Corrosion Science 53 (2011) 25982610

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Effect of the micro-plasma arc welding technique on the microstructure and pitting corrosion of AISI 316L stainless steels in heavy LiBr brines
R. Snchez-Tovar, M.T. Montas, J. Garca-Antn
Ingeniera Electroqumica y Corrosin, Departamento de Ingeniera Qumica y Nuclear, Universitat Politcnica de Valncia, Camino de Vera s/n, 46022 Valencia, Spain

a r t i c l e

i n f o

a b s t r a c t
The effects of the micro-plasma arc welding technique on the microstructure and pitting corrosion of different zones of an AISI 316L stainless steel were studied using different microscopy and electrochemical techniques. Galvanodynamic measurements and laser scanning confocal microscope were used to evaluate the corrosion evolution in situ. Results show, in general, the worst corrosion behaviour for the heat affected zone. Furthermore, there is a relation between the effects of the micro-plasma arc welding process on the materials microstructure and their pitting corrosion resistance. The weld zone was always in the cathodic position of the possible galvanic pairs. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 4 February 2011 Accepted 23 April 2011 Available online 29 April 2011 Keywords: A. Stainless steel B. Polarization C. Pitting corrosion C. Welding

1. Introduction Absorption cooling systems are a suitable alternative to refrigeration compression systems because the use of chlorouorocarbons (CFCs) has been banned (Montreal Protocol [1], 1987) and their substitutes, i.e. hydrochlorouorocarbons, are submitted to severe regulations (Kyoto Protocol [2], 1997), since they are responsible for the ozone layer depletion and climate change. Lithium bromide (LiBr) heavy brines are one of the most widely used absorbents in heat transformers because LiBr possesses favourable thermo-physical properties [3,4]. Nevertheless, LiBr contains bromides which are aggressive ions and, thus, they can cause serious corrosion problems in the materials which form these machines [5,6]. Stainless steels (SS) and their welded forms are widely used as structural elements in LiBr absorption machines [79]. Austenitic stainless steels possess excellent resistance to general corrosion [10], however, they are susceptible to localised corrosive attacks, such as pitting corrosion, intergranular corrosion and stress corrosion cracking in highly electrical conducting media, such as heavy LiBr brines [1114]. Furthermore, welding procedures often worsen this situation by introducing residual stresses and metallurgical changes [1519]. Moreover, these changes in materials increase the dissimilarity of the base metal-weld metal pair causing galvanic corrosion [20]. Pitting corrosion is directly related to the thermal energy associated with welding processes [21,22]. Weldments are indispensable in the manufacture of most components [23]. Austenitic stainless steels can be readily welded through various arc welding processes [24]. Plasma arc welding
Corresponding author. Tel.: +34 963877632; fax: +34 963877639.
E-mail address: jgarciaa@iqn.upv.es (J. Garca-Antn). 0010-938X/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2011.04.019

(PAW) can be dened as a gas-shielded arc welding process where the coalescence of metals is achieved via the heat transferred by an arc that is created between a tungsten electrode and a workpiece. The plasma is formed through the ionisation of a portion of the plasma gas. The PAW process uses three current modes: microplasma, medium current plasma and keyhole plasma. This categorisation is primarily based on the level of welding current. The micro-plasma mode is usually dened in the current range from 0.1 to 20 A. The advantages of the PAW process are primarily intrinsic to the keyhole mode of operation, because greater thicknesses of the metal can be penetrated in a single step, compared with other processes, such as gas tungsten arc welding (GTAW). This greater penetration reduces preparation time. In some materials, for example, a square-grooved butt joint preparation can be used for thicknesses up to 12 mm. The PAW process can produce high weld integrity (similar to GTAW) while minimising weld steps and, hence, welding times and labour costs [25]. Disadvantages include the higher equipment costs, when compared with the GTAW process [26]. Several authors have studied the micro-plasma arc welding (MPAW) technology. Specically, Karimzadeh et al. [27,28] studied the effect of MPAW process parameters on grain growth and porosity distribution of a Ti6Al4V alloy weldment. On the other hand, metallurgical examination of AISI 304 micro-plasma arc welded alloys have been used in aerospace industries [29,30]. However, there is little research concerning the inuence of the micro-plasma arc welding technique on the corrosion resistance of stainless steels [31]. In particular, no works were found that study the effect of MPAW on the corrosion behaviour of the different zones of a welded alloy. The objective of this work is to study how the micro-plasma arc welding procedure affects the corrosion behaviour of an AISI 316L

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austenitic stainless steel in a heavy LiBr brine by means of microscopy and electrochemical techniques. In particular, galvanodynamic measurements together with the laser scanning confocal microscope were used to evaluate corrosion evolution in situ. In this way, three distinct zones were studied: weld zone (WZ), heat affected zone (HAZ) and base zone (BZ). Pitting corrosion mechanisms and the galvanic corrosion among the different parts of the micro-plasma arc welded alloy were also studied. Furthermore, the mechanical properties of the different parts of the AISI 316L micro-plasma arc welded SS were analysed by means of microhardness tests. 2. Materials and methods 2.1. Materials The materials studied in this work were made of micro-plasma arc welded AISI 316L SS. They were made from tubes 14 mm and 16 mm in inner and external diameter, respectively, and 10 mm in length. Thus, a tube 20 mm in length was obtained. Both the base material and the ller alloy were AISI 316L SS; Table 1 presents its chemical composition, as given by the manufacturer. The composition of the ller alloy is more noble than that of the base material. In spite of this, the compositions of both the base and the ller alloy are similar in order to avoid future galvanic problems. Table 2 shows the welding parameters used in the micro-plasma arc welding procedure. The argon backing gas was used to protect the inner surface of the materials during welding [32]. 2.2. Microstructure analysis The aim of the microstructural analysis was to study the effect of micro-plasma arc welding on the microstructure of AISI 316L SS. In order to estimate the possible microstructural variations produced by MPAW, the welded alloy was cut lengthwise and covered in cold mounting acrylic resin for the embedding of specimens. Then, the samples were wet abraded from 220 silicon carbide (SiC) grit to 4000 SiC grit (in several steps; i.e. 220, 500, 1000, 2500 and 4000). Afterwards, the mounted samples were polished with 1 and 0.3 lm alumina and were rinsed with distilled water, followed by ethanol. Once the samples were polished, metallographic etching was carried out according to ASM International [33]. Samples were immersed in the etching solution during 90 s and then rinsed with distilled water, followed by ethanol. The etchant composition consisted of 10 mL of nitric acid (65 wt.%), 10 mL of acetic acid (99100 wt.%), 15 mL of hydrochloric acid (3738 wt.%) and 5 mL of glycerine (100 wt.%). Once etched, the materials were examined by light microscopy (LM) and scanning electron microscopy (SEM) to estimate possible microstructural variations during the MPAW procedure. Energy dispersive X-ray analyses (EDX) were carried out to trace the changes in the composition of the welded materials. Then, the laser scanning confocal microscope was used to analyse the corrosion process in situ. 2.3. Microhardness tests In order to know how the micro-plasma arc welding process affects the different zones of the welded alloy, Vickers microhardness

