Trans. Indian Inst. Met. Vol.57, No. 6, December 2004, pp.

593-610

REVIEW

PITTING CORROSION OF HEAT-TREATABLE ALUMINIUM ALLOYS AND WELDS: A REVEIW

K.Srinivasa Rao and K.Prasad Rao
Department of Metallurgical and Materials Engineering, IIT-Madras,Chennai-600036 E-mail:arunaraok@yahoo.com (Received 12 April 2004 ; in revised form 18 October 2004)

ABSTRACT
This review attempts to present the current understanding of the mechanism of pitting corrosion of heat treatable aluminium alloys and their welds. The role of alloying elements and intermetallic phases on the corrosion behavior of these alloys has been discussed. Pitting mechanism of aluminium- copper alloys is specifically discussed. Finally effect of welding on the pitting corrosion of these alloys is also presented.

1. INTRODUCTION
Heat treatable aluminum alloys are widely used in aircraft structural applications and are susceptible to localized corrosion in chloride environments, such as pitting, crevice corrosion, intergranular corrosion, exfoliation corrosion and stress corrosion cracking. This article reviews the some aspects of passivity and pitting of Al alloys. Specifically, metastable and stable pits, pitting mechanism, effect of intermetallics and effect of welding parameters on pitting corrosion of age hardenable Al-alloys.

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: pitting initiation, metastable pitting, and pitting growth. 2.1 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 initiation3-9. Three main models are 1) adsorption mechanism 2) penetration mechanism and 3) film breaking mechanism (Fig. 2). These models have been reviewed in depth in the literature10-11. 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. MacDonald and coworkers5-7 have developed a point

2. PITTING ALLOYS

CORROSION

OF

Al

Pitting corrosion 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 surface1. 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. The pit growth usually takes a variety of shapes2 (Fig. 1). Pit shapes can be simply divided into isotropic and anisotropic groups. Shapes in Fig. 1 a-e are isotropic, while those in Fig. 1f are anisotropic and are called microstructural orientated

TRANS. INDIAN INST. MET., VOL. 57, NO. 6, DECEMBER 2004

Fig. 1

: Variations in shape of Pits

defect model as a modified or related penetration model. The point defect model addresses the transport of cationic vacancies to the metal/oxide 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 stresses due to electrostriction and surface tension cause the passive film 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. In summary, these models address important aspects of pit initiation such as aggressive ion adsorption,

ion penetration and migration, and stress-induced breakdown of passive film. Although these models obtained some experimental support, no comprehensive or universal model can account for pitting corrosion in all metal/environment systems. This indicates that pit initiation is rather complicated and a combination of these models could explain pitting for a certain metal/environment system. 2.2 Metastable Pitting Metastable pits are pits 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 during the induction time prior to the onset of stable pitting. Figure 3 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

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Fig. 2

: Schematic of pit initiation models

repassivation process. Since metastable pits experience initiation, growth, and repassivation, a better understanding of these three stages for the stable pit can be gained through study of metastable pitting. Metastable pitting phenomenon was first observed in stainless steel in the early 1970s12. Frankel and coworkers used the term of metastable pitting for the first time13. 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 stable pits appears to be identical to that of metastable pits, and the probability of stable 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. Pride14 et al. studied metastable pitting on pure Al. They found that the number of metastable pits and the current

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Fig. 3

: Metastable pit transients observed on 302 stainless steel polarized at 420mV SCE in 0.1M NaCl solution.

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. 2.3 Pit Growth 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 15-18. 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/r2 1/r. From Faradays law, 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 1/r, thus i t-1/2. i is E independent.

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 19. 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 20,21. 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 22-25. 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 26 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 depth d and current density i were time dependent: d t1/2 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 13 found that the high current density increased linearly with potential and reached a limiting value at higher potentials (Fig. 4). Therefore, the pit growth at the beginning is controlled by ohmic control and after some time controlled by the mass transport 27-29. 2.4 Pitting Stability Local pit environment and chemistry are believed to be very important for pit growth and repassivation.

