Effect of the Current Density on Electrodepositing Alpha-Lead

Acta Metall. Sin.(Engl. Lett.)Vol.22 No.5 pp373-382 October 2009

Eﬀect of the current density on electrodepositing alpha-lead dioxide coating on aluminum substrate Buming CHEN, Zhongcheng GUO ∗, Hui HUANG, Xianwan YANG and Yuandong CAO Faculty of Materials and Metallurgical Engineering, Kunming University of Science and Technology, Kunming 650093, China Manuscript received 22 September 2008; in revised form 13 March 2009

The α-PbO2 electrodes are prepared by anodic electrodeposition on A1/conductive coating electrode from alkaline plumbite solutions in order to investigate the effect of the different current densities on the properties of α-PbO2 electrodes. The physicochemical properties of the α-PbO2 electrodes are analyzed by using SEM, EDS, XRD, Tafel plot, linear sweep voltammetry (LSV) and A.C. impedance. A compact and uniform layer of lead dioxide was obtained at the current density of 3 mA·cm−2. A further increase in current density results in smaller particles with high porosity. EDS and XRD analyses have shown that the PbO2 deposited in alkaline conditions is highly non stoichiometric, and the PbO impurities are formed on the surface layer besides the α-PbO2. The corrosion resistance of α-PbO2 at the low current density is superior to that of the high current density. It can be attributed to a porous layer of deposited films at high current densities. When used as anodes for oxygen evolution 2+ −1 −1 in aqueous Zn 50 g·L ,H2SO4 150 g·L , the Al/conductive coating/α-PbO2 exhibits lower potential compared to Pb electrode. Al/conductive coating/α-PbO2 electrode with the best electrocatalytic activity was obtained at current density of 1 mA·cm−2. The lowest roughness factor was obtained at 1 mA·cm−2. KEY WORDS Alpha lead dioxide; Electrodeposition; Current density; Anodes; Oxygen evolution

1 Introduction

At present, the lead alloys[1,2] containing small amounts of silver, tin, calcium or an- timony have been widely used as insoluble anodes in zinc electrowinning industry. The anodes can meet the need of zinc electrowinning, but oxygen overpotential of the anodes is still high. Lead ions dissolved in the electrolyte can be produced at the cathode and con- taminate the zinc metal[3]. Various kinds of the metal oxides anodes for oxygen evolution [4] [5,6] [7] reaction (OER) were developed, such as RuO2+TiO2 , IrO2+MnO2 , IrO2+Ta2O5 . All of these anodes, so called dimensionally stable anodes (DSAs), have better electrocatal-

∗Corresponding author: Professor, PhD; Tel.: +86 871 8352598. E-mail address: [email protected] (Zhongcheng GUO)

DOI: 10.1016/S1006-7191(08)60111-8 · 374 · ysis. However, DSAs are of limited service life at high anode potential[8] and have not been used extensively in electrowinning operations mainly due to cost. Lead dioxides have been used frequently in electrocatalysis and industrial application because of its excellent properties such as good conductivity, low cost, high stability and relatively high service life. The lead dioxide of electrodepositing is known to exist in two polymorphs: orthorhombic α-lead dioxide and tetragonal β-lead dioxide[9]. It is well known that the crystal structure of PbO2 deposited depends on the pH of the electroplating [9] solution: α-PbO2 is obtained from bases, β-PbO2 from acids . The α-PbO2 has a more compact structure than β-PbO2, which results in better contact between the particles. The more compact structure makes the α-PbO2 more difficult to discharge compared to the β- [10] [11] [12] PbO2 . Rüetschi and Feng et al. show that the α–PbO2 has a higher catalytic activity than β-PbO2 in dilute H2SO4 solution. [13,14] A new type of PbO2-coated metal anode has been widely used in electrolysis . This electrode consists of four layers: the base is a titanium plate, which is covered with a conductive undercoating (such an undercoating is necessary for protecting the substrate from passivation) as bottom, on which an α-PbO2 coating as the intermediate layer and finally β-PbO2 as the surface layer. Titanium is not, however, a viable substrate for practical electrodes in electrodepositing nonferrous metals. Aluminum is relatively cheap and has good conductivity. The electrode material by electrodepositing lead dioxide on Al substrate has a huge market prospects. A stress-free intermediate α-PbO2 coating is produced by electrodeposition from an alkaline lead bath[15]. It plays a role of binder on the top β-PbO2 coating and can improve the serve life of electrode. However, the alpha-lead dioxide films deposited from basic solution are of highly porosity[16,17] and the research work is confined to the internal stress measurement[15]. Methods of preparation of alpha lead dioxide as well as their characteristics have been reviewed[9]. The alpha-form, deposited from neutral and alkaline solution, has the cobumbite form[12,18]. It is claimed that the current density has significant effect on the phase composition and properties of alpha lead dioxide[17]. In this study the method of electrochemical anodic deposition was adopted to obtain alpha lead dioxide coating from alkaline plumbite solutions by different values of current density on Al/conductive coating substrate. The effect of the current density on the structure and physicochemical properties of the deposited lead dioxide coating were discussed.