Table 2 Welding parameters. Welding process Process type Backing gas Flow rate Plasma gas ow rate Number of passes Step 1 Current Voltage Welding speed Step 2 Current Voltage Welding speed Micro-plasma arc welding (MPAW) Manual Argon (99.9%) 2.5 L/min 6.5 L/min 2 11.3 A 20 V 2.6 mm/s 13 A 20 V 2.6 mm/s

measurements were taken with a microhardness tester (Struers Duramin) with a diamond pyramid indenter at a load of 300 g for 15 s [34]. Hardness values were obtained as the mean of six readings. 2.4. Corrosion analysis 2.4.1. Corrosion experiments set up An electrochemical mini-cell designed by the research group was used to perform the corrosion analysis [35]. Fig. 1 shows a scheme of the parts of the mini-cell. The cell was made of glass and it was composed of two pieces. One of them has the function of supporting the micro-plasma arc welds (Fig. 1c) and the other piece (Fig. 1a and b) was located at the top. The latter piece possesses the inlets and the outlets of the cell. In particular, it has two inlets: one for the reference electrode (RE), which is a reference mini-electrode of Ag/AgCl 3 M KCl, and another for taking out the electrical connection of the working electrode (WE, the micro-plasma arc weld). The inlets of the cell also help to introduce the solution into the system. The counter electrode (CE) consists of two platinum laments that pass through the glass and are connected outside the cell to the potentiostat. To conduct the electrochemical tests, the samples were cut lengthwise and covered with an epoxy resin; then, they were wet abraded from 220 silicon carbide (SiC) grit to 4000 SiC grit (in several steps; i.e. 220, 500, 1000, 2500 and 4000) and nally, they were rinsed with distilled water, followed by ethanol. The electrochemical connection to the potentiostat was done by means of a conductor wire. Furthermore, an insulating lacquer was used to study a specic zone of the stainless steel. In this way, an area of 1.5 mm2 of each different part of the welded alloy was exposed to the LiBr solution (the area of the samples was determined for every test by image analysis). In this way, any morphological change could be detected in detail. Micro-plasma arc welded materials were tested in an 850 g/L LiBr solution (a heavy brine like the commercial solutions commonly used in absorption machines). Nitrogen was bubbled into the solution for 20 min, prior to introducing the solution into the cell. Then, the mini-cell was tight closed to keep these conditions. Experiments were performed at 25 C. 2.4.2. Electrochemical tests Two different electrochemical techniques were used in the corrosion studies: cyclic polarisation and galvanodynamic

Table 1 Composition (wt.%) of the AISI 316L SS base material and ller alloy used in this work according to the inspection certicate supplied by the manufacturer. Material Base Filler alloy Cr 16.957 18.160 Ni 10.171 12.100 Mn 1.337 1.860 Mo 2.298 2.540 S 0.004 0.007 Si 0.368 0.760 P 0.030 0.018 C 0.022 0.010 Cu 0.080 N 0.050 Fe Bal. Bal.

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RE inlet WE connection oulet

CE

(a)

(b)

Sample location

(c)
Fig. 1. Minicell scheme: (a) main view of the top of the cell, (b) cross view of the top of the cell, and (c) cross view of the base of the cell (all the measurements are in millimetres). RE: reference electrode; WE: working electrode; CE: counter electrode.

measurements. To perform the tests, a potentiostat (Solartron 1285 provided with the Corrware software) was used. All the tests were repeated at least three times for reproducibility. 2.4.2.1. Cyclic polarisation measurements. Before obtaining the cyclic potentiodynamic curves, the open circuit potential (OCP) was recorded for one hour. After the OCP test, the potential was reduced progressively to 1000 mVAg/AgCl; then, the working electrode potential was scanned from 1000 mVAg/AgCl to the anodic direction until the current density reached 10 mA/cm2, where the potential scan was reversed. A scan rate of 0.5 mV/s was used. As mentioned above in the introduction section, the microplasma arc welding procedure introduces changes in the materials, creating different parts with diverse microstructures in the alloys, which could cause galvanic corrosion problems. In order to evaluate the galvanic corrosion caused by micro-plasma arc welding, the mixed potential theory (MPT) was used [36]. The mixed potential theory was evaluated from the cyclic polarisation curves, by superimposing the potentiodynamic curves of the different parts of the micro-plasma arc welded material. The predicted coupled potential (Ecoup) and the coupled current density (icoup) of the possible pairs were estimated. 2.4.2.2. Galvanodynamic measurements. Before the galvanodynamic measurements, the open circuit potential (OCP) was recorded for 1 h. After the OCP test, the current density was reduced to 0 mA/ cm2 in order to start all the experiments with the same conditions. Then, the galvanodynamic curves were scanned from 0 mA/cm2 to positive current densities using a scan rate of 105 mA/s. 2.4.3. In situ corrosion analysis by LSCM The electrochemical mini-cell makes it possible to use laser scanning confocal microscopy to analyse the corrosion process in situ. Furthermore, the galvanodynamic tests permit controlling