The similar i-t relationship for ohmic control and mass transport control makes it difficult to distinguish. For a 3D bulk sample, the non-steady state nature of

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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, they will roughly scale with acidification. Thus the critical value x.i (sometimes Ipit/rpit used) can be used as criteria for pitting stability. Williams et al.32 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 (AlCl 3 ) or aluminum oxy-chlorides such as Al(OH)2Cl and Al(OH)Cl2 according to measured pH and possible hydrolysis processes 33-36 . 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 an active/passive transition in the pit environment 37-39. 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 effect of environment factors need to be investigated further. 2.5 Criteria for Evaluation of Pitting Corrosion in Al Alloys Many electrochemical studies of pitting corrosion have found that there exist characteristic potentials. Using cyclic polarization techniques, two characteristic potentials can be determined, which correspond to pit initiation and repassivation (Fig. 6). One is pitting potential (EP), sometimes called critical potential or breakdown potential (EB), above which stable pits initiate and grow rapidly. The other is repassivation potential (ER), sometimes called protection potential,

Fig. 4

: Anodic and net current densities change as a function of potential for 100 nm Al film in 0.1M NaCl solution.

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 30, 31 calculated the acidification in 1D pits, 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. 5). This critical product can be used to explain

Fig. 5

: 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.

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(a)

Fig. 6

: Schematic cyclic polarization showing EP and ER

below which growing pits repassivate and stop growing. It should be noted that the values of these two characteristic potentials can depend somewhat upon the methods used and potential scan rate. Moreover, since pitting corrosion is considered to be stochastic, stochastic approaches have been developed to handle the scatter of pitting potential 40 . Both EP and ER have been extensively used to evaluate the susceptibility to pitting corrosion of various materials in a given environment. It is generally recognized that materials exhibiting higher EP and ER are more resistant to pitting corrosion. Electrochemical impedance spectroscopy (EIS) uses a range of low magnitude polarizing voltages, like linear polarization. However, EIS voltages cycle from peak anodic to cathodic magnitudes using a spectrum of alternating current (AC) voltage frequencies, instead of a range of single magnitude and polarity direct current (DC) voltages. Data recorded in the form of Bode and Nyquist plots can provide electrode capacitance and charge-transfer kinetics and as the method does not involve a potential scan, measurements can be made in low conductivity solutions with high accuracy. Figure 7 shows a simple electrochemical equivalent circuit and the corresponding data plots41. The magnitude of the high frequency impedance where the impedance magnitude is independent of frequency corresponds to Rs. The difference in magnitude between the low frequency and the high frequency independent regions corresponds to Rp.These resistances are identical to those on the Nyquist format plot. Low frequency

(b)

(c)

(d) Fig. 7 : (a) Equivalent electrical circuit model for simple corroding electrode, (b), (c) its Bodes and (d) Nyquist plots

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impedance value (Ohm.cm2), where the phase angle approaches zero is accurate polarization resistance of the alloy in a given environment. Recently EIS technique has been recognized as the accurate method of determining the corrosion resistance of aluminium alloys in solutions containing aggressive halide ions. Determining polarization resistance of the alloys immersed in sodium chloride solution as function of time and its variation may be criteria for the measuring pitting corrosion resistance of aluminium alloys. Recently Q.Meng et..al 42 studied the corrosion behaviour of 7xxx alloys with varying Copper content using immersion tests in aerated chloride solutions (Fig.8) and concluded that the polarization resistance decreases as the Cu content increases, which has been attributed to the Cu enrichment on the surface.

Coarse intermetallic particles play a crucial role in the corrosion behavior of Al alloys. The micro galvanic coupling between the matrix and the intermetallic particles is generally believed to result in pitting corrosion and further develop intergranular cracking (IGC) into the deep structure of Al alloys. In this section, the role of alloying elements in solid solution and intermetallic particles in pitting corrosion of Al alloys will be reviewed. 3.1 Alloying Elements Muller and Galvele43 first studied the role of alloying elements in pitting corrosion of Al-Zn, Al-Mg, and Al-Cu binary alloys in dearated 1 M NaCl. Zn, Mg, and Cu as alloying elements have different effects on the pitting potential of Al alloys (Fig. 9). Pitting potential decreased greatly with increasing Zn content up to 3wt% and remained the same with further increase in Zn content. There was no influence of Mg on pitting potential. Pitting potential increased

Fig. 8

: Polarization resistance determined by EIS tests as a function of immersion time for AA7xxx-T6 in aerated 0.5 M NaCl.

