Materials and Corrosion 2010, 61, No.

DOI: 10.1002/maco.200905246

51

The influence of tin and silver as microstructure modifiers on the corrosion rate of PbCa alloys in sulfuric acid solutions
ekerevac*, E. Romhanji, Z. Cvijovic and L. N. Bujanovic M. I. C
The effect of microstructure modifiers, Sn and Ag, on the corrosion rate of commercial PbCa alloy in H2SO4 electrolyte was investigated by the potentiodynamic polarization and by the weight loss corrosion rate measurement at the open circuit potential. The effect of microstructure modification of the PbCa alloy, provoked by the alloying with tin and silver as well as by the proper thermo-mechanical treatment, is recorded by optical microscopy. The weight loss experiments have shown three- to five-fold decreases in the corrosion rate of ternary PbCaSn and quaternary PbCaSn Ag alloys, compared to the results for primary PbCa alloy. It is largely in accordance with the results of potentiodynamic polarization measurements that showed comparable decrease in the passive current density of the modified alloys. The obtained results are discussed in terms of the synergetic effect of the addition of modifiers and the thermo-mechanical treatment on to the PbCa alloy microstructure refinement, and accordingly the increase in their corrosion resistance.

1 Introduction
In the leadacid battery industry, various compositions of PbCa alloys are used for the manufacturing of the electrode grids for maintenance-free leadacid batteries for decades. Those alloys are characterized by relatively high hydrogen evolution overpotential and good mechanical and electrical characteristics. High value of hydrogen overpotential is very important for the elimination of premature capacity loss of maintenance-free leadacid batteries caused by water decomposition and deterioration of electrode grids caused by corrosion. However, very fine-grained microstructures of PbCa alloys might have negative impact on their corrosion stability, because of the increased intercrystalline area that promotes higher intercrystalline corrosion rate of grid material. Another disadvantage of those alloys is the formation of low conductivity passive layer at the deep discharges of leadacid battery or in the course of active mass curing during the production of electrodes. Both of these effects cause the loss of the electric contact between active mass and electrode grid. The
ekerevac, L. N. Bujanovic M. I. C Science and Technology Park Zemun, Research and Development ki put 23, (Serbia) Centre, 11080 Beograd, Batajnic E-mail: ihis@eunet.rs E. Romhanji, Z. Cvijovic Faculty of Technology and Metallurgy, University of Belgrade, 11000 Beograd, Karnegijeva 4, (Serbia)

modification of the PbCa alloy compositions and their microstructure by additional alloying with metals such as tin, aluminum, and silver and proper thermo-mechanical treatment could overcome noticed disadvantages. PbAgCa alloys are characterized by good corrosion resistance in sulfuric acid solutions, but a bad combination of mechanical characteristics. The addition of tin, as a microstructure modifier, in quaternary PbCaSnAg alloys remarkably improves cycle-life of leadacid batteries and other exploitation characteristics. Addition of tin improves both the mechanical strength of electrode grids and their corrosion resistance and improves the electric conductivity of PbCa alloys. Incorporation of tin in the corrosion layer, as semi-conducting tin oxide, suppresses electrical isolation of active mass, eventually caused by passivation of the electrode grid/active mass interface [15]. The surface porosity of PbCaSn alloys, which usually appears in the process of grid casting, can be avoided by proper thermo-mechanical treatment and the production of wrought electrode grids. The parameters such as the degree of deformation, the conditions of recrystallization, and the number of repetitions of such steps are useful tools to obtain adequate alloy microstructure that is more resistant to creeping as well as to corrosion [2]. The optimal concentrations of calcium, tin, and silver in alloys of PbCaSnAg and their relative ratios are reported in the known literature. In the industry, the mostly accepted concentration of Ca in PbCa alloys is in the range between 0.06 and