the current applied. In this way, the corrosion process can be analysed in situ by obtaining images of the surface of the different parts of the micro-plasma arc welded materials with the laser scanning confocal microscope. The laser scanning confocal microscope is an Olympus LEXT OLS3100 microscope, which uses LEXT OLS 6.0.3 software. The LSCM uses a Laser Diode with a wavelength of 408 nm, an outstanding horizontal resolution of 0.22 lm and a vertical resolution of 0.01 lm (z-axis). 3. Results and discussion 3.1. Effect of MPAW on AISI 316L microstructure As indicated in Section 2.2 of the experimental procedure, the materials were etched in order to observe their microstructure after the micro-plasma arc welding. Fig. 2 shows a LM image of the lengthwise surface of the micro-plasma arc welded alloy. This gure also shows the microstructure of the main areas of the welded material obtained by scanning electron microscopy. In spite of the fact that the micro-plasma arc welding procedure was performed along two small AISI 316L SS tubes (each tube 10 mm in length) and all the tube can be considered heat affected zone, three major areas were differentiated: the weld zone, WZ, (Fig. 2a), the zone which is closer to the weld, referred to as heat affected zone, HAZ, (Fig. 2b) and the zone farther from the weld, called base zone, BZ (Fig. 2c). Fig. 2 shows that the microstructure of AISI 316L changes due to the micro-plasma arc welding process. As Fig. 2a shows, the microstructure of the weld zone possesses a vermicular morphology characterised by columnar grains with delta-ferrite [37]. This fact is expectable since fast cooling in welding does not last enough time to complete phase transformation. As a result, a large portion of delta-ferrite is retained in the WZ of the micro-plasma arc welded alloy and an incomplete

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a a

100 m
b b

100 m
c c

1 mm

100 m

Fig. 2. Length ring surface of the MPA welded alloy obtained by means of LM. Images of the weld zone (a), HAZ (b) and base zone (c) using SEM.

transformation results in the retention of the skeletal dendritic delta-phase within the austenite matrix [38]. A small amount of delta-ferrite is necessary to avoid the problem of hot cracking during weld solidication [39,40]. In fact, the weld zone of austenitic stainless steels has a cast structure with 210 wt.% delta-ferrite in the austenite matrix [10]. However, delta-ferrite contents could lead to many Cr-depleted zones which are likely to form due to micro-segregation and, consequently, to a reduction in corrosion resistance due to the formation of a less stable passive lm [41].

The HAZ which is closer to the weld zone presents an austenitic microstructure with the typical recrystallisation and grain growth [42]. In general, the HAZ is characterised by a heterogeneous microstructure relative to grain size. In Fig. 2b and c the differences in grain size due to the micro-plasma arc welding process can be observed. The zone which is farther from the weld zone also has an austenitic microstructure but the grain does not undergo considerable enlargement of the grain size; thus, this zone will be referred to as base zone. BZ microstructure also has polygonal austenitic grains where twins are visible.

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An energy dispersive X-ray analysis (EDX) was performed in order to observe variations in the composition of stainless steel due to the micro-plasma arc welding procedure. In this way, the main components of the alloy (i.e. Cr, Mo and Ni) were analysed. Table 3 shows that the compositions of HAZ and BZ are similar, with Cr values of 17.4317.32 wt.%, Mo contents of 2.38 wt.% and Ni values from 10.57 to 10.45 wt.%. Table 3 also shows higher contents of all these elements (Cr, Mo and Ni) in WZ. This could be due to the fact that the composition of the ller alloy presents larger amounts of Cr, Mo and Ni. A composition analysis was performed on WZ to distinguish between the delta-ferrite grains and the austenite matrix composition. Fig. 3 shows that accumulations of Ni were found in the austenite matrix (A-zone) while the Ni content is lower in the delta-ferrite zone (F-zone) [40]. On the other hand, the delta-ferrite regions present higher Cr values. Using transmission electron microscopy, Brooks et al. [43] proved that during cooling transformation there is a separation of Cr to ferrite and Ni to austenite.

3.2. Effect of MPAW on AISI 316L microhardness Fig. 4 shows the microhardness values obtained for the different zones of the micro-plasma arc welded AISI 316L SS. The base zone presents the highest microhardness value. The microhardness values of HAZ and WZ are similar (174.33 and 181.67 HV300g, respectively). The different microhardness values between the weld and base zone could be due to the presence of delta-ferrite in the former [44]. As it can be observed, the micro-plasma arc welding process leads to different microhardness values depending on the zone. In general, there is a positive correlation between hardness and strength: the higher the hardness, the higher the strength. Therefore, the weld strength is weaker in HAZ and WZ than in BZ. 3.3. Effect of MPAW on AISI 316L corrosion 3.3.1. Cyclic polarisation measurements 3.3.1.1. Open circuit potentials. Previous to the polarisation curves of the different zones of the micro-plasma arc welded material, an open circuit potential measurement was performed. The OCP values, obtained as the arithmetic mean of the last 5 min values of open circuit potential measurements [45], for WZ, HAZ and BZ in the LiBr solution are 173 21, 189 29, 81 4 mVAg/AgCl, respectively. According to these results, the most noble open circuit potential is obtained for the base zone whereas the most active one for HAZ. However, the OCP values for HAZ and WZ are similar. The most positive open circuit potential values of the base zone could be related to the better Cr2O3 protective lm formed on the metal surface due to its homogeneous austenitic microstructure [24]. Fig. 5 shows the cyclic potentiodynamic curves of BZ, HAZ and WZ of the micro-plasma arc welded alloy in the LiBr solution. As tests were reproducible, the curves shown in Fig. 5 illustrate one of the recorded measurements. Fig. 5 shows that the obtained curves are typical of passivable materials with a current plateau in the anodic branch; thus, micro-plasma arc welded materials passivate in 850 g/L LiBr solutions. On the other hand, as it can be observed in Fig. 5, the OCP values are in the passivity range for the three micro-plasma arc welded zones of AISI 316L stainless steel. This means that, at the open circuit potential, the MPA welded alloy spontaneously passivates. 3.3.1.2. Corrosion parameters. Table 4 shows the typical corrosion parameters (corrosion potential: Ecorr and corrosion current

