Materials and Design xxx (2011) xxxxxx

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Materials and Design

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Comparison of corrosion behaviour of friction stir processed and laser melted AA 2219 aluminium alloy
K. Surekha, B.S. Murty , K. Prasad Rao
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600 036, India

a r t i c l e

i n f o

a b s t r a c t
Dissolution of second phase particles (CuAl2) present in AA 2219 aluminium improves the corrosion resistance of the alloy. Two surface treatment techniques, viz., solid state friction stir processing and fusion based laser melting lead to the reduction in CuAl2 content and the effect of these processes on the corrosion behaviour of the alloy is compared in this study. Potentiodynamic polarization and electrochemical impedance spectroscopy tests were carried out to compare corrosion behaviour. The corrosion resistance achieved by friction stir processing is comparable to that obtained by the laser melting technique. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 16 December 2010 Accepted 15 March 2011 Available online xxxx Keywords: A. Nonferrous alloy C. Surface treatments E. Corrosion

1. Introduction Good weldability and high strength-to weight ratio of AA 2219 aluminium alloy makes it an ideal candidate for strategic applications. However, its corrosion resistance is poor owing to the formation of galvanic cells between the CuAl2 intermetallic and the Al matrix. Surface treatments can improve the corrosion resistance of the alloy by homogenization/renement of microstructure, dissolution/redistribution of precipitates. In the present study, the samples of AA 2219 were subjected to fusion based approach, laser melting (LM), and a relatively new solid state approach, friction stir processing (FSP), to improve the corrosion resistance. Surface treatments are generally carried out to tailor the surface properties without affecting the bulk properties to improve strength, toughness, corrosion and wear resistance. In LM, an intense laser beam locally heats the surface and produces a rapidly solidied surface layer to a depth of a few hundred microns and the remainder of the material acts as an effective heat sink and hence the surface material solidies under a relatively high rate of cooling. This alters the microstructure and the distribution of second phase particles and hence affects the surface properties. In FSP, a non-consumable tool rotating at a constant speed is inserted into the plates to be processed and the tool is responsible for heating of work piece and deformation of the material [1]. FSP being a solid state process is free from many solidication defects like cracks, porosity, etc. Li et al. [2] studied the localized corrosion behaviour of LM AA 2024-T351 alloy and found that the pits were uniformly distributed, while in the base metal the pits were more in the rolling
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direction. This difference in corrosion behaviour was attributed to changes in the distribution and composition of the second phase particles present in the alloy. Liu et al. [3] studied the corrosion mechanisms of LM AA 2014 and AA 2024 alloys and noticed an improvement in pitting corrosion resistance of AA 2014 due to the cathodic nature of CuAl2 phase relative to the a-Al matrix and the corrosion resistance of AA 2024 alloy decreased due to the anodic nature of Al2CuMg phase relative to the a-Al solution. Liu et al. [4] found that corrosion behaviour after laser treatment depends on the electrochemical nature of various intermetallics with respect to the solid solution matrix. Watkins et al. [5] reviewed the literature on the corrosion properties of various aluminium alloys after laser surface melting and laser surface alloying and found promising improvement in the critical pitting potential compared to the conventional alloys. Surekha et al. [6,7] studied the effect of FSP parameters namely, rotation speed and number of passes on the corrosion behaviour of AA 2219 alloy and found an improvement in the corrosion resistance that was attributed to the fracture and dissolution of the second phase particles. Jariyaboon et al. [8] reported the effect of welding parameters during friction stir welding (FSW), especially rotation speed and traverse speed, on corrosion behaviour and reported that rotation speed has a signicant inuence on the rate of corrosion. Fonda et al. [9] studied the microstructure, mechanical properties, and corrosion behaviour of friction stir welded AA 5456 and found that the anodic reactivity was highest in the weld nugget, particularly towards the lower advancing side, since nanoscale b precipitates were dispersed throughout the matrix of the susceptible regions. Hatemleh et al. [10] studied the effect of laser and shot peening on stress corrosion cracking susceptibility of friction stir welded AA 7075 aluminium found that surface treatment decreased

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Fig. 1. SEM micrographs of (a) BM, (b) FS1, (c) FS2, (d) LM10 and (e) LM20 samples.

the corrosion rate. Paglia and Buchheit [11] studied the effect of time, temperature and corrosion susceptibility of FSW AA 7050T7451 and found that exposure to temperature above 180 C for more than 25 min. increases the resistance to localized corrosion resistance. Elangovan and Balasubramanian [12] studied the effect

of tool prole and rotation speed on AA 2219 and AA 6061 and found that square tool prole gave sound welds. Parameter optimization (for FSP) in the current work was done based on the work of Elangovan and Balasubramanian [12]. In this study, the corrosion behaviour of FSP and LM AA 2219 is compared.