2 Experimental

2.1 Preparation of the PbO2/Al anode The PbO2/Al anode was produced by applying to an Al substrate with a conductive undercoating, then covering the undercoating with a coating consisting of the α-PbO2 deposit. The substrates were aluminum rods with 60 mm in length and 9 mm in diameter, which were roughened by sand-blasting, degreased and chemically etched, then coated with a conductive coating. The procedure was described as follows: ﬁrstly, the conductive coating solution was applied to the substrate by brushing; secondly, the substrate was dried under ultraviolet lamp for surface drying, and ﬁnally dried in electricity box at 423 K for 2 h. The undercoating produced in this study was about 20 µm thick. The electrodeposition of · 375 ·

the α-PbO2 was carried out under the following condition; 4 M NaOH with PbO(s) (the − −2 soluble Pb(II) species were HPbO2 anions), pH>14, anode current density 1–5 mA·cm , mild stirring using a magnetic stirrer, bath temperature 40 ◦C, and electroplating time 2 h.

2.2 Characterization of PbO2/Al electrode The surface morphology of the coatings was examined by SEM (XL30 ESEM, Philip, Holand). The crystalline compositions of the films were determined by using EDS (PHOENIX, EDAI, USA). The crystalline structure of the films was studied by X-ray diffractometer (using CoKα radiation, D8ADVANCE, Bruker, Germany). 2.3 Electrochemical measurement A single three-electrode compartment cell system was employed. Al/conductive coating/α-PbO2 anode as the working electrode, Hg/Hg2Cl2 (KCl, saturated) as the reference electrode, and a graphite as the auxiliary electrode. Typical anodic potentiodynamic polarization curves and anodic polarization curves were measured at 25 ◦C in Zn2+ −1 −1 50 g·L +H2SO4 150 g·L solutions with a CHI660C electrochemical workstation. Electrochemical impedance measurement was carried out in the 4 M NaOH solution at 25 ◦C with frequency range from 0.1 Hz to 100 kHz. The amplitude of the ac signal was 5 mV. The operating potential of 0.1 V was selected. The impedance data were converted into Nyquist data format, and then fitted to appropriate simulative circuits.