Table 3 EDX (wt.%) analysis on the MPA welded zones: WZ, HAZ and BZ. Material WZ HAZ BZ Cr 18.05 17.43 17.32 Mo 2.54 2.38 2.38 Ni 11.49 10.57 10.45

A-zone

F-zone

50 m
b
25
F-zone A-zone

300 250 200

20

223.44 174.33

EDX (wt. %)

15

181.67

HV300 g
Cr Mo Ni

10

150 100

50
0

Elements
Fig. 3. Images of the WZ: austenite and ferrite zones (A-zone = austenite zone; F-zone = ferrite zone) (a) and EDX (wt.%) composition of the WZ of the MPA welded material (b).

0 BZ HAZ WZ

Material zone
Fig. 4. Microhardness values of the different zones of the MPA welded alloy.

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100
BZ HAZ WZ

IiI (mA/cm)2

potential values due to its higher Cr, Ni and Mo content. In fact, Pardo et al. [13] proved that Mo additions shifted the corrosion potential to more noble values. Table 4 also shows that HAZ has the highest corrosion current density and the BZ the lowest. Since the corrosion current density is a parameter related to the corrosion rate, higher values involve greater corrosion rates. Thus, the heat affected zone of the microplasma arc welded stainless steels possesses the worst corrosion resistance in terms of corrosion rate values.

0.01
3.3.1.3. Pitting susceptibility and passivation parameters. Cyclic curves also provide information about the pitting, passivation and repassivation behaviour of the materials with parameters such as pitting potential (Ep) and passivation current density (ip), which are also shown in Table 4. Pitting potential (Ep) is the potential at which current density reaches 100 lA/cm2 [56]. Pitting potential determines the pitting corrosion susceptibility of the micro-plasma arc welded zone, that is, susceptibility to local breakdown and pit initiation. All the micro-plasma arc welded zones of AISI 316L SS are susceptible to pitting corrosion since bromides are very aggressive ions that promote passive lm breakdown of stainless steels [5658]. Table 4 shows that BZ presents the most positive Ep value and WZ the most negative value. Ep value for the HAZ lies between the ones obtained for the base and the weld zones. In fact, Luo [24] observed that the coarse grains in HAZ have a negative inuence on corrosion resistance. By contrast BZ is more resistant to pitting corrosion and, consequently, the breakdown of the passive lm and the initiation of pits can occur at more positive potentials. The residual stresses induced by MPAW will make WZ more sensitive to localised corrosion [10]. According to Lee et al. [21], a fully austenitic structure has the lowest susceptibility to pitting corrosion attack since the passive lm on such homogenous microstructure is more resistant to pitting corrosion. According to the literature [5961], the presence of chromium-depleted regions is related to pit nucleation and growth. As shown in Fig. 3, the delta-ferrite microstructure of WZ promotes the formation of Cr-depleted regions (in the austenite matrix). Furthermore, delta-ferrite has been proved to be detrimental because of its susceptibility to be attacked in chloride media [62,63] and the same effect may occur in the presence of bromide ions. This could lead to a decrease in pitting potential, which could explain the most negative OCP values of the weld zone. Passivation current densities (ip) were obtained from the cyclic potentiodynamic curves as the mean values where current density remains stable when potential shifts to the anodic direction. The ip values determine the corrosion rates of the different zones of the MPA welded alloy in the passivity range. Table 4 shows that passivation current densities are higher than their corresponding corrosion current densities in all the zones studied. This fact means that only partial passivation is possible due to the formation of a passive layer in the MPA welded SS zones in LiBr solutions. It is generally accepted that Cr2O3-based products form barrier layers and they are responsible for the superior corrosion resistance of stainless steels [64]. Cr2O3-based barrier layers tend to form on Cr-containing iron based alloys if the Cr content of the alloy exceeds 1215 wt.%. Bromide ions can be adsorbed by the lm and replace oxygen, forming a soluble metal bromide, destroying the

0.0001 -1 -0.5 0 0.5

E (VAg/AgCl)
Fig. 5. Cyclic polarisation curves of the different zones of the MPA welded stainless steels in 850 g/L LiBr solutions.

