bearing constituents on the grain boundary. The 6xxx series alloys generally resist this type of corrosion, although slight intergranular attack has been observed in a aggressive environments [7] as shown in Fig.(4).

Fig.(4) Interganular Corrosion [8] 5

Dr. Hani Aziz Ameen 6- Exfoliation corrosion

Types of Corrosion

Exfoliation is yet another special form of intergranular corrosion that proceeds laterally from the sites of initiation along planes parallel to the surface, generally at grain boundaries, forming corrosion products that force metal away from the body of the material, giving rise to a layered appearance. Exfoliation is sometimes described as lamellar, layer, or stratified corrosion. In this type of corrosion, attack proceeds along selective subsurface paths parallel to the surface. It is possible to visually recognize this type of corrosion if the grain boundary attack is severe otherwise examination under a microscope is needed [9]. microstructure

Fig.(5) Exfoliation Corrosion In An Aluminum Alloy[10] Mechanisms Exfoliation is a special type of intergranular corrosion that occurs on the elongated grain boundaries by heavy deformation during hot or cold rolling and where no recrystallization has occurred. The corrosion

product formed has a greater volume than the volume of the parent metal. The increased volume forces the layers apart, and causes the metal to exfoliate or delaminate. Aluminum alloys are particularly susceptible to this type of corrosion. Exfoliation is characteristic for the 2000(Al 6 Cu), 5000 (Al

Dr. Hani Aziz Ameen Types of Corrosion Mg), and 7000 (Al Zn Mg) series alloys which grain boundary precipitation or depleted grain boundary regions. Exfoliation corrosion (as shown in figure(2-6)) can be prevented through:

the use of coatings selecting a more exfoliation resistant aluminum alloy using heat treatment to control precipitate distribution[ 9]

Fig. (6) Exfoliation of Al Alloys[11] 7- Erosion Corrosion Erosion Corrosion of aluminum occurs in high velocity water and is similar to jet impingement corrosion. Erosion Corrosion of aluminum is very slow in pure water, but is accelerated at pH > 9, especially with high carbonate and high silica content of the water. Aluminum is very stable in neutral water; however it will corrode in either acidic or alkaline waters.

Dr. Hani Aziz Ameen Types of Corrosion To prevent erosion corrosion, one may change the water chemistry or reduce the velocity of the water, or for the water chemistry, the pH must be below 9, and the carbonate and the silica levels must be reduced [1]. 8- Stress Corrosion Cracking (SCC) Stress corrosion cracking (SCC) (as shown in Fig.(7)) is the bane of aluminum alloys. SCC requires three simultaneous conditions, first a susceptible alloy, second a humid or water environment, and third a tensile stress which will open the crock and enable crack propagation. SCC can occur in two modes intergranular stress corrosion cracking (lGSCC) which is the more common form, or transgranular SCC (TGSCC). In TGSCC, the crack follows the grain boundaries. In transgranular stress corrosion cracking (TGSCC), the cracks cut through the grains and are oblivion to the grain boundaries. The general trend to use higher strength alloys peaked in 1950 with alloy 7178 T651 used on the Boeing 707, then the industry charged to using lower strength alloys. The yield strength of the upper wing skin did not exceed the 1950 level until the Boeing 777 in the 1990s. The reason behind selecting the lower strength alloys for the Boeing 747 and the L.1011 was the aircraft designers chose an alloy with better SCC resistance rather than the higher yield strength .[1]

Fig.(7 ) Crack Initiation From The Pit Root At Weld Pool [12] 8

Dr. Hani Aziz Ameen 9- Corrosion Fatigue

Types of Corrosion

Corrosion fatigue (as shown in Fig.(8)) can occur when an aluminum structure is repeatedly stressed at low stress levels in corrosive environment. A fatigue crack can initiate and propagate under the influence of the crackopening stress and the environment. Similar striations may sometimes be found on corrosion fatigued samples , but often the subsequent crevice

corrosion in the narrow fatigue crack dissolves them Fatigue strengths of aluminum alloys are lower in such corrosive environments as seawater and other salt solutions than in air , especially when evaluated by low stress long duration tests . Like SCC of aluminum alloys, corrosion fatigue requires the presence of water. In contrast to SCC, however, Corrosion fatigue is not appreciably affected by test direction, because the fracture that results from this type at attack is predominantly Transgranular. [4]

(a) (b) Fig.(8) (A) Corrosion Fatigue Curve In Different Environments (B) Appearance Of Fatigue Crack

10- Filiform Corrosion Filifrom corrosion (as shown in Fig.(9)) (also known as worm track corrosion) is a cosmetic problem for painted aluminum. Pinholes or defects

in the paint from scratches or stone bruises can be the initiation site where 9

Dr. Hani Aziz Ameen Types of Corrosion corrosion begins with salt water pitting. The mechanism of filiform corrosion (as shown in Fig.(10)) requires chlorides for initiation and both high humidity and chlorides for the propagation of the track. The propagation depends on where and how the alloy is used. The filament must be initiated by Chlorides, and then it proceeds by a mechanism similar to crevice corrosion. The head is acidic, high in chlorides and

deaeratied and is the anodic site. Oxygen and water vapor diffuse through the filiform tail, and drive the cathodic reaction [3].