3 Results and Discussion

3.1 Surface morphological studies Fig.1 shows the SEM of deposited alpha lead dioxide on Al/conductive coating electrode from solution containing 4 M NaOH saturated with PbO(s) at different current densities. Figs.1a–e are the microstructures at 2000 amplification with the current density of 1, 2, 3, 4 and 5 mA·cm−2 respectively, Figs.1a0–e0 are that at 10000 amplification with the −2 current density of 1, 2, 3, 4 and 5 mA·cm respectively. The surface of PbO2 deposited at 1 mA cm−2 consisted of crystals of large size with surface uniformity (Fig.1a0). At −2 0 current density of 2 mA·cm (Fig.1b ), the PbO2 surface becomes more uniform consisted of rod-like grains. Further increasing the current density, there are a large number of small crystals without clear crystal edges (Fig.1c0). The film exhibits a fiber texture with good orientation and is recrystallized into the oriented fiber texture on standing in surface layer −2 of the formed film. At current density of 4 mA·cm or higher, however, the PbO2 films of the fiber texture are randomly oriented and highly porous. A comparison between Fig.1d0 and e0 reveals that the clear crystal edges are appeared at 4 mA·cm−2. It is interesting to note that increasing of current density from 1 to 5 mA·cm−2 causes to decrease the diameter of the fiber. The fiber structure of the alpha lead dioxide deposit may be the result of complex- ity of lead cation in the electrodeposition solution. It has been reported[17,19] that PbO − dissolve in alkaline solutions with formation of biplumbite ion HPbO2 and, to a lesser extent, polynuclear complexes. It seems probably that oxidation of such complexes can 2− lead to polynuclear complexes containing PbO3 . The hydrolysis of such species follows the oxidation on the electrode, thus the deposition rate of α-PbO2 is slow. At high current densities the solid oxide may precipitate at some distance from the electrode surface due to the increased concentration of the complexed Pb(IV) cations. The agglomeration of · 376 ·

◦ Fig.1 SEM photographs of α-PbO2 prepared from 4 M NaOH saturated with PbO(s) (40 C) on Al/conductive coating electrode for 2 h at a current density of (a) 1, (b) 2, (c) 3, (d) 4, (e) 5 mA/cm2, a0, b0, c0, d0 and e0 are at higher magniﬁcation of Fig.1(a), (b), (c), (d) and (e), respectively · 377 · such precipitates on the surface coatings can lead to a randomly oriented surface, also, at − the high current, the oxidation of HPbO2 to PbO2 (reaction 1) in an aqueous electrolyte, Oxidation of water to oxygen (reaction 2) can also take place simultaneously.

− + HPbO2 = PbO2 + H + 2e (1) + 2H2O = O2 + 4H + 4e (2) As a result, at higher current densities the increase in pores of the coating is due to an increased rate of oxygen evolution (reaction 2) or due to the loss of the PbO2 deposit. At low current densities precipitation would take place near the electrode and at a slower rate, allowing enough time for the crystal nucleus to find the most suitable position and equilibrium state forming the particles of α-PbO2. The adsorption of anions on the crystallites might lead to the stability of an ordered fiber structure. 3.2 Compositional and crystallographic analysis EDAX spectra of PbO2 films deposited at different conditions are shown in Table 1. It shows a remarkable change of the Pb contents in alpha PbO2 film at different current densities. The Pb content raises from 32.17% to 40.42% between 1 and 4 mA·cm−2 and then fall to a value of 33.59% for current densities of 5.0 mA·cm−2. This phenomenon may + be explained as follows. The H ions are generated at the anode during PbO2 deposition. This results in a decrease of the local pH at the interface. Delahay and Pourbaix[19] show that the solubility of Pb(II) exhibits a minium at pH=9.4. Therefore, the local decrease of the pH from a highly alkaline solution induced a decrease of the solubility of Pb(II) at the interface, and precipitation of lead hydroxide was possible from the concentrated plumbite solution, our results are in agreement with those of Devillers[18] who reported that the PbO2 deposited in alkaline conditions is highly non stoichiometric. The corresponding X-ray spectra are presented in Fig.2. Attribution of the peaks is performed by using JCPDS data. The XRD results obtained for the α-PbO2 prepared at various current densities are given in Table 2. The XRD pattern of α-PbO2 prepared from alkaline solution indicates the presence of

PbO. The impurity is attributed to the co- 00) deposition of an insoluble Pb(II) compound (2

-PbO

from the alkaline plating solution containing PbO

lead hydroxide Pb(OH)2 or the oxide PbO. ) ) ) 2 3

[20,21] 0 00 (132

In agreement with literature , the (200) ( (2

1 mA/cm

line has the highest intensity. At the high 2

2 mA/cm Intensity / cps

2 densities, PbO may be present (the peaks at 3 mA/cm

2 ) ◦ 4 mA/cm 0)