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2. Experimental procedure The material used in this work is AA 2219T87 alloy with the nominal composition (in wt.%) of Cu-6.1, Mn-0.25, Zr-0.16, V-0.09, Ti-0.05, Fe-0.2 and Si-0.15 and the rest Al. The AA 2219 T87 (T87-solutionized at 535 C, cold worked and articially aged at 190 C for 18 h) plates (250 150 5 mm in size) were friction stir processed, with an indigenously developed machine (3000 rpm, 15 HP and 25 kN) at a constant axial force of 12 kN with a non-consumable threaded tool made up of high-speed tool steel. The samples were processed at a rotation speed of 1600 rpm and a traverse speed of 0.37 mm/s to a depth of 2 mm. Multi passing up to two passes was carried out with 100% overlap. Samples were named as FS1 and FS2 according to the number of passes. Laser melting was carried out on 9 kW CO2 laser with a focal spot size of 18 mm at a power of 4 kW at two different scan rates viz., 10 and 20 mm/s on a plate with the dimensions of 200 30 5 mm. The samples were identied as LM10 and LM20. The surface was coated with a layer of graphite to increase absorption of laser and decrease reectivity. Surface treated samples were examined microscopically by scanning electron microscope (SEM). The samples were etched with Kellers reagent to reveal the grain boundaries. Particle size, grain size and volume fraction analysis were carried out with the help of an optical microscope attached with an image analyzer. Microhardness measurements were carried out using Matsuzawa Vickers micro hardness tester at 25 g load for 30 s. The amount of second phase reduction during FSP and LM was quantied by differential scanning calorimetry (DSC). Software based PAR basic electrochemical system was used to conduct potentiodynamic polarization tests as per ASTM G5 [13] and electrochemical impedance tests (EIS) as per ASTM G106 standards [14]. A at cell was used for all the experiments and the surface treated samples were used as working electrode, graphite was used as auxiliary electrode and saturated calomel electrode as reference electrode. 3.5% NaCl prepared by dissolving 35 g of NaCl in double distilled water and adding 0.4 g of NaOH to maintain the pH at 10 was used as electrolyte. Tests were conducted at a scan rate of 10 mV/min. The breakage of the passive lm was denoted by Epit value and hence the corrosion current increases drastically with the applied voltage after Epit. For the electrochemical impedance tests, the samples were immersed in the electrolyte for 30 min before the test. The samples were exposed (0.16 cm2) such that only the stir zone and LM region are subjected to the corrosion tests and the rest of the areas were masked. EIS measurements were carried out in the frequency range of 10 mHz to 100 kHz.

3. Results and discussion 3.1. Microstructural characterization Fig. 1ae shows the SEM images of the base metal and the surface treated samples. In Fig. 1ac, it is observed that the grain size has become ner in the FSP samples in comparison to the base metal. The average grain size of the base metal is 67.4 lm and that of FS1 and FS2 samples is 9.6 and 12 lm, respectively. The decrease in grain size is attributed to the dynamic recrystallization during FSP [15,16]. Rhodes et al. [17] have reported that increase in peak temperature during FSP leads to coarse recrystallized grains. Multi passing increases the peak temperature attained and hence the small increase in grain size of FS2 compared to FS1 can be attributed to this increased temperature. Fig. 1d and e shows the SEM images of LM samples. In the LM samples, solidied grains that were grown epitaxially from the unmelted region are seen. The dendrites were coarser in size at lower scan speeds with an average dendrite arm