3. ROLE OF ALLOYING ADDITIONS AND INTERMETALLICS IN LOCALIZED CORROSION OF Al ALLOYS

Addition of alloying elements, especially Cu, can significantly increase the mechanical strength of Al alloys such as Al-Cu-Mg alloys (2xxx series) and Al-Zn-Mg-Cu alloys (7xxx series) by precipitation hardening. Due to the limited solubility of many elements in aluminum, alloying elements are often distributed not only in the Al solid solution, but also in fine precipitates and coarse intermetallic particles.

Fig. 9

: Variations of pitting potential as a function of alloying element content of a) Al-Cu b) Al-Zn and c) Al-Mg binary alloys.

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dramatically with increasing Cu content up to 5wt%. Furthermore, they studied the corrosion morphology of these three binary alloys. It was found that tunnellike pits formed on Al-3Zn, and crystallographically shaped pits on Al-3Mg and Al-3Cu. Sato4 studied metastable pitting on Al-Zn alloys. They found that the rate of pit nucleation was potential dependent regardless of the alloying addition. It was suggested that Zn addition influenced the pit growth instead of the pit nucleation events. Since the mid 1980s, many studies have been conducted on surface chemistry and corrosion properties of stainless Al alloys containing W, Ta, Mo, Nb, and Cr 44-49. These studies provide some clues to explain the role of alloying elements on pitting potential. Due to the low solubility of the above alloying elements in aluminum, thin films of supersatuarated Al binary alloys have been prepared by non-equilibrium methods such as sputter deposition. The electrochemical studies revealed that the pitting potential of aluminum can be dramatically increased by the addition of these elements. One of explanations is that enrichment in the passive film plays an important role in improving pitting resistance. Moshier and coworkers44-45 using X-ray Photoelectron Spectroscopy (XPS) conducted surface analysis of the passive films formed on Al-Mo, Al-Ta, Al-Cr, and Al-W alloys. They found significant incorporation of the alloying elements into the passive film. It was suggested that a more protective passive film enriched with the solute atoms was responsible for improved pitting resistance by impeding the ingress of chloride ion through the passive film. Smialowska 50 suggested that the solute elements in the active pit surface play the critical role instead of solute in the passive film. She proposed that the low solubility of the solute oxide in the acidic pit environment is responsible for improved pitting resistance. Another explanation has been proposed by Frankel and coworkers27-29 based on their measurement of thin film pit growth kinetics for Al-Nb, Al-Mo, and Al-Cr thin films by sputter deposition. They found that stable pits initiated at potentials only about 30 mV higher than they repassivated (Fig. 10). It was suggested that the addition of noble alloying elements increased the pitting and repassivation potential by ennobling the dissolution kinetics of pit growth rather than the passive film effect. However, the exact mechanism by which alloying elements alter the dissolution

Fig. 10 : Pitting potentials for freshly deposited samples, Ep and aged samples Epa along with repassivation potentials ER, for pure Al and AlNb alloys.

kinetics is still unclear. Regardless, this dissolution kinetics viewpoint provides a new insight to understand the role of alloying elements such as Zn, Mg, and Cu in Al alloys in pitting corrosion. In the light of the dissolution kinetics viewpoint, Ramgopal and Frankel21 recently studied the dissolution kinetics of Al-Zn, Al-Mg and Al-Cu binary alloys using the artificial crevice electrode technique. It was found that Zn, Mg, and Cu addition had different effects on repassivation potential and the dissolution kinetics. The addition of Cu increased the repassivation potential and lowered the dissolution kinetics. The addition of Zn decreased the repassivation potential and enhanced the dissolution kinetics. The addition of Mg had little or no effect on the repassivation potential by changing the dissolution kinetics. They suggested that the role of alloying elements was to mainly change the surface overpotential and thus shifted the repassivation potentials. 3.2 Intermetallic Particles Intermetallic particles (IMCs) can be grouped into coarse intermetallic particles and fine precipitates. In Al alloys, coarse intermetallic particles form during the solidification process, while fine precipitates including hardening precipitates in the matrix and grain boundary precipitates form during the aging process. The type and composition of intermetallics varies with the Al alloy composition and heat treatment 51. The primary coarse intermetallics found in Al-Cu-Mg alloy such as AA2024-T3 are Al2Cu