2θ=57.96, 59.22 and 68.21 ), but only a few 22 0 ( (22 2

5 mA/cm Table 1 Compositional analysis of PbO2 ﬁlms

deposited at diﬀerent current densities 40 50 60 70 80

2 / deg. Atomic Current density/mA·cm−2 (Fig.1) Fig.2 XRD spectrums of α-PbO2 prepared from percentage 1 2 3 4 5 4 M NaOH saturated with litharge PbO(s) ◦ O 67.83 65.53 61.14 59.58 66.41 (40 C) on Al/conductive coating electrode for 2 h at a current density of 1, 2, 3, 4, Pb 32.17 34.47 38.86 40.42 33.59 and 5 mA·cm−2. · 378 ·

Table 2 XRD data for α-PbO2 electrodeposited at various current densities Current Relative intensity of (hkl) indexation JCPDS data density/mA·cm−2 (002) (200) (132) (203) (022) (220) 1 0.71 100 5.81 1.82 2 0.90 100 4.94 1.53 3 0.84 100 9.27 2.74 4 0.67 100 12.95 2.6 5 0.78 100 23.55 4.79 4.10 1.19 amounts are found. The (132) line of the

α phase is increased with the increasing of -1.5 −2 the current density from 2 to 5 mA·cm . -2.0

-2.5

It is important to note that the preferred 4 orientation of α phase strongly depends on -3.0 3 ) 5 [17,21,22] -2 -3.5 the electrodeposition current density . 2 cm

-2

-4.0 1(1 m A cm ) / A Especially, at low current densities, α-PbO2 i ( -2

2(2 m A cm ) lg

-4.5 deposits are highly oriented. -2

3(3 m A cm )

-2

-5.0

4(4 m A cm )

-2

5(5 m A cm ) 3.3 Corrosion performance -5.5

Typical anodic potentiodynamic polar- 1.4 1.5 1.6 1.7 1.8 1.9

Potential / V(vs.SCE) ization curves of α-PbO2 obtained from 4 M NaOH saturated with PbO(s) (40 ◦C) Fig.3 Polarization curves obtained for α- PbO2 prepared from 4 M NaOH on Al/conductive coating electrode for ◦ 2+ saturated with PbO(s) (40 C) on 2 h at different current densities in Zn Al/conductive coating electrode for −1 −1 50 g·L +H2SO4 150 g·L solutions at 2 h at different current densities in ◦ 2+ −1 −1 25 C are presented in Fig.3. The corrosion Zn 50 g·L +H2SO4 150 g·L solutions at 25 ◦C. The current den- potential (Ecorr) and corrosion current den- −2 −2 sity (i ) calculated from the intersection of sity: (1) 1 mA·cm , (2) 2 mA·cm , corr (3) 3 mA·cm−2, (4) 4 mA·cm−2 and the cathodic and anodic Tafel curves using (5) 5 mA·cm−2. the Tafel extrapolation method are summa- rized in Table 3. By utilizing the informa- Table 3 Corrosion potential (Ecorr) and corro- tion in Fig.3 and Table 3, it can be observed sion current (icorr) for α-PbO2 coatings 2+ −1 −1 prepared at different current densities that in Zn 50 g·L +H SO 150 g·L −1 ◦ 2 4 in 150 g·L H2SO4 at 25 C solutions the corrosion potential has little changed, while the corrosion current density Medium Current density Ecorr icorr mA·cm−2 (V/SCE) A·cm−2 of α-PbO2 coating changes greatly. At the current density of 5 mA·cm−2, the corrosion 1 1.448 8.12×10−4 current density is the highest. While at the 150 g·L−1 2 1.450 1.18×10−4 −2 −4 current density of 2 mA·cm , the corrosion H2SO4 3 1.456 1.70×10 current density is the lowest. This reveals 4 1.449 5.03×10−4 that the coating with less porous possesses 5 1.457 8.97×10−4 a better corrosion resistance. The higher −2 corrosion rate of α-PbO2 coating produced at the current density of 1 mA·cm may be attributed to the lower corrosion resistance of the (200) plane as the preferred orientation.