spacing of 16 lm compared to faster speeds (10 lm) since cooling rate is high at faster scan rates compared to slower scan rates. In the melted region, the solidied microstructure consisted of continuous network of second phase particles which appear as white particles along the dendrite boundaries enveloping the Al matrix in the SEM images (Fig. 1d and e). The laser melted sample depth was 2 and 0.6 mm at 10 and 20 mm/s scan rates respectively. Table 1 lists the average grain size and dendritic arm spacing of the FSP and LM samples, respectively. The average grain size of the base metal is 67 lm and it decreased by 86 and 82% in FS1 and FS2, respectively. Decrease in size and volume fraction of the second phase particles was also observed during FSP. This is mainly due to the thermo-mechanical deformation in the nugget zone which results in a temperature increase up to 400550 C [18,19]. At such high temperature, precipitates in aluminium alloys can coarsen or dissolve into aluminium matrix depending on the type of alloy and the maximum temperature reached [1]. It is noticed that there is 80% reduction in average particle size at FS2 compared to the base metal. Hence, it can be inferred that dissolution of second phase has occurred during the present study and is conrmed by DSC studies. Li et al. [18] observed both coarsening and dissolution of precipitates in the nugget zone of AA 6061-T6 alloy. The actual average particle size decrease was from 20.9 to 4 lm. Decrease in size of second phase particles was also observed in LM alloys. This decrease in size is attributed to the micro segregation during LM. Numerous small volumes of liquid enriched with the solute are formed and the liquid is surrounded by the solid dendrites having low solute concentration (solute-poor) as a result of micro segregation [20]. The reduction in particle size was 79 and 83% at 10 and 20 mm/s scan velocity, respectively. Table 1 shows the average particle size of the surface treated samples along with that for the base metal. Liu et al. [4] also observed a similar behaviour in which the solid solubility of copper in a-Al matrix increased with increase in cooling rate. The volume fraction analysis of second phase particles complements the SEM studies. Table 1 shows the volume fraction analysis of second phase at different parameters after FSP and LM. It is noticed that there is a marginal decrease in the volume fraction of the second phase particles with increase in number of passes in FSP samples and with scan velocity in LM samples. This is attributed to increased heat input with increase in number of passes in FSP [6,21] and to the higher cooling rate at faster scan velocities in laser melting. Micro segregation generally decreases with increasing cooling rate. Hence at higher cooling rates, the rejection of the solute in liquid phase is less and an enriched solid phase is formed. It is noticed that 27.3% and 36.3% second phase have been redistributed into a-Al matrix at LM10 and LM20, respectively. The increased redistribution at LM20 is attributed to higher cooling rate compared to LM10.

Table 1 Average grain size, particle size and volume fraction of second phase particles in surface treated samples along with base metal. Parameter Average grain size/ Dendrite arm spacing (lm) Base metal FS1 FS2 LM10 LM20 67.4 3.0 9.6 2.8 12.0 3.0 16 10 Average % Decrease particle in grain size (lm) size % Decrease in particle size % of second phase dissolved (microscopy) % of second phase dissolved (DSC) 27.5 34.8 28.3 35.4

86 82

20.9 4.0 4.6 1.7 4.0 1.9 4.4 3.5 78 81 79 83

26.3 35.5 27.3 36.3

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Fig. 2. SEMEDX line scan analysis of FS1 and FS2 samples along with the BM.

SEMEDX line scan studies were carried out to show the reduction in second phase particles in surface treated alloys compared to the base metal. Figs. 2 and 3 shows the SEMEDX line scan results of FSP and LM samples along with the base metal. It is inferred from the line scan analysis that the fraction of second phase particles has reduced indicating the redistribution of Cu into the Al matrix in the surface treated samples compared to the base metal. The amount of reduction/redistribution of second phase particles during FSP and LM was quantied by DSC studies. In the DSC traces shown in Fig. 4 for different surface treated samples, the endothermic peak corresponds to the dissolution of second phase particles. The amount of reduction/redistribution of precipitates was estimated from DSC traces by considering the area under the endothermic peak corresponding to the precipitate dissolution. For a particular parameter, the difference between the area under the endothermic peak of the base metal and the surface treated metal divided by the area under endothermic peak of the base metal gives the fraction of precipitates present (x) at a particular parameter. From this, the fraction of second phase dissolved is calculated by subtracting (x) from unity. Similar dissolution of particles on heavy deformation has been reported earlier by Venkateswarlu et al. [22] and Muruyama et al. [23]. Table 1 lists the extent of reduction/redistribution of second

phase by both FSP and LM. It is noticed that the reduction/redistribution is slightly higher with increase in number of passes and scan velocity. 3.2. Hardness High strength aluminium alloys have good mechanical properties because of the strengthening precipitates. However, since the reduction/redistribution of the second phase particles occurs in both FSP and LM, a decrease in hardness is expected. The hardness values of the surface treated samples are shown in Table 2. It is observed that there is a decrease in hardness in both the surface treated samples. The percentage decrease in hardness is high in LM samples (47%) compared to the FSP samples (29%) owing to the localized melting in the sample and subsequent changes in the microstructure. This can be attributed to the dendritic structure in LM samples. Micro segregation is the rejection of the solute into liquid phase by solute-poor solid phase. Decrease in hardness values can be attributed to this poor solute concentration in solid phase. In high strength aluminium alloys like AA 2219, distribution and morphology of the second phase particles have more inuence on the mechanical properties rather the grain size. Since the second phase particles are dissolved in the matrix, there is a decrease in hardness value in FSP samples though the grain size is ner

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Fig. 3. SEMEDX line scan analysis of LM10 and LM20 samples.

compared to the base metal. In general, wear resistance increase when hardness increases. Hence, the hardness values give an insight that the wear properties of FSP samples will be better compared to its LM counterparts.