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( ),Al2CuMg (S) and Al20Cu2(Fe Mn)3 52-53. The coarse intermetallics Al3Fe, Al7Cu2Fe, Al2CuMg, and Mg2Si are found in Al-Zn-Mg-Cu alloys such as AA7075-T6. The fine precipitates for AA2024-T3 and AA7075-T6 are Al2CuMg and Mg (Zn Cu Al)2, respectively. As mentioned earlier, intermetallic particles play a crucial role in localized corrosion of Al alloys. The coarse intermetallic particles mentioned above can be further divided into two groups: active and noble particles relative to the Al matrix. Al2Cu, Al3Fe, Al7Cu2Fe, and Al20Cu2 (Fe Mn)3 are found to be noble to the matrix, while Al2CuMg and Mg2Si are active to the matrix. Buchheit 54 compiled the corrosion potentials of various intermetallic phases in Al alloys, showing that the intermetallics exhibit different electrochemical properties from the matrix. Pits are readily found at the periphery of noble particles in Al alloys during exposure to chloride solution. It is generally accepted that noble Fe- or Cu-containing intermetallic particles act as cathodes and support oxygen reduction. As a result, a high pH local environment is established at the noble particles, which causes grooving of the surrounding Al matrix by alkaline dissolution. The alkaline attack must then somehow switch to acid attack to result in a stable pit, which requires an acid environment. Electrochemical studies have been conducted on Al3Fe and Al2Cu 55-57. Nisancioglu found that near the open circuit potential in NaOH solution, Al3Fe underwent a preferential dissolution of Al, which resulted in an Fe rich surface55. It was suggested that Fe enrichment on the Al3Fe surface is detrimental to cathodic behavior due to the formation of a protective Fe oxide. The presence of Mn and Si in Al3Fe can reduce the effect of Fe on both anodic and cathodic rates. Mazurkiewicz and Piotrowski57 found that Al2Cu underwent dissolution to form Al and Cu ions at the open circuit potential and under anodic polarization in sulfate solutions. Cu ion release was also found in Rotating Ring-Disk Electrode (RRDE) experiments on Al2Cu and Al7Cu2Fe at the OCP and under anodic and cathodic polarization in chloride solution . The corrosion potentials for Mg2Si ( ) and Al2CuMg (S) particles in chloride solution are -1.59 and -0.92 V SCE, respectively. Both Mg-containing phases are active to the matrix and act as anode. They are susceptible to active dissolution or Mg dealloying

when exposed in acidic solution or chloride solution. Mg 2Si phase in AA6000 dealloyed in 0.1 M phosphoric acid and MgO was found on the Mg2Si particles. Buchheit and coworkers58,60-62 studied the electrochemical behavior of S (Al2CuMg) phase in the form of both synthesized bulk and real phases in AA2024-T3. They found that S phase supported rapid anodic and cathodic reaction kinetics and selective dissolution of Mg and Al readily occurred under anodic and cathodic polarization. Dealloying of active S phase left Cu-rich remnants, which was cathodic to the matrix and therefore caused grooving by alkaline dissolution and then pitting at the dealloyed S phase. They also proposed that decomposition of Cu-rich remnants of S phase resulted in Cu release and redistribution, which further accelerated corrosion of the Al alloys. This hypothesis has been supported by RRDE experiments on S particles. The details about Cu enrichment and redistribution will be reviewed below. In summary, alloying addition and various intermetallic particles play an important role in the corrosion properties of Al alloys. 3.3 Cu Enrichment and Redistribution The critical role of intermetallic particles in localized corrosion of Al alloys was described previously. Many studies revealed that Cu-containing intermetallic particles govern the corrosion of high strength Al alloys due to the noble nature of the Cu rich particles. In chloride environment, Cu-rich particles, particularly Al2CuMg (S) particles, often lead to Cu enrichment and redistribution, which in turn is detrimental to corrosion resistance. Buchheit and coworkers58,60-62 attributed Cu enrichment in AA2024 to dealloying of S-phase, which accounts to about 60% of total intermetallic particles (Fig. 11). S phase is susceptible to dealloying in acidic solution or chloride solution. Selective dissolution of Mg and Al leaves behind Cu rich sponge remnants. Buchheit et..al62 further pointed out that Cu redistribution was attributed to the formation and re deposition of Cu ions although the corrosion potential of AA2024 is well below the reversible potential for Cu/Cu2+. There are two possible explanations for this seemingly thermodynamic contradiction. They proposed that the Cu rich sponge remnants undergo physical coarsening, which results in non faradaical liberation of mechanically and electrically isolated metallic Cu clusters.