3.4 Polarization curves Fig.4 shows the anodic polarization curves of the Al/conductive coating/α-PbO2 electr- · 379 · odes anodically deposited at diﬀerent current

densities. The anodic polarization curve of 0.40

0.35 -2 1

Pb electrode is also shown for comparison. 1(1 m A cm )

-2

2 0.30 2(2 m A cm ) The experimental polarization data obtained -2

-2

3(3 m A cm )

0.25 cm from the Fig.4 are handled with the linear re- -2 4(4 m A cm ) 4

0.20 -2

5 gression analysis by computer. On the basis 5(5 m A cm ) 3

Pb 0.15 of the overpotential (η) and current density Pb (i) relationships, some of the electrode ki- 0.10

0.05 netics parameters for oxygen evolution are Current density / A 0.00

shown in Table 4. The overpotential η(V) at -0.05 any current density is given by the following 1.6 1.8 2.0 2.2 2.4

Potential / V(vs SCE) Tafel equation[23]: Fig.4 Polarization curves of Pb and α- η = a + blogi (3) PbO2 prepared from 4 M NaOH saturated with litharge PbO(s) (40 ◦C) The value of the constant a, for the an- on Al/conductive coating electrode for 2 h at different current density in Zn2+ odic process, is −1 −1 ◦ 50 g·L , 150 g·L H2SO4 at 25 C, respectively. a = −2.303RT/γnF logi0 (4) and that of b is b = 2.303RT/γnF (5) where, a is the Tafel constant, V; b is the Tafel slope, V·dec−1; i is the current density, A·cm−2; R is the universal gas constant, 8.314 J·K−1·mol−1; T is the Kelvin temperature, K; n is the number of electrons transferred in the reaction; γ is the transferred coefficient; −2 i0 (A·cm ) is the exchange current density; F is the Faraday constant (96 487 C). The activity of electrocatalysts depends on electronic as well as geometric factors[24]. For a given current density the corresponding electrode potential is the function of the parameters affecting the OER kinetic (e.g. anode kinds, electrode morphology, electrolyte). Therefore, a simple way to study the electrocatalytic activity for OER is comparing, for a fixed current density, the dependence of the electrode potential on α-PbO2 and Pb, as shown in Fig.4 and Table 4. For a fixed current density, the overpotential and potential of −2 the Al/conductive coating/α-PbO2 electrodes deposited at 1 to 5 mA·cm are lower than that of Pb electrode. From these results, it is apparent that the catalytic activity of the

Table 4 Eﬀect of the electrode on the overpotential and kinetic parameters

−2 Electrode η/V a b i0/A·cm 10 mA·cm−2 100 mA·cm−2 −2 −4 α-PbO2 (obtained at 1 mA·cm ) 0.417 0.724 1.031 0.307 4.4×10 −2 −4 α-PbO2 (obtained at 2 mA·cm ) 0.425 0.734 1.043 0.309 4.18×10 −2 −4 α-PbO2 (obtained at 3 mA·cm ) 0.446 0.790 1.134 0.344 5.02×10 −2 −4 α-PbO2 (obtained at 4 mA·cm ) 0.475 0.782 1.090 0.308 2.86×10 −2 −4 α-PbO2 (obtained at 5 mA·cm ) 0.516 0.790 1.064 0.273 1.3×10 Pb 0.570 0.852 1.134 0.282 9.55×10−5 · 380 ·

Al/conductive coating/α-PbO2 is much superior to that of Pb for the anodic evolution of −2 oxygen. By contrast, the Al/conductive coating/α-PbO2 electrode obtained at 1 mA·cm maintains the best electrocalytic activity. It is clearly illustrated that the morphology of α- PbO2 has a fundamental eﬀect on the electrochemical behavior of the anode. It is suggested [25] that the anodic evolution of oxygen is related to the morphology of the α-PbO2 . On the other hand, the deposit thickness decreases with the decreasing of deposition current density, thus the conductivity of the electrode increases. This may be due to a decrease in [26] the contact resistance between the interlayer and the α-PbO2 layer .