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0.08 wt%. Alloys that contain less than 0.06 wt% of Ca are characterized by worse mechanical characteristics and prolonged aging time. Alloys with Ca content beyond the given limit, solidify very fast but corrode faster, and due to this reason the higher Ca concentration at the alloy surface causes the increase in alkalinity of the electrolyte nearby, caused by the increase in dissolved Ca concentration. Namely, it is well known that lead and lead alloys corrode faster in alkaline solution, because of the increased solubility of lead compounds in alkaline solutions [19]. Precipitation of Pb3Ca at grain boundaries improves the mechanical strength of PbCa alloys, but simultaneously Ca at the surface makes the nearby electrolyte more alkaline [3]. On the other hand, tin with calcium forms Sn3Ca that is more corrosion resistant. At lower Sn/Ca ratios a mixed and discontinued [Pb(1x) Snx]3Ca (0  x  1) precipitate is formed in the alloy, which worsens corrosion resistance. When concentration ratio of Sn/Ca in the alloy is beyond 9:1 primary precipitate at grain boundary is Sn3Ca. Practically, Sn/Ca ratio is usually chosen to be 12, while some authors prefer ratios near 20. In addition, tin improves and stabilizes wrought microstructure of alloys [29]. Here, the corrosion characteristics of the thermo-mechanically treated basic commercial PbCa alloy and three additionally alloyed PbCaSnAg alloys are explored in 15 and 36 wt% water solution of sulfuric acid. The corrosion behavior of the alloys is discussed in terms of the influence of tin and silver addition as well as their thermo-mechanical treatment on their microstructure. The intention of this research is to obtain adequate material for the production of rolled sheet metal, suitable for cutting of the electrode grids for leadacid batteries, by modification of the starting commercial PbCa alloy that is previously used for continuous casting of electrode grids, by additional alloying with tin and silver, and by proper thermo-mechanical treatment.

Table 2. Chemical composition of the alloys after preparation and thermo-mechanical treatment (main alloying elements)

Alloy Ca
1 2 3 4 0.070 0.070 0.075 0.075

Composition, wt% Sn
0.00096 1.10 0.72 1.10

Ag
0.00045 0.0003 0.0003 0.02

Mechanical preparation of samples for optical microscopy is provided by standard procedures of grinding and polishing [4, 10]. The chemical etching at room temperature in two reagents exposed the microstructure of alloys. The primary reagent was a solution of three parts of acetic acid and one part of hydrogen peroxide in water, and the following one was a solution of 10 g ammonium molibdate and 10 g citric acid in 100 cm3 of deionized water [10]. 2.3 Potentiodynamic polarization experiments The dependencies E-log j are obtained by potential sweep technique in three-compartment electrochemical cell. The potential sweeps with rates of 0.3 and 1 mV s1 are generated with potentiostat/galvanostat PAR model 273, coupled with computer equipped with analog/digital converter ED 2000, Electronic Design, for data acquisition and recording. The chosen concentrations of experimental solution, 15 and 36 wt% of sulfuric acid in water, correspond to the electrolyte in the discharged and fully charged states of the leadacid SLA battery, respectively. The temperature of experimental solution was approximately 25 8C. The electrolyte is prepared with analytical grade reagents and deionized water. The samples for potential sweep measurements are prepared from the sheet metal, obtained after thermo-mechanical treatment, by cutting in rectangular shape and isolation of the sides with the acid-resistant epoxy resin, leaving uncovered 1 cm3 of the surface. Before measurements, electrode surface is cleaned by grit paper and polishing. Electrode potentials are measured against Hg/Hg2Cl2 (3.5 M KCl) reference electrode. 2.4 Weight loss measurement of corrosion rate

2 Experiments
2.1 Materials One PbCa and three PbCaSnAg alloys, with composition shown in Tables 1 and 2, are examined on the influence of their microstructure on the corrosion behavior in 15 and 36 wt% water solution of sulfuric acid. The alloying of commercial base alloy is completed in laboratory conditions according to the proper technological procedure. 2.2 Microstructure determination The micrographs of the alloy microstructure after the thermomechanical treatment are obtained by optical microscopy.

The corrosion resistance of the alloys at open circuit potential (OCP) is examined by measuring of the weight loss of sheet samples (thickness of 1.5 mm with base area of 10 20 mm2)

Table 1. Chemical composition (wt%) of basic commercial Pb0.0882Ca alloy

Element
wt%

Ca
0.0882

Fe
0.00055

Ni
<0.00010

Cu
0.00019

Al
0.0120

Ag
0.00045

Cd
<0.00010

Sn
0.00096

Element
wt%

As
0.00078

Sb
0.00092

Bi
0.0165

S
<0.00030

Se
<0.00020

Te
0.00029

Zn
0.00033

Pb
99.9

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Corrosion rate of PbCa alloys in sulfuric acid solutions

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after 32 days of corrosion in 36 wt% water solution of sulfuric acid at a temperature of 40 1 8C. After exposure to the corroding solution, samples (five of each of the alloys) were thoroughly rinsed in deionized water. The corrosion products, from the samples, are removed by their dissolution in water solution of 100 g l1 KOH 50 g l1 KI 200 g l1 Na-tartarate at 30 8C [11]. Samples, previously washed in deionized water and then in absolute methanol and dried in warm air, are weighted on the analytical balance.