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Fig.11

: (a) Optical picture and (b) Schematic representing Cu enrichment redistribution during localized corrosion in AA2024-T3

Metallic Cu clusters suspended in the solution or isolated in the corrosion product can achieve a corrosion potential that is not controlled by the alloy potential. In an aerated solution, metallic Cu is oxidized into Cu ions. Dissolved Cu2+ ions can drift around by solution convection and redeposit on the alloy surface, reducing back to metallic Cu. This then leads to the localized corrosion in other places. Sieradzki and coworkers proposed a different viewpoint that Cu ions are formed directly from Cu rich sponge remnants on the alloy surface. In this
63-64

view point, the curvature effect is thought to be responsible for the formation of Cu ions rather than the liberation of metallic Cu clusters. The curvature of Cu rich clusters on the surface shifts the reduction potential for Cu in the anodic direction (equation 1), dramatically when the radius r is very small.

E Cu = E Cu

2 Cu Cu nFr

(1)

where E Cu is the potential of the Cu rich remnant, E Cu is the reversible potential for Cu, n is

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2 equiv/mol, F is faradays constant (96487 C/equiv), Cu is the molar volume of Cu, r is the radius of the surface curvature and Cu is the surface energy of Cu. The formation of Cu ion is possible at the alloy corrosion potential when the radius is about 40 nm. Besides the Cu enrichment and redistribution from the S phase, other arguments have been made to explain Cu surface enrichment, which do not require any Cu oxidation or long-range redistribution of Cu from the S phase. An argument is that Cu on the surface around the intermetallics comes from the surrounding matrix 65.According to this viewpoint, the active intermetallic particles such as the S phase rapidly dealloy leaving behind the porous Cu rich remnants, which act as local cathodic sites. The oxygen reduction reaction occurring at these cathodic sites increases local pH to alkaline. In local alkaline solution, adjacent Al matrix around intermetallics dissolves also leaving behind Cu, which is originally in the Al matrix. Cu enrichment from both S phase dealloying and matrix dealloying is possible. Cu enrichment and redistribution from the S phase is dominant when AA2024-T3 is immersed in chloride solution for a short time, whereas, matrix dealloying contributes to Cu enrichment and redistribution more than S phase delloying after long time immersion.

Table 1 Solid solution or constituent Ecorr, the corrosion potential Volts rel. N.H.E., 25C +007 noble -040 -052 active

Cu CuAl2 Al

Al + 4% Cu in solid solution -036 Al + 2% Cu in solid solution -042

corrosion potential (see Table 1). The difference of 100mV in the Ecorr values for pure aluminium and aluminium with 2% copper in solid solution is quite large and can lead to markedly different corrosion rates across the different phases in a sheet of metal. The copper corrosion products were formed by the oxidation of the CuAl2 units in the metal structure. A very com-mon mineral formed during the corrosion of copper in seawater (pH 82) is cuprous oxide (Cu2O). Under the same conditions an aluminium oxide (Al203) will form as aluminium corrodes. Because of the more reactive nature of aluminium compared with copper, Cu20 or any other copper mineral can be converted back to the metal by reaction with aluminium metal, 2A1 + 3Cu20 A1203 + 6Cu (2) The formal cell potential for the above reaction is +198 volts and so the process is spontaneous. Examination of the Pourbaix diagram (Fig. 12) (Eh vs pH) for copper in seawater 67 and for aluminium 68 shows that none of the copper corrosion products can co-exist in contact with aluminium metal under equilib-rium conditions. In the light of this it is not surprising to find that copper deposits on parts of the aluminium surface. In the pitting of aluminium (Fig. 13) the deposited copper acts as a cathodic site for the facile reduction of oxygen 69, viz. 02 + 2H20 + 4e 40H (3)