density: icorr) determined from the polarisation curves shown in Fig. 5. Ecorr was obtained as the potential at which the net current density (sum of the anodic partial current density and the cathodic partial current density) was equal to zero. Corrosion current densities were determined by the extrapolation of the cathodic apparent Tafel slopes to the point that yields the corrosion potential. Extrapolation started over about 50 mV away from Ecorr and the same range of potential values was used throughout the tests. The most precise determination of the corrosion current density values by Tafel extrapolation is when both the anodic and cathodic branches show linearity. However, it is also possible to make an accurate evaluation of the corrosion current densities if one of the branches of the polarisation curves displays a sufciently long linear tendency around the corrosion potential [4649]. In fact, two rules of thumb should be applied when using Tafel extrapolation. First, at least one of the branches of the polarisation curve should exhibit Tafel behaviour (i.e., linear on semilogarithmic scale) over about one decade of current density. Second, extrapolation should start at least 50100 mV away from Ecorr. These two rules improve the accuracy of manual extrapolation [50]. This allows a precise evaluation of the effect of micro-plasma arc welding on the corrosion process of the alloy. Previous works also used the cathodic Tafel slope to evaluate icorr in passivable materials [51,52]. Regarding the corrosion potentials, Table 4 shows that the most active values (more negative) are obtained for the base and heat affected zones (902 and 784 mVAg/AgCl, respectively). The corrosion potentials obtained from the potentiodynamic curves are more negative than the OCP values; this is due to the polarisation applied during the potentiodynamic sweep [5355]. During the open circuit measurements a protective lm could be formed on the metal surface, shifting the potential to more positive values. However, at the beginning of the potentiodynamic sweep the potential diminished to 1 VAg/AgCl. At this negative potential the metal surface is modied (the surface of the samples is activated by the cathodic polarisation) and the corresponding Ecorr calculated from the potentiodynamic curve is more negative than the potential obtained under open circuit conditions (OCP value). Under these conditions, the weld zone presents the most noble corrosion

Table 4 Parameters of the MPA welded materials obtained from the cyclic polarisation curves in 850 g/L LiBr solutions. Material WZ HAZ BZ Ecorr (mVAg/AgCl) 676 31 784 42 902 18 icorr (lA/cm2) 5.8 1.1 7.0 1.2 4.3 1.7 Ep (mVAg/AgCl) 288 3 366 18 593 37 ip (lA/cm2) 13.9 3.2 25.1 7.3 19.2 0.3 irp (mA/cm2) 37.1 10.6 60.1 16.4 35.8 1.6 Erp (mVAg/AgCl) 79 3 89 14 100 1

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lm and increasing corrosion rates [65]. Additionally, alterations in the microstructure and composition of the welded stainless steel can affect the structure of the passive lm. HAZ has the highest passivation current densities (ip values 1.8 and 1.3 higher than for WZ and BZ, respectively) and WZ the lowest due to its higher Cr, Mo and Ni content (Table 4). 3.3.1.4. Repassivation parameters. The parameters related to the repassivation characteristics of the materials, repassivation current density (irp) and repassivation potential (Erp), were also determined from the cyclic polarisation curves of the different zones in the micro-plasma arc welded materials (Table 4). irp values represent the maximum current reached since the current does not begin to decrease immediately after scan reversal [22]. Repassivation current density is an inverse measure of the ability of materials to repassivate and, hence, of the extent of propagation once corrosion has initiated. Table 4 shows that the highest repassivation current density is obtained for HAZ, with the worst ability to repassivate. This is related with the high susceptibility to pitting corrosion and high passivation current density of the heat affected zone. Garcia et al. [38] also determined a sharp increase in the repassivation current density value of HAZ. Erp was recorded at the crossing point between the backward and forward scans. This parameter refers to the limit below which the metal remains passive and active pits repassivate. If Erp is more positive than the corrosion potential, the material is able to regenerate an eventual breakdown of the passive lm; however, if Erp is more negative than the corrosion potential, the material is not able to completely repassivate the pits. The Erp values obtained are more positive than the corrosion potential in all cases; thus, the material can repassivate the pits. The repassivation potentials are of the same order of magnitude in all stainless steel zones (79, 90 and 100 mVAg/ACl for WZ, HAZ and BZ, respectively), though they are slightly more positive for WZ, which exhibits better repassivation characteristics. This could be attributed to its high nickel [57] and molybdenum [66] content, which are elements that promote pit repassivation. Fig. 6 shows the different zones of the passivity range. This range is a measure of the tendency to nucleation pitting. The greater the difference, the higher the resistance of the material to pitting corrosion [65]. The repassivation potential could differentiate two zones in the passivity range of the materials (EpEcorr) which were dened by Bellezze et al. [67], i.e. a perfect or stable passivity region (ErpEcorr) between the corrosion potential and Erp (where pitting corrosion cannot initiate and existing pits cannot propagate) and an imperfect or unstable passivity region (EpErp) between Erp and Ep, (where pits cannot initiate but existing pits can propagate). In addition, the last region (EpErp) also denes the hysteresis loop. The narrower the hysteresis loop, the easier it becomes to repassivate the pit. Furthermore, the reasons why the hysteresis loop narrows must be considered since it is associated with a shift of the Erp to more positive values as indicative of good repassivation properties. In this study Fig. 5 shows that the hysteresis loop narrows due to the welding process (in WZ and HAZ); however, the Erp values are similar in all zones studied (Table 4). Hence, this fact cannot be associated with a less difcult repassivation of pits in BZ. Indeed, the widest imperfect passivity region of BZ is due to its high positive Ep value. Fig. 6a also shows that the highest passivity range is obtained in the base zone of the micro-plasma arc welded alloys. The ne crystalline grains facilitate the formation of the Cr2O3 passive lm [24]. HAZ and WZ microstructural changes decrease the resistance of AISI 316L SS to pitting corrosion, in particular, the weld zone, which possesses the smallest passivity range. Fig. 6b and c show the perfect or stable passivity region and the imperfect or unstable passivity region, respectively. As it can be seen there, the size of the

a. Passivity range

E p - E corr = 964 mV

WZ

E p - E corr = 1150 mV

HAZ

E p - E corr = 1495 mV

BZ

E corr

Ep

-1000

-400

200

800

E (mVAg/AgCl)

b. Perfect passivity region

E rp - E corr = 597 mV

WZ

E rp - E corr = 694 mV

HAZ

E rp - E corr = 802 mV E corr

BZ

E rp

-1000

-400

200

800

E (mVAg/AgCl)

c. Imperfect passivity region

E c - E corr = 367 mV

WZ

E c - E corr = 456 mV

HAZ

E c - E corr = 693 mV E rp Ep

BZ

-1000

-400

200

800

E (mVAg/AgCl)
Fig. 6. Passivity ranges (a), perfect passivity region (b) and imperfect passivity region (c) of the MPA welded zones in 850 g/L LiBr solutions.