Fig.(9) Filiform Corrosion [13]

Fig.(10) Mechanism Of Filiform Corrosion[3] 10

Dr. Hani Aziz Ameen Types of Corrosion Filiform corrosion can be prevented by sealing defects with point or wax, and keeping the relative humidity low. Filiform corrosion occurs with all types of paints: acrylic lacquers, epoxy-polyamides, epoxy-amines and polyurethanes, and whatever the classic mode of application, whether with liquid paint or electrostatic powdering. It does not occur under sealed coatings such as electricians tape.[3]

11-

Microbiological Induced Corrosion Microbiological Induced Corrosion (MIC) applies to a corrosive

situation which is caused aggravated the biological organisms. A classic case of MIC is the growth of fungus at the waterfuel interface in aluminum aircraft fuel tanks. The fungus consumes the high octane fuel, and excretes an acid which attacks and pits the aluminum fuel tank and causes leaking. The solution for this problem is to control the fuel quality and prevent water from entering or remaining in the fuel tanks. If fuel quality control is not feasible, then fungicides are sometimes added to the aircraft fuel.[1] As already identified, MIC operates as an individual nodule covering a pit. The development of this process occurs in three phases, which are follows: attachment of microbes. growth of nodule and initial pit. mature pit and nodule.[12]

Fig.(11 ) Shows Multiple Nodules .[14] 11

Dr. Hani Aziz Ameen

Types of Corrosion

One nodule is broken open, showing black corrosion products inside the nodule. Pits are found under most large nodules.[14] The phase recognition of desirable site ( metallurgical feature desirable to bacteria) as shown in Fig.(12 a ). Phase two- colony formation and development of crevice corrosion as shown in Fig.(12 b ) and phase three nodule as formed over nature pit as shown in Fig.(12 c ).

(a)

(b)

(c)

Fig.(12) Microbiological Induced Corrosion

12-

Pitting Corrosion of Aluminum Alloys

Pitting corrosion (as shown in Fig(13)) is defined as localized

accelerated dissolution of metals that occurs as a result of a breakdown of the protective passive film on the metal/ alloy surface. In an aggressive environment, typically containing halide ions, pits initiate and grow in an autocatalytic manner, where the local environment within the pits becomes more aggressive because of decrease in pH and increase in chloride concentration, which further accelerates. The pit growth usually takes a variety of shapes [15].

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Dr. Hani Aziz Ameen

Types of Corrosion

Fig.(13) Mechanism of Pitting Corrosion of Aluminum [3]

Pit shapes can be simply divided into isotropic and anisotropic groups. Shapes are isotropic, while those in Fig.(14), are isotropic and are called microstructural orientated pitting. The variation in pit shape could mainly depend on the microstructure of metals or alloys such as alloy composition and aspect ratio of grains. Even though there are some differences in pitting corrosion between stainless steels and Al alloys, e.g., hydrogen bubbles form at the active pit surface in Al alloys; both materials basically share a similar mechanism. In general, pitting corrosion involves three stages: 1) pitting initiation 2) metastable pitting 3) pitting growth.

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Dr. Hani Aziz Ameen

Types of Corrosion

Fig.(14) Pit Shapes [15]

12.1

Pit Initiation
As mentioned above, aggressive anions such as chloride are believed to

cause passive film breakdown. However, the exact mechanism of the passive film breakdown is still unclear. A number of models have been proposed to explain passive film breakdown or pit initiation [15]. Three main models are as shown in Fig.(15): 1) adsorption mechanism 2) penetration mechanism and 3) film breaking mechanism. These models have been reviewed in depth in the literature [16]. The adsorption theory emphasizes the importance of adsorption of aggressive anions like chloride ions. A competitive adsorption of chloride ions and oxygen finally may lead to film thinning. The penetration model emphasizes the importance of anion penetration and ion migration through the passive film. The point defect model addresses the transport of cationic vacancies to the metal/oxide 14

Dr. Hani Aziz Ameen Types of Corrosion interface controlling pit initiation instead of anion penetration. The point defect model has been fitted to experimental data such as pitting potential and induction time for pitting corrosion of Al and Al alloys in halides. However this model cannot explain metastable pitting, and some assumptions such as the electrode potential and vacancy migration in extremely high electric field (on the order of 106 to 107 V/cm) are suspicious. The film-breaking model involves the breakdown and repair of the passive film simultaneously mechanical stress due to electrostriction and

surface tension cause the passive breakdown which is repaired rapidly . According to this film-breaking model, pits initiate as a result of the passive film breakdown only when stable pits grow afterward.