4. PITTING MECHANISM IN Al-Cu ALLOYS

Although the addition of copper increases the strength of aluminium it dramatically decreases the corrosion resistance of the metal to seawater. Copper has a limited solubility in aluminium (2wt%) and unless the liquid metal is rapidly cooled, copper will not be uniformly distributed throughout the grains of the aluminium phase 66. If precipitation hardening (increase in hardness of the metal due to the precipitation of the CuAl2 inter-metallic phase) occurs, the areas around the grain boundaries become depleted in copper and as such become more anodic (more reactive) than the rest of the grain. Under these conditions the metal is subject to inter-granular corrosion. In the absence of complicating factors the more reactive metal or Corrosion potentials for a solution containing 53g 1 1 NaCl, 3g 1-1 H202 from65 metal phase will have a more negative

Noble impurities such as Al3Fe act in a similar fashion. Chloride ions are known to be absorbed

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There is an equilibrium between the formation of aluminium oxide and AlCl3, at the interfacial region (the area between the metal and the corrosive medium) viz. A12O3 + 6H+ + 6Cl2AlCl3 aq + 3H2O (7)

When aluminium chloride is formed a pit develops and when alumina (Al2O3) forms the pit will passivate. The chloride ions directly affect the corrosion potential of aluminium in fresh water. The higher the chloride ion concentration the more negative is the corrosion potential and the faster the metal will corrode (in the absence of complicating factors). Chloride ions accelerate the corrosion process but whether this is due to oxide film breakdown or assisting the anodic reaction, is not known. To be effective in arresting further corrosion the treatment process must remove the re-deposited copper from the remaining metal surface and also remove chloride ions.
Fig. 12 : Potential pH diagram for the system Cu NH3 Cl H2O Al. The diagram is based on data from [68] and [74]. Region 1 is the stability domain for Cu(NH3)12+ region 2 for Cu(NH3)22+ and region 3 for Cu(NH3)32+. Solution conditions are NH3 = NH4 = 025M, Cl = 2 X 10-3M, Al = 10-6M, CU = 1 X 10 4M.

5. CORROSION OF WELDS
Welding is an important method of fabrication and leads to physical, chemical and metallurgical changes in aluminium alloys. One of the reasons for the chemical changes in the welds is due to the different chemical compositions of the filler materials used. Weld thermal cycle also causes microstructural changes in the weld metal and heat affected zone (HAZ). These alloys after welding will be subjected to either postweld natural aging (T-4) or post weld artificial aging (T-6). AA6061 and AA2014 alloys are subjected to single step aging while 7020 alloys is subjected to two step aging. Though artificial aging results in higher strength values compared to natural aging, some times natural aging is preferred from the viewpoint of toughness. Though literature on the corrosion behaviour of aluminium alloys is available, the same cannot be said of their welded counterparts presumably in view of the chemical and microstructural changes caused by welding. The literature survey also indicated that there were no detailed and comparative studies available on corrosion behavior of welds of heat treatable aluminium alloys with respect to changes in welding and heat treatment conditions.

onto aluminium 70 and as little as 15ppm chloride can initiate pit growth due to breakdown of the protective oxide film 71. The anodic reaction occurs at the bottom of the pit Al Al3+ + 3e (4)

and the aluminium ions migrate towards the inter-facial region where hydrolysis occurs, Al3+ + 3H20 Al(OH)3 + 3H+ (5)

which makes the pit acidic. Chloride ions migrate into the pit to form aluminium chloride (A1Cl3) which dissolves in the solution. Because of the low pH the aluminium may also corrode with the evolution of hydrogen . 2A1 + 6H+ 3H2 + 2A13+ (6) There is a critical bulk chloride concentration needed to keep the pit propagating (16M) which is higher than normal seawater (057M)