3 Results and discussion

The basic commercial PbCa alloy, of the composition shown in Table 1, is used as a starting material for manufacturing of ternary and quaternary alloys and as reference material for the evaluation of characteristics of new alloys. The chemical composition of examined alloys is shown in Table 2. 3.1 Thermo-mechanical treatment of cast alloys into sheet metal The material for electrochemical and corrosion tests of the alloys is prepared by thermo-mechanical treatment of the casted ingots by the procedure shown in Fig. 1, in course to afford required microstructure. The microstructure of the alloys is controlled through suitable sequence of thermo-mechanical treatments of the casted alloy block: the annealing, the dissolving annealing, and the controlled aging in argon atmosphere, before and after cold rolling. After each step, annealing samples are quenched in cold water. Finally, obtained sheet samples were aged at 90 8C and stored at a room temperature. 3.2 Metallographic analysis of microstructure Figures 25 show typical microstructure of prepared samples of the examined alloys. It is obvious from Fig. 2 that, because of pronounced segregation of Ca as Pb3Ca, alloys with content of 0.060.07 wt% Ca need further alloying with 1.01.2 wt% of Sn [6] to obtain homogenous microstructure, like that in Figure 3. Preferred formation of Sn3Ca at the expense of Pb3Ca is possible with the ratio of Sn/Ca which must be at least 9:1, because Sn segregates in much greater extent at grain boundaries, than in the central zones, and Ca segregates primarily in central zones. Given the Ca concentration of 0.08 wt% in the alloy, Sn/Ca ratio needs to be 12:1 or even 15 to 20:1. It is seen from Figs. 4 and 5 that concentration of tin in the alloy should be 1.1 wt% to obtain its positive effect on the microstructure refinement, as well as the addition of 0.02 wt% of silver [1, 5, 6, 10, 11]. 3.3 Electrochemical measurements The OCP of the alloys in the corresponding electrolyte, Ee, is shown in Table 3. OCP is virtually independent of the alloy composition, and very close to the equilibrium potential of Pb/ PbSO4 couple in such solutions. Shift of Ee toward more negative
Figure 2. Alloy no. 1: A fine precipitate of Pb3Ca in the central zone of grains is seen, as Pb3Ca precipitates rather in central than in boundary zones [6]. Rolling direction !

Figure 1. Regime of thermo-mechanical processing of cast alloys into sheet

Figure 3. Alloy no. 2: Much bigger grains with much shorter grain boundaries, and more homogenous microstructure compared to Fig. 2 is obvious. Rolling direction !

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Figure 4. Alloy no. 3: Less homogenous, longer grain boundaries, and Sn3Ca segregate at grain boundaries compared to alloy no. 2, as seen in Fig. 3. Rolling direction ! Figure 6. Dependencies E-log j for alloys in 15% H2SO4 solution, at potential sweep rate of 1 mV s1

Figure 5. Alloy no. 4: Big grains and more regular grain boundaries with segregates at inter-crystalline zones are characteristics of quaternary alloy [10, 11]. Rolling direction !

fold decrease in 36 wt% solution. In addition, the passive current density is the smallest for alloy 4 under all experimental conditions. The differences in electrochemical behavior of the alloys are possibly consequences of different chemical compositions and the microstructure of the alloys. The microstructure of the alloys 24 is noticeably more homogenous, particularly that of the alloys 2 and 4, with bigger and more regularly shaped grains, as seen from Figs. 25. Such a microstructure is in favor of the increased corrosion resistance in those alloys, which are already discussed in the literature [6, 1214]. The difference of E-log j dependencies in the potential region between 0.5 and 0 V against Hg2Cl2 (3.5 M KCl) electrode between alloys 12 and alloys 34 may be consequences of a longer (3 months) room aging of the first two. It seems that

values in the solutions of higher acid concentrations is expected, because of the increased acidity. Figures 69 show E-log j dependencies for the alloys in the two electrolytes. The E-log j dependencies recorded for the primary alloy 1 and the modified alloys 24, seen on Figs. 69, show clear differences between them in the passive region. Values of the current densities in the passive region are noticeably smaller for the alloys 24 in relation with alloy 1, and show approximately two- to threefold decrease in 15 wt% sulfuric acid solution and more that five-