perfect and imperfect passivity regions is similar in all MPA welded zones, the former being slightly larger. 3.3.1.5. Evaluation of galvanic corrosion. The results show that the micro-plasma arc welding procedure alters the microstructure of the materials causing local variations in the composition and struc-

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ture of the alloy. Changes in the parameters determined from the polarisation curves have also been analysed. The dissimilarities in properties and microstructural morphologies of the regions of a welded alloy such as MPA welded AISI 316L SS, can result in different corrosion sensitivities and may promote the formation of galvanic pairs [39]. Open circuit potentials of the different samples play an important role in galvanic interactions. However, the magnitude of the galvanic current is only in part a function of the open circuit potentials of these samples. The anodic and cathodic behaviours have strong inuences on this interaction. As a consequence, it is necessary to consider the cathodic and anodic polarisation curves in each particular case, which provides a better predictive technique for the galvanic corrosion rate [68,69]. The mixed potential theory has been widely used to study the galvanic corrosion [7073] and, in particular, to analyse the galvanic corrosion behaviour between non-welded/welded couples [74]. Fig. 5 shows that the base zone is located in the anodic position with respect to both HAZ and WZ. The galvanic pairs are BZ/HAZ and BZ/WZ, where HAZ and WZ remain protected and BZ corrodes. The heat affected zone has a more active corrosion potential than the weld zone; thus, the formation of the galvanic pair HAZ/WZ is also possible, where HAZ corrodes and WZ remains protected. This fact could be attributed to the higher chromium, molybdenum and nickel content of the ller alloy (18.16 wt.%, 2.54 wt.% and 12.10 wt.%, respectively) used in the micro-plasma arc welding with respect to the base metal composition (16.96 wt.%, 2.30 wt.% and 10.17 wt.%, respectively). Dadfar et al. [62] worked with AISI 316L SS in saline solutions and their study revealed that, when the base and weld zones were adjacently placed together in an electrolyte, the base metal was the anodic member of the pair. The same result was obtained in Lee et al. [21] for AISI 304 welds and base material in NaCl solutions. The galvanic pile formed at the interface will not endanger the weld with other forms of corrosion (crevice, pitting, or intergranular corrosion) resulting from the galvanic coupling [74]. Table 5 shows the different galvanic parameters of the pairs according to the mixed potential theory [36]. The predicted coupled potential (Ecoup) and the galvanic current density (icoup) of the pair were estimated from the intersection point between the anodic branch of the less noble material and the cathodic branch of the most noble material of the polarisation curves (Fig. 5). Letters A and C in Table 5 refer to the anode and the cathode, respectively, and the position of the micro-plasma arc welded zones in the galvanic pair. Other parameters of the importance in the galvanic pair were also analysed. Minimal differences of 100 130 mV between the corrosion potential of the cathode and the anode of the pair (Ecorr_CEcorr_A) are necessary to consider the galvanic effect signicant [75]. According to Mansfeld and Kendel [76] the relative increase in the corrosion rate of the anode of the galvanic pair can be expressed by the ratio icoup/icorr, where icorr is the corrosion current density of the uncoupled anode. The magnitude of this ratio may be used as a guide to reect the severity of the galvanic effect and it was suggested that a icoup/icorr value lower than 5 implies compatibility of the members in a galvanic pair [77].

Table 5 shows that the most noble coupled potentials were obtained for the HAZ/WZ pair whereas the most active Ecoup values were obtained for the BZ/HAZ pair. Regarding the coupled current densities, all pairs present higher values than the respective corrosion current density obtained for the uncoupled anode of the pair. BZ duplicates and triplicates its corrosion current density when it is coupled with HAZ and WZ, respectively (from 4.3 lA/cm2 to 10.7 and 15.9 lA/cm2, respectively). The heat affected zone increased its corrosion current density by 64%. The values of the difference between the corrosion potentials of the cathode and the anode indicate a signicant galvanic effect in the BZ/WZ pair whereas the galvanic pairs BZ/HAZ and HAZ/WZ are in the limit to be considered signicant. As for the severity of the galvanic pair, icoup/icorr values indicate compatibility between the members of the pair in all cases, although, the BZ/WZ galvanic pair presents the highest icoup/icorr value (3.7). This is in agreement with the results obtained for the minimal differences (Ecorr_CEcorr_A) to consider the galvanic effect signicant. Consequently, the pair with the worst galvanic behaviour in terms of highest coupled current density and severity of the pair is the BZ/WZ galvanic pair, which also presents the highest icoup/ icorr ratio. This could be due to the fact that the base and the weld zones have the greatest differences in terms of composition and microstructure.

Table 5 Galvanic corrosion parameters of the possible pairs among the different MPA welded zones. Couple (A/C) BZ/HAZ BZ/WZ HAZ/WZ Ecoup (mVAg/AgCl) 822 21 766 29 731 11 icoup (lA/cm2) 10.7 2.8 15.9 2.0 11.5 2.1 Ecorr_CEcorr_A (mV) 118 226 108 icoup/icorr 2.5 3.7 1.6