Fig. (15) Three Main Models [15]

12.2

Metastable Pitting[16]
Metastable pits are these that survive for a very short lifetime in the

order of seconds or less. They can initiate and grow to the micron size at potentials far below the pitting potential and also above the pitting potential 15

Dr. Hani Aziz Ameen Types of Corrosion during the induction time prior to the onset of stable pitting. Fig. (16) shows typical metastable pit current transients on stainless steels, in chloride solution under an applied anodic potential. The current increases corresponding to the growth of metastable pit followed by a sharp current decrease due to repassivation process. Since metastable pits experience initiation, growth, and repassivation, a better metastable pitting. Understanding of these three stages for the metastable pit can be gained through study of metastable pitting phenomenon was first observed in stainless steel in the early 1970s. Frankel and coworkers used the term of metastable pitting for the first time. Over the past 30 years, metastable pitting has been systematically investigated by analyzing pit current density for individual metastable pits and stochastic approaches to groups of metastable pits. These detailed studies show that the early development of metastable pits appears to be identical to that of metastable pits, and the probability of metastable pitting is directly correlated to the intensity of metastable pitting events. Metastable pits repassivate probably when the porous cover ruptures and the pit electrolyte is diluted. In contrast to a huge amount of studies on corrosion of stainless steels, literature on corrosion of Al or Al alloys is limited. Pride et al. studied metastable pitting on pure Al. They found that the number of metastable pits and the current. Spikes increase with increasing applied potential below pitting potential and the chloride concentration. A critical transition from metastable pitting to stable pitting in Al has been found in their study.

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Dr. Hani Aziz Ameen

Types of Corrosion

Fig.(16) Metastable Pit Transients Observed [17]

12.3

Pit Growth[16] Above the pitting potential, stable pits grow at a rate depending on

alloy composition, local pit environment and pit bottom potential. Due to the autocatalytic nature of pitting corrosion, the local pit environment and bottom potential is severe enough to prevent repassivation. Pit growth can be controlled by each or combinations of three factors mainly chargetransfer, ohmic and mass transport. For a hemispherical pit, different rate controlling factors would lead to specific relationships between current I, current density i, pit radius or depth r, time t, and potential E. . Under charge transfer control, Tafels law describes ( i exp E ) . . Under ohmic control, it can be derived I r and i I / r 2 I / r . From Faradays law, 17

Dr. Hani Aziz Ameen Types of Corrosion i dr / dt , leading to r t 1 / 2 and thus I t 1 / 2 and i t 1 / 2 . Ohms law determines i E . . Under mass transport control, according to Ficks laws, i I / r , thus
i t
1 / 2

. i is E independent.

The similar i-t relationship for ohmic control and mass transport control makes it difficult to distinguish For a 3D sample, the non-steady state nature of pit deepening and the problem with accurate measurements of pit current density complicate the clear identification of the i-E relationship. In a conventional measurement of i-E relationship, current may come from several pits with unknown active surface areas and presumably is evenly distributed on the pits. However, the assumption of even distribution is not possible since different pits initiated at different potentials grow at different rates. Artificial pit electrodes, formed by imbedding a wire in epoxy have been extensively used to study iron and stainless steel behavior. The artificial pit electrode geometry forms a single pit in which the whole electrode area is active, generates a natural pit environment, and provides an ideal one-dimensional transport condition. For Al and Al-alloys, similar to artificial pit electrodes, artificial crevice electrodes have been used since large crevice area facilitates the escape of H2 bubbles. The results indicate that pits can grow either in the active state without salt film precipitation or in a salt-film-covered state. The active state is dominated by ohmic control while a salt-film-covered state is dominated by mass transport control. Other single pit techniques include the exposure of small area, laser irradiation of a small spot, and implantation of an activating species at a small spot. These studies suggested different viewpoints of either ohmic control or mass transport control. Besides the electrochemical methods, non-electrochemical techniques have been also used. Hunkeler and Bohni measured the time for pit to penetrate Al foils of varying thickness to determine the pit growth rate. They found that at fixed applied potential, pit 18

Dr. Hani Aziz Ameen Types of Corrosion depth and current density i were time dependent: d t 1 / 2 and i t 1 / 2 . Pit growth on Al was ohmic controlled since the growth rate was correlated to the conductivity of the electrolyte. Detailed studies of 2D pit in Al and other types of thin films by Frankel and coworkers found that the high current density increased linearly with potential and reached a limiting value at higher potentials (Fig.(17)). Therefore, the pit growth at the beginning is controlled by ohmic control and after some time controlled by the masstransport.[16]