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When localized corrosion does occur in aluminum welds, it may take the form of preferential attack of the weld bead, pitting, intergranular attack or exfoliation may occur in a HAZ a short distance from weld bead. Welds in Al-Mg-Si alloys (AA6061) generally have a good resistance to atmospheric corrosion, but in specifically corrosive environments like seawater localized corrosion may occur. Welds in Al-Cu alloys (AA2014, AA2219, AA2026), AlZn-Mg-Cu alloys (AA7075) and Al-Zn-Mg alloys (7039) have less corrosion resistance, due to metallurgical changes in the HAZ. Reheat treatment of the welded part might restore the original corrosion resistance, but this is rarely possible. Some of the heat treatable alloys particularly those containing substantial amounts of copper and zinc, may have their resistance to corrosion lowered by the heat of welding. These alloys exhibit grain boundary precipitation in the HAZ and of this zone is normally anodic to the remainder of the weldment. In a corrosive environment selective corrosion on the grain boundaries may take place and in the presence of stress this corrosion can proceed more rapidly. Post weld heat treatment provides a more homogeneous microstructure and improves the corrosion resistance of these alloys. Welds in Al-Zn-Mg alloy were seen to be attacked preferentially in an area adjacent to the weld bead when exposed to a corrosive environment in the as welded condition. Post weld aging for a sufficient at a high enough temperature eliminated this preferential attack. Insufficient aging resulted in

a knife-edge attack parallel to at some distance from weld. Gas tungsten arc welding (GTAW) and Gas Metal Arc Welding (GMAW) processes are widely used for joining aluminium alloys for various applications like aerospace, defence and automotive industries. The resistance to corrosion of aluminium alloy welds is affected by the alloy being welded and by the filler alloy and the technique used. Galvanic cells that cause corrosion can be created because of the corrosion potential differences among the base metal, the filler metal and the heat-affected regions where microstructural changes have been produced. In the Aluminium-copper alloys, the heat-affected zone (HAZ) becomes cathodic, where as in aluminumzinc alloys, it becomes anodic to the remainder of the weldment The corrosion potentials across the weld zone for a 5xxx, 2xxx and 7xxx series weldment are shown in Fig. 14.These differences in potential can lead to localized corrosion as demonstrated by corrosion of the alloy 7005 shown in Fig. 15. The HAZ in the 5xxx alloy is mildly cathodic, where as the 2xxx alloy exihibits a greater cathodic potential. The 7xxx series HAZ is anodic to the unaffected material and would be of great concern. Selection of proper filler wire is important to avoid cracking during welding and to optimize corrosion resistance. When the solution potential of the filler is same as that of the base metal (4043 for 6061-T6 alloy), optimum corrosion resistance is obtained. In some cases,

Fig. 13 : Schematic diagram showing pitting corrosion in aluminium

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Fig. 14 : Effect of the heat of welding on microstructure, hardness and corrosion potential of welds of three aluminium alloys. (a) Alloy 5456-H3 with 5356 filler (b) Alloy 2219-T87 base metal with 2319 filler (c) Alloy 7039-T6 base metal with 5183 filler

intermetallic phase formed by the base metal and filler wire determines the final corrosion resistance of the weld, for example magnesium silicide formed during welding 5xxx alloy with 4043 filler can be highly anodic to all other parts of the weldment 72. In general, the welding procedure that has the least

influence on microstructure has the least chance of reducing the corrosion resistance of aluminium weldments. The alloy with the more negative potential in the weldment will attempt to protect the other part. Thus if the weld metal is anodic to the base metal (as 5356 weld in 6061-T6), the small weld can be attacked preferentially to protect the larger surface area of the base metal.

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Fig. 15 : Welded Jiont of alloy 7005 with 5356 filler after a one year exposure to sea water (a) As welded joint showing severe localized corrosion in HAZ (b) Post weld aged effect. Corrosion potentials measured in 53g/l NaCl plus 3g/l H2O2 versus SCE.

Unpublished work of the authors on age-hardneble Al-alloys (AA2014,AA6061,AA7020) deposited with Al-5% Si (AA4043) and Al-5%Mg (AA5356) fillers showed a strong dependence of corrosion behaviour on the chemical and metallurgical changes of Alalloy welds due to welding and post weld heat treatments.