3.3.2. Galvanodynamic measurements The best approach to study corrosion evolution is the in situ observation technology. As it was previously mentioned in the experimental procedure, galvanodynamic tests were performed in order to analyse the corrosion process in situ by means of an electrochemical mini-cell connected to a laser scanning confocal microscope since these experiments make it possible to control the applied current. Like with the cyclic potentiodynamic curves, prior to the galvanodynamic tests, an open circuit potential was registered for 1 h. The mean values of the OCP, obtained as the arithmetic mean of the last 5 min values of open circuit potential measurements [45], are 159 5, 162 17 and 62 5 mVAg/AgCl for WZ, HAZ and BZ, respectively in the LiBr solution. The OCP values follow the same tendency as that of the potentiodynamic curves, i.e. the most noble open circuit potential is obtained for the base zone whereas more active open circuit potentials are obtained for HAZ and WZ. Fig. 7 shows the galvanodynamic scans obtained for the different micro-plasma arc welded zones studied: WZ, HAZ and BZ. Table 6 shows the parameters obtained from the galvanodynamic test of Fig. 7. The corrosion potential (Ecorr) was calculated as the mean value when current density was equal to zero (before starting the test and after the open circuit potential recordings). The potential and current density at which the rst pit was observed in situ were named rst pitting potential (Efp) and rst pitting current density (ifp). The values shown in Table 6 are in accordance with those obtained from the polarisation curves (see Table 4). Corrosion potentials follow the same tendency as in the polarisation measurements, that is, the most active value is obtained for BZ whereas WZ presents the most noble corrosion potential. The corrosion potentials are more negative than the OCP values due to the applied polarisation. On the other hand, ifp was very close to 100 lA/cm2 in all cases (Table 6), which is the current density value that determined the pitting potential from the cyclic polarisation measurements. Thus, the rst pit observed on the surfaces of the materials occurs close to the pitting potential. The trend of the Efp values is the same as that of the pitting potentials in the cyclic polarisation tests (see Table 4), that is, the most positive Efp is obtained for BZ, followed by HAZ and the most negative corresponds to WZ.

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1000
BZ HAZ WZ

500

100 0 -0.3 0 0.3 0.6

E (VAg/AgCl)
Fig. 7. Galvanodynamic curves of the different zones of the MPA welded stainless steel in 850 g/L LiBr solutions.

Table 6 Parameters of the MPA welded materials obtained from the galvanodynamic curves in 850 g/L LiBr solutions. Material WZ HAZ BZ Ecorr (mVAg/AgCl) 665 26 788 34 941 21 Efp (mVAg/AgCl) 324 46 424 12 520 17 ifp (lA/cm2) 102.2 4.5 105.4 20.8 102.9 11.6

of the different parts of the micro-plasma arc welded materials (Figs. 811). These Figures show that the corrosion mechanism of AISI 316L SS in LiBr solutions is typical of pitting corrosion since stainless steels in the presence of aggressive ions (such as bromides) are susceptible to pitting corrosion [11,13]. Susceptibility to pitting corrosion increases due to the micro-plasma arc welding procedure as reported in the literature [21,22,78] and proved in this work (see Tables 4 and 6). Despite the fact that pits propagate at very high current densities, the surface area of an initial pit growing is very small and even a high current density can result owing to low values of the absolute current owing out of the pit [79]. Thus, galvanodynamic tests are an interesting technique to analyse pitting corrosion susceptibility because they allow the control of the current density values. Pitting corrosion phenomena are favoured by the anodic dissolution of the metal with metallic cations inside the pit. As a consequence of the hydrolysis of the metallic ions, the local pH is reduced and Br- ions migrate to the pit due to electroneutrality [8082]. This effect generates more aggressive local conditions and the metal dissolution continues. The release of aggressive anions from pits and their diffusion over the electrode surface may cause weakening of the protective passive lm and each active pit is more likely to create further pits in its vicinity [8385]. The next Sections (3.3.2.13.3.2.3) describe the different processes of pitting corrosion which occur in the different parts of the micro-plasma arc welded zones. 3.3.2.1. WZ corrosion. Figs. 8 and 9 show the corrosion process which occurs in the weld zone of the micro-plasma arc welded materials. The WZ galvanodynamic curve in Fig. 7 shows that the potential rst shifts to more positive values increasing current density and when the current density reaches a certain value the potential remains constant (Efp). Then, the potential shifts to more negative values and some potential peaks in the galvanodynamic register are observed. Efp is related to the formation of pits on the WZ surface. The potential peaks that appear after the shift of

Since the OCP values of the different zones of the MPA welded alloy were more negative than their corresponding rst pitting potentials, pits were not observed during the OCP measurements. Galvanodynamic tests together with LSCM allow the in situ analysis of the corrosion process by obtaining images of the surface

IiI (A/cm2)

160 m

160 m

80 m

80 m

a.

A = 1.4103 m2

b.

A = 3.1103 m2

c.

A = 3.4103 m2

d.

A = 4.4103 m2

80 m

80 m

80 m

80 m

e.

A = 6.2103 m2

f.

A = 8.3103 m2

g.

A = 11.5103 m2

h.

A = 16.3103 m2

80 m

160 m

160 m

160 m

i.

A = 37.4103 m2

j.

A = 42.9103 m2

k.

A = 183.6103 m2

m.

A = 268.5 103 m2

Fig. 8. Images of a pit evolution in the WZ obtained by means of LSCM during the galvanodynamic test in 850 g/L LiBr solutions after reaching Efp. Images are temporarily ordered. A = surface area of the pit.

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a (t = 220 s)

b (t = 490 s)

160 m

160 m

c (t = 880 s)

d (t = 1280 s)

160 m

160 m

Fig. 9. Images of the corrosion process of the WZ obtained by means of LSCM during the galvanodynamic test in 850 g/L LiBr solutions after reaching Efp. Images are temporarily ordered.