Fig.(17) Anodic And Net Current Densities Change As A Function Of Potential For 100 Nm Al Film In 0.1M Nacl Solution [16]

12.4

Pitting Stability Local pit environment and chemistry are believed to be very important

for pit growth and repassivation. Among the various species present within pits such as metal cations, metal hydroxide, Cl- and H+, acidification within pits as a result of hydrolysis is generally recognized to be a critical factor. Galvele calculated the acidification in 1D pit, based on metal dissolution, hydrolysis, and mass transport. He found that a critical value of the product x.i (x is pit depth and i is current density), was the critical acidification within pits to sustain pit growth Fig.(18). This critical product can be used to explain 19

Dr. Hani Aziz Ameen Types of Corrosion the pitting potential and repassivation potential, and determine the current density required to initiate pitting and to sustain pit growth at a defect of a given size in passive film such as crack. Although, for some metals, other factors like chloride concentration are more important than acidification. Thus the critical value x.i (sometimes Ipit/rpit used) can be used as a criterion for pitting stability. Williams et al. correlated pit stabilization with metastable pitting. They suggested that Ipit/rpit for metastable pits formed on steels must exceed 4 10-2 A/cm2 for stable growth. At a higher current density during pit growth, a salt film may form on the pit surface due to saturation of ionic species. For Al pits in chloride solution, this salt film was considered to be aluminum chloride AlCl3 or aluminum oxy-chlorides such as Al (OH) 2Cl and Al (OH) Cl2 according to measured pH and possible hydrolysis processes. Upon salt film precipitation, as described above, the pit growth is under mass transport control. A salt film can enhance pitting stability by acting as buffer of ionic species that can dissolve into pit to sustain a severe condition in the pit environment such as high acid concentration. The potential distribution in pits is considered to be another important factor to stabilize pit growth. When the IR drop is less than a critical value, pit growth stops due to repassivation, if the alloy undergoes active/passive transition in the pit environment . In fact, all of the factors above might be generalized to pit growth current density, since a pit must maintain a minimum current density for stabilized growth However, the critical pit current density and the effect of environment factors need to be investigated further.[16]

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Dr. Hani Aziz Ameen

Types of Corrosion

Fig.(18) Concentration of Al3+ , Al(OH)2+ , and H+ As A Function of The Product of The Depth X and The Current Density In A Unidirectional Pit[16] References [1] Corrosion of Aluminum and its Alloys: form of corrosion , key to Metals Nonferrous ,2008. [2] FONTANA M. and GREENE N D. CORROSION ENGINEERING 2nd MC Graw- Hill,1978. [3] Michel Jacques Corrosion of aluminum Member of the commission of Experts with in International Chamber of commerce .Paris. France .2004 [4] Rollason E.C. Metallurgy for Engineering Edward Arnold Publishers, 4th Edition, 1973. [5] Williams DE, stewartds and Balk will P, corrosion, science, 36, p.1213,1994. [6] Pierre R. ROBERGE, P Crevice corrosion Model six of 28lcorrosion: Impact, Principles, and Practice-PHD, P Eng. 1999-2009 [7] Dr. Zuhair M. GasemME 472-062- Corrosion Engineering Uniformed 21

Dr. Hani Aziz Ameen Types of Corrosion and Galvanic Corrosion ME DEPT KFUPM Dhahran, Saudi Arabia , 2008. [8] T.D.Burleigh, E. Ludwiczak and R.A.PetriIntergranular corrosion Of an Aluminum Magnesium-Silicon copper alloy corrosion science vol51,NO. 1 ,January 1995. [9] Randy K. K and Kent and Roy Baggerly Corrosion Related Failures Intergranular corrosion AE Engineers, Inc.p777.,1998. [10] Different Types of Corrosion Recognition, Mechanisms &Prevention Intergranular Corrosion: Exfoliation Corrosion ,2009. [11] http: II Kogas - Corrosion needs Microscopic study.,2003 [12] Abhay k. Tha; G Naga shiresha, k stress corrosion cracking in aluminum alloy. AFNOR 7020 T6 water tank adaptor for liwuid propulsion system organization trivandrum G95 .022 India may 2007. [13] Corrosion AT SEA A&M ENVIRONMENTAL TECHNOTESBOEING Volume 5 Number 1,February, 2000. [14] Roland J. Huggins, P.E. Article Microbiology Influenced corrosion What its and how works,2000. [15] Chemical & Process TechnologyPitting corrosion Mechanism & Prevention, August 2007. [16] K. Srinivasa Rao Pitting corrosion of heat treatable Aluminum alloys and weld: Trans. India in St. Met, vol 57. No. 6, pp (503-610)., December 2004. [17] Ch .9 pitting corrosion http:// Corrosion .Kaist .ac.Kr.,2001

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