Table 3. OCP of alloys after 1 hour of immersion

Alloy no.
1 2 3 4

Ee, mV vs. Hg/Hg2Cl2 (3.5 M KCl) 15% H2SO4

545 540 540 547

Ee, mV vs. Hg/Hg2Cl2 (3.5 M KCl) 36% H2SO4

578 579 567 571

Figure 7. Dependencies E-log j for alloys in 15% H2SO4 solution, at potential sweep rate of 0.3 mV s1

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Corrosion rate of PbCa alloys in sulfuric acid solutions

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Figure 8. Dependencies E-log j for alloys in 36% H2SO4 solution, at potential sweep rate of 1 mV s1

tin-rich [Pb(1x)Snx]3Ca (x 0 1) faces inside grains are more pronounced in alloys 3 and 4. Stability of the corrosion layer at anodic polarization of lead and its alloys depends on the possibility of establishment of the conditions necessary for the formation of lead sulfate (PbSO4), tri(3PbO PbSO4 H2O) and tetra- (4PbO PbSO4) basic lead sulfates, lead hydroxide [Pb(OH)2] and at higher potentials lead dioxide and higher lead oxides [15, 16]. Within pores of the corrosion layer solubility of lead increases, because of the more or less alkaline electrolyte caused by the sulfate ions deficit. As noticed earlier, the alkalization of corrosion layer is furthermore increased by the presence of calcium on the surface of PbCa alloys. Tin also forms soluble species in the process of anodic polarization, see Table 4. All of these processes explain instability of passive layer at lower anodic potentials, what is seen from the E-log j dependencies. At the higher anodic potentials higher tin oxides engender in corrosion layer and stabilize it. Positive influence of tin on the stability of anodic layer on ternary (PbCaSn) and quaternary (PbCaSnAg) alloys is further discussed [2] in terms of the following chemical reactions, PbOH2 Sn ! Pb SnO H2 O PbOH2 SnO ! Pb SnO2 H2 O In that way tin suppresses formation of soluble lead hydroxide, that emerges in alkaline solutions within pores of corrosion layer of the calcium containing alloys, by its oxidation to tin oxide and reduction of lead hydroxide to lead. The passivation potential of the alloys that contain tin (and silver) is shifted toward positive potentials for 0.20.3 V, probably because of the tin dissolution that disturbs formation of uniform protective layer, but at more positive potentials the effect of tin present in the corrosion layer overcomes the negative one and the uniform layer forms suppress further corrosion [1214]. Instability of the corrosion layer is more pronounced for the freshly prepared alloys 3 and 4, probably because of the unfinished process of recrystallization. It is to be noted that current density of the passive region is constant in 15 wt% sulfuric acid solution while in 36 wt% solution passive current density gradually increases with the race of anodic potential, what is more evident for basic PbCa alloys. Evidently, in 36 wt% solution, the corrosion layer of the alloys in the state of the process of permanent formation and disruption, is stabilized in the presence of tin compounds in the corrosion layer. The pitting potential of the modified alloys is, for about 150 mV, shifted toward the cathodic direction (pitting appears earlier) in relation to the same of the primary PbCa alloy, which

Figure 9. Dependencies E-log j for alloys in 36% H2SO4 solution, at potential sweep rate of 0.3 mV s1

prolonged aging gave effect in further homogenization of the grains in alloy 2 compared to alloys 3 and 4, which obviously were not fully completed in the process of homogenization at 90 8C after rolling. Incomplete homogenization of the alloys is already seen in Figs. 25, where dark regions of segregated
Table 4. Possible electrochemical reactions at tin electrode

Reaction
Sn2 2e ! Sns Sn4 2e ! Sn2 Sn4 2e ! Sn2 HSnO2 3H 2e ! Sns 2H2 O 2 H2 O SnO2 3 3H 2e ! HSnO 2 2 ! Sn 3H2 O SnO3 3H 2e

Ee, V vs. 3.5 M KCl Hg2Cl2

0.410 0.110 0.096 0.083 0.124 0.594

Comment
(1 M HClO4) (1 M HCl)

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Materials and Corrosion 2010, 61, No. 1

Table 5. Weight loss data and the rates of corrosion for alloys in 36% sulfuric acid at 30 8C