Conventional Continuous current welding (CCW) technique of gas tungsten arc welding (CCTIG) limits the use of base metal property like strength and corrosion resistance73. Due to steep thermal gradients, characteristic of CCW, the segregation of elements and liquid film formation at the grain boundaries leads to hot cracking in the fusion zone and poor corrosion resistance. Combination of pulsed current and magnetic arc oscillation technique using AC TIG process will improve the hot cracking resistance, reduce the grain size and micro segregation, and hence improve corrosion resistance of fusion zone. The intermetallic phases like CuAl2 in AA2219 and Mg2Si in AA 6061 Al-alloys are harmful with respect to weldability and corrosion resistance. These intermetallic particles induce liquation in the partial melted zone(PMZ) of the weldment leading to cracking and galvanic coupling effect of these phases with the surrounding matrix results in poor corrosion resistance. Recently, Huang and Kou75 studied the liquation mechanisms in AA2219, 6061, 2014 and 7075 alloys and suggested that proper care has to be taken in selecting parameters and filler during GMA and GTA welding of Al-alloys to avoid liquation cracking. It is difficult to avoid the PMZ in Alalloys completely, but can be minimized by

Fig. 16 : PMZ areas of GTA Welds of 2219-T6 after Corrosion Testing.

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controlling the welding parameters and selecting proper filler wire suitable for the base metal composition and thermal temper. Recent unpublished work of the authors proved that PMZ is a strong function of prior thermal temper of the Al-alloy like T-4, T-6 and T-87.Similarly it was also found that width of the PMZ is less in pulsed current (PC) GTA welding compared to that of continuous current (CC) GTA welding of Al-alloys. Improvement in corrosion resistance in Pulsed GTA welds of 2219 and 6061 alloys has been attributed to the decrease in segregation and refinement of eutectic network of the weld metal. Corrosion studies on Heat Affected Zones with PMZs in CC and PC GTA welds of AA2219 (T6 and T87) and AA6061 (T4 and T6) indicated the significant influence of prior welding technique and prior thermal temper. HAZs of PC GTA welds of 2219-T87 and 6061-T4 are found be having higher corrosion resistance when compared to that of T-6 temper. Corrosion damage is extensive in the PMZ area of the HAZ due to grain boundary eutectic enrichment and segregation of alloying elements during welding and this is evident from the optical microscopy and scanning electron microscopy studies on GTA welds of 2219-T6 alloy (Fig. 16). Authors76 recently made an attempt to study the effect of prior copper removal treatment on the corrosion resistance of the CC GTA Welds of 2219-T6 and uniform pitting potential has been achieved in all three zones of the weldment. To summarize welding will have a strong influence on the pitting corrosion of heat-treatable Al-alloys, mainly microstructural changes in heat affected zone and partially melted zone might lead to non-uniform pitting potential across the weldment. Proper care has to be taken in the selection of welding technique and the filler wire, depending on the base metal history of the Al-alloy.

number of metastable pits and the current spikes increase with increasing applied potential below pitting potential and the chloride concentration. The potential distribution in pits is considered to be another important factor to stabilize pit growth and a pit must maintain a minimum current density for stabilized growth. 2. Pitting potential ( EP) and Repassivation potential ( ER) can be used to evaluate the susceptibility to pitting corrosion of aluminium alloys and recently Electrochemical Impedance Spectroscopy (EIS) has been recognized as the accurate method of determining the corrosion resistance of aluminium alloys in solutions containing aggressive halide ions. The role of alloying elements was to mainly change the surface over potential and shifting the repassivation potential. Intermetallic particles weaken the passive film and are sites for pit nucleation. Cathodic intermetallics produce a galvanic cell with aluminium matrix and act as cathode for the oxygen reduction.These particles selectively dissolve and remnants from the particles dissolution- metallic Cu, Fe are still more cathodic than the intermetallics. High pH local environment is established at these particles, which causes grooving of the surrounding almatrix by alkaline dissolution. Copper enrichment and re-distribution is the root cause of pitting in aluminium-copper alloys. Chloride ions which accelerate the corrosion process may be attributed to oxide film break down or assisting the anodic reaction. Pitting corrosion resistance of heat-treatable aluminium alloy welds depend strongly on welding technique and the prior thermal temper. Partially melted zone of the Al-alloy welds is severely damaged by corrosion and is attributed to the grain boundary eutectic enrichment and segregation.

3.

4.

5.

6. CONCLUSIONS
1. In general, pitting corrosion involves three stages: pitting initiation, metastable pitting, and pitting growth. Three main models of pit initiation are i) adsorption mechanism ii) penetration mechanism and iii) film breaking mechanism and these models address important aspects of pit initiation such as aggressive ion adsorption, ion penetration and migration, and stress-induced breakdown of passive film respectively. The

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