Fig. 4. DSC traces of surface treated samples along with the base metal.

Table 2 Average hardness of surface treated samples. Parameter Base metal FS1 FS2 LM10 LM20 Average hardness (VHN) 148.3 105.2 111.8 78.0 85.3 % Decrease in hardness 29.1 24.6 47.4 42.4

Fig. 5. Potentiodynamic polarization curves surface treated samples along with the base metal.

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Table 3 Corrosion values of surface treated samples after pitting and impedance tests. Parameter Base metal FS1 FS2 LM10 LM20 Epit vs SCE (mV) 585 485 463 485 458 Icorr (lA) 868.4 11.0 2.9 3.4 1.2 Z (kX) 0.480 16.2 19.5 17.1 20.2

3.3. Corrosion behaviour The potentiodynamic polarization curves for the friction stir processed and LM samples are shown in Fig. 5. The Epit values increased from 585 mV in the base metal to 485 and 463 mV, respectively, in FS1 and FS2 samples. Similarly, Icorr values decreased from 868.4 lA to 11.0 and 2.9 lA, in FS1 and FS2 samples, respectively. LM alloys also showed similar improved corrosion resistance. The Epit increased from 585 mV in the base metal to 485 mV in LM10 and 458 mV in LM20 and Icorr values decreased from 868.4 lA to 3.4 and 1.2 lA, in LM10 and LM20 samples, respectively. The increase in Epit and decrease in Icorr values as shown in Table 3 vividly show that the corrosion resistance has improved by both the surface treatments. The lower corrosion rate of these surface treated alloys is further observed from the shift in passive current density to the left compared to the base metal. The increase in corrosion resistance is attributed to the redistribution of second phase particles in both FSP and LM. Fig. 6 shows the inuence of extent of reduction/redistribution of second phase (volume fraction results) on pitting potential from both FSP and LM studies. There is almost a linear relation between the corrosion

Fig. 8. Inuence of amount of second phase redistributed on impedance values.

resistance and the amount of second phase redistributed irrespective of surface treatment used. Fig. 7 shows the Bodes plots of FSP and LM samples. High impedance value at low frequency indicates better corrosion resistance. From Table 3, it can be noticed that the impedance values of the base metal are in the order of few ohms whereas that of FSP and LM samples are of the order of few kilo ohms. Fig. 8 shows the inuence of extent of reduction/redistribution of second phase (volume fraction results) on impedance values. This result is also similar to that observed in Fig. 6 and conrms that the corrosion resistance can be linearly related to the amount of second phase dissolved during the surface treatments. In AA 2219 alloy, corrosion initiates in the Al crystal region and the noble CuAl2 particles impede the initiation and growth of pitting since the matrix (corrosion potential, 0.73 V) is anodic compared to the intermetallics (corrosion potential, 0.64 V). Due to the huge strain and temperature introduced into the sample during FSP and LM, some CuAl2 particles dissolve into the matrix and the amount of Cu in aAl is increased. This increase in the amount of Cu of the matrix raises the corrosion potential of the aluminium matrix and thereby decreasing the potential difference between the matrix and the second phase and hence decreases the driving force for corrosion. Liu et al. [4] also reported that the extension of the copper solubility in the aAl matrix was considered to be the key factor in the pit initiation in the laser-melted aluminium alloys. The poor corrosion resistance of the base metal is attributed to the numerous second phase particles [24]. 4. Conclusions

Fig. 6. Inuence of amount of second phase redistributed on Epit values.

(1) Both FSP and LM lead to dissolution of second phase particles in AA 2219 alloy, which has led to an improvement in the corrosion resistance of the alloy. (2) The corrosion resistance is almost linearly proportional to the extent of reduction/redistribution of second phase, irrespective of the technique used for their dissolution. (3) The improvement in corrosion resistance achieved by FSP is equivalent to that of LM. (4) The hardness values of the FSP samples are higher compared to the LM samples. This is an indication of better mechanical properties of the FSP samples over LM samples.

Acknowledgements The authors gratefully acknowledge the help and support rendered in FSP by Prof. V. Balasubramanian of Department of Manufacturing Engineering, Annamalai University, Chidambaram. The

Fig. 7. EIS curves for surface treated samples along with the base metal.

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authors extend their sincere thanks to Dr. Padmanadhan, Head and Mr. Shariff, SO/F, Centre for laser processing, ARCI, Hyderabad for their help in laser melting experiments. References
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