Alloy no.
1 2 3 4

m1, g
33.4533 34.1576 30.7699 31.8248

m2, g
33.0626 34.0264 30.6519 31.6990

Dm, g
0.3907 0.1312 0.1180 0.1258

Dm/m1, mg g1
11.68 3.84 3.83 3.95

Dm/m1 100, %
1.18 0.38 0.38 0.40

(Dm/m1)/n, mg g1 day1
0.37 0.12 0.12 0.12

Vcorr , mg cm2 day1

3.05 1.03 0.92 0.98

Note: m1 initial sample mass; m2 sample mass after corrosion; Dm m1m2 weight loss; Dm/m1 relative weight loss; (Dm/ m1) 100% percentage of weight loss; n days of corrosion exposure (n 32); Dm/(m1 n) relative corrosion rate (mg g1 per day); Vcorr corrosion rate (mg cm2 per day). is the consequence of Sn dissolution and its influence on the homogeneity of the passive layer [17]. The picture of the corrosion process is obviously very complex and it is hard to give a clear explanation of all the processes that take part in it, but it is clear that alloying of the Pb Ca alloy with tin and silver give very positive contributions to the corrosion stability of the alloys throughout refinement of their microstructure. 3.4 Determination of corrosion rate at open circuit potential (OCP) The corrosion rate at OCP is determined from the average weight loss of each alloy (five samples of each alloy), presented in Table 5. From the results seen from Table 5, it is obvious that the alloying of the PbCa alloy (alloy 1) with tin (alloys 2 and 3) and tin and silver (alloy 4) has a positive influence on the increase in the corrosion resistance of the modified ones. The corrosion rate of the modified alloys 24 has shown approximately three-fold decrease relative to the PbCa alloy. Those results are in agreement with the results obtained in potential sweep measurements. The increase in corrosion stability of the alloys with the addition of tin and silver is explained not only by the change in composition of the corrosion layer but also by the refinement of the microstructure of modified alloys. Addition of tin to primary PbCa alloy provokes formation of the new phase [Pb(1x) Snx]3Ca (0  x  1) at grain boundaries, that is more corrosion resistant than in Pb3Ca phase, formed in the PbCa alloy. In our experiments the ratio of Sn/Ca was 10:1 in the alloy with 0.7 wt% Sn, while this ratio exceeds 15.7:1 in the alloy with 1.1 wt% Sn, which confirmed the positive effect of the Sn3Ca precipitation at the grain boundaries [1]. In addition, tin species present in the corrosion layer of the alloys gave positive influence on its stabilization. Thermal treatment after the rolling process, fast quenching in cold water, gave additional beneficial effect on corrosion stability of the alloys. In course of the solidification process, tin and silver segregates at the grain boundaries, in the inter-dendrite space as well as inside the grains. As a result, very small corrosion resistant cells are formed in those regions, as seen in Figs. 4 and 5. The additional constriction of the spaces between the grains during the quenching process, beneficially suppresses the intercrystalline corrosion [14, 15, 1820]. In course of thermal treatment, tin from the alloys segregates preferentially at grain boundaries reacting with calcium that precipitates in that zone with formation of Sn3Ca which, besides having a positive impact on mechanical strength, significantly improves the corrosion stability of the alloys [25, 21].

4 Conclusions
The procedure of successful modification of PbCa alloy designed for continuous casting of the electrode grids for leadacid batteries into the alloy intended for mechanical preparation of the electrode grids by cutting is developed. The microstructure and corrosion resistance in the sulfuric acid electrolyte of the alloys obtained in the process of modification are explored. Several conclusions are drawn from this investigation: (1) The considerable enhancement of corrosion resistance of modified PbCaSnAg alloys, reflected in three- to five-fold increase in corrosion resistance, is recorded because of the modification. (2) Photomicrographs taken by optical microscopy have shown that the increase in the addition of tin and the increase in silver content gave positive effect on the microstructure refinement of the primary PbCa alloy. (3) The microstructure of the alloys can be successfully controlled in the course of suitable thermo-mechanical treatments of the casted alloy block in the following sequence: the annealing, the dissolving annealing, and the controlled aging in argon atmosphere, before and after cold rolling. Acknowledgements: Authors gratefully acknowledge the financial support for this work from the Ministry of Science, Republic of Serbia, under project no. 401-00-236/2007-01/41. from Institute of Authors are also indebted to Dr. Ilija Bobic a, Belgrade, Materials, Institute of Nuclear Sciences Vinc Serbia, for the careful preparation of the specified casted alloy ingots used in this project.

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