80 m

(a)
30 m m
Fig. 10. Image of the corrosion process of the HAZ during the galvanodynamic test in 850 g/L LiBr solutions after reaching Efp obtained using the LSCM.

the potential to more negative values are due to the formation of new pits and the spread of the corrosion products. Fig. 8 shows the evolution of a pit (where more than one pit is shown, the evolution refers to the pit highlighted with a circle) from Efp (Fig. 8a) until the end of the test (Fig. 8m). The pit grows uniformly in all directions from the initiating defect as the current density applied is higher (the area values of the pit evolution are also indicated in Fig. 8). The surface of the material shown in Fig. 9 presents multicorrosion attack where small pits cover the surface of the alloy (an interdendritic attack of the WZ surface). This fact was also observed in the work of Lin et al. [86], where a great number of pits were obtained in the WZ. First (Fig. 9a) all pits have the same size and their surface increases with time (Fig. 9bd). A delta-ferrite microstructure could be associated with a large number of interfaces where austenite particles can nucleate and grow [22]. Some authors [10,62,87] agree that while delta-ferrite increases during

(b)
Fig. 11. Images of the corrosion process of the BZ obtained by means of LSCM during the galvanodynamic test in 850 g/L LiBr solutions after reaching Efp. 2-D image (a) and 3-D image (b).

welding many chromium-depleted zones may form because of microsegregation of Cr at the ferrite-austenite interphase bound-

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aries, leading to the formation of a large number of pits throughout the WZ of the MPA welded alloy. Kwok et al. [88] also observed that austenitic stainless steel regions, which were depleted in Cr, can act as nucleation sites for pits in chloride media. 3.3.2.2. HAZ corrosion. Fig. 10 shows the surface of the heat affected zone after the galvanodynamic test. Contrarily to what occurs in the weld zone, the multicorrosion process is not observed in HAZ. Fig. 7 shows that potential shifts to more positive values with current density until a sharp shift to more negative potential values is observed, indicating the formation of a pit on the HAZ surface. Then, the potential remains almost constant. From the rst pit, corrosion products spread out continuously around the initial damage. Corrosion products form a new hemisphere and, subsequently, corrosion affects a large area of the HAZ surface. HAZ microstructure composed only of austenite grains leads to the formation of single pits instead of multicorrosion processes. Fig. 10 shows a photograph of the pit obtained by LSCM. Pits may be crystallographic in nature with at walls and etched interior surfaces (formed at relative low potentials) or could be approximately hemispherical with polished interiors (formed at higher potentials) [12]. According to Fig. 10, this might be a polishing pit. Sato [89] showed that pits initiated above Ep (in this case above Efp), grew as hemispherical polishing state pits, but if the potential is then reduced, the pits either repassivate or propagate as active (etching) pits. 3.3.2.3. BZ corrosion. Fig. 11 shows the corrosion process affecting the base zone. Like in HAZ, no signal of multicorrosion was detected. This is in agreement with the galvanodynamic curve obtained for BZ, which shows a single peak corresponding to the rst pitting potential (see Fig. 7). BZ has a homogeneous austenitic microstructure with fewer defects associated with pit initiation sites. As it happened in HAZ, potential shifts to more positive values with increasing current density until the potential reaches a constant value followed by a drop in potential (pit formation). Then, the potential remains constant. Fig. 11 shows that BZ surface presents two pits after the test in LiBr solutions; both pit surfaces increase with time and are dish-shaped. Large pits are often found to be dish-shaped rather than perfectly hemispherical because without a pit cover, the pit edges have lower associated solution or diffusional resistances and dissolve more rapidly [12]. Pistorius and Burstein [90] believed that all pits grew under diffusional control with a salt on their surface, even before the cover was lost. Fig. 11b shows a three dimensional (3-D) image of the pits. This image shows that the pits generate an accumulation of corrosion products on the BZ pit surface (volume is higher where corrosion begins).

(3) According to Vickers microhardness values, the joining strength is weaker in the HAZ and WZ than in BZ. (4) BZ presents the best overall corrosion behaviour compared to the other micro-plasma arc welded zones. However, HAZ shows the highest corrosion, passivation and repassivation current densities, i.e. greater corrosion rates and a worse ability to repassivation. (5) The galvanic pairs BZ/HAZ, BZ/WZ and HAZ/WZ could be formed according to the Mixed Potential Theory, where the WZ remains protected. BZ doubles and triples its corrosion current density when coupled with HAZ and WZ, respectively and HAZ increases its corrosion current density by 64%. (6) The pair which presents the worst galvanic behaviour in terms of highest coupled current density and severity is the BZ/WZ galvanic pair, which also presents the highest icoup/icorr ratio. (7) Corrosion potentials follow the same tendency regardless of the electrochemical technique used. ifp was very close to 100 lA/cm2 in all cases indicating that the rst pit observed on the surfaces of the materials appears close to the pitting potential. The trend of the Efp values is the same as that of the pitting potentials. (8) All the micro-plasma arc welded zones (WZ, HAZ and BZ) of AISI 316L SS are susceptible to pitting corrosion. A relation between the pitting corrosion behaviour and the microstructure of the different MPA welded materials was found. Multicorrosion attack occurs in the weld zone (due to microsegregation of Cr at the ferrite-austenite interphase bondaries); however, no evidence of multicorrosion was detected in HAZ and BZ, which are zones with austenitic microstructure.

Acknowledgements The authors would like to express their gratitude to the MICINN for the nancial support (project CTQ2009-07518), to the FPU grant given to Rita Snchez Tovar, to FEDER, to the Generalitat Valenciana for its help in the LSCM acquisition (MY08/ISIRM/S/ 100) and to Dr. Asuncion Jaime for her translation assistance.

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4. Conclusions In this work the effect of the micro-plasma arc welding technique on the microstructure and pitting corrosion susceptibility of AISI 316L stainless steels in a heavy LiBr brine has been studied by means of microscopy and electrochemical techniques. The main conclusions obtained from this work are presented below: (1) The microstructure of AISI 316L stainless steel changes due to the micro-plasma arc welding process. The weld zone (WZ) possesses vermicular morphology characterised by columnar grains containing delta-ferrite. Both the HAZ and base zone (BZ) present an austenitic microstructure but the former has typical recrystallisation and grain growth. (2) X-ray analysis reveals similar compositions in HAZ and BZ whereas WZ presents higher contents of chromium, nickel and molybdenum.

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