3.5 Electrochemical impedance spectroscopy

EIS of the prepared anodes in the 4 M NaOH solution at open circuit potential

(OCP∼0.1 V) has been measured (shown in 80

Fig.5). The EIS data are accurately ﬁtted 2 cm to a Rs(Rf Qf )(RctQdl)L equivalent circuit in -2 1(1 m A cm )

-2

2(2 m A cm ) Fig.6 using Zsimpwin software. In the circuit -Z" /

-2

3(3 m A cm )

-2 the parallel (Rf Qf ) combination describes 4(4 m A cm )

-2

5(5 m A cm ) properties of the oxide ﬁlm, while (RctQdl) 0

combination presents the behavior of the in- 0 50 100

2 terface between oxide and electrolyte. Rs Z' / cm refers to uncompensated solution resistance. Fig.5 Impedance diagrams obtained for Al/ It is not exactly clear for the source of the conductive coating/α-PbO2 electrode at diﬀerent current density in 4 M small inductive element, L, possibly result- NaOH solution at E=0.1 V vs SCE. ing from wiring and measuring equipment components[27]. A typical order of this type of magnitude inductance is 1 µH, which is in good agreement with that observed in this work. Fig.6 Equivalent circuit used in the simula- Table 5 lists the parameter changes tion. in simulated circuit. It can be seen that −2 −2 with the increase of current density from 1 mA·cm to 5 mA·cm , the Qdl increased. The higher the current density is, the larger the Qdl is. The Qdl is coupled with the charge transfer resistance, the double layer capacitance, Cdl, can be evaluated from the following Eq.(6)[28].

Table 5 Impedance parameters of α-PbO2 electrodes in 4 M NaOH solution obtained ﬁtting to Rs(Rf Qf )(RctQdl)L circuit. Eappl.=0.1 V (SCE)

2 2 −1 −2 n 2 −1 −2 n Electrode Rs/Ω·cm Rf /Ω·cm Qf /Ω ·cm ·S n1 Rct/Ω·cm Qdl/Ω ·cm ·S n2 L/µH 1 0.51 310 1.0×10−2 0.88 26 1.2×10−2 0.76 0.92 2 0.56 304 1.2×10−2 0.85 24 1.6×10−2 0.73 0.93 3 0.61 300 1.4×10−2 0.82 20 1.9×10−2 0.77 0.87 4 0.46 310 1.0×10−2 0.81 8.7 2.3×10−2 0.79 1.02 5 0.74 222 5.9×10−3 0.65 16 2.5×10−2 0.90 0.77 · 381 ·

n −1 −1 (1−n) Q = (Cdl) [(Rs) + (Rct) ] (6)

The Cdl values are obtained from the Qdl values through Eq.(6), and n is a power factor related to the depression angle. Alves et al.[28] proposed a new approach for the in situ characterization of rough/porous oxide electrodes. Based on the procedure proposed, the double layer capacitance, Cdl, can be used as a relative measure of the surface area of the electrode. Table 6 lists the calculated capacitance and roughness factor. Roughness factors ∗ ∗ (RF) are calculated from Cdl/C assuming a reference value for the capacitance, C , −2 [29] of 20 µF·cm proposed for the smooth Hg electrode . RF values ranging between −2 −2 1 mA·cm and 5 mA·cm are obtained. The RF values normally observed with lead dioxide are frequently due to their characteristic morphology[30]. The lowest one is ob- −2 −2 tained at 1 mA·cm , after a sharp increase at 5 mA·cm . The increase of RF with current density suggests that surface roughening is enhanced when mass transfer limita- tions become signiﬁcant. This is in agreement with the observation from the SEM images.

Table 6 Calculated capacitance and roughness factor

−2 Electrode Cdl/µF·cm Calculated roughness factor −2 α-PbO2 (obtained at 1 mA·cm ) 2390 119.5 −2 α-PbO2 (obtained at 2 mA·cm ) 2770 138.5 −2 α-PbO2 (obtained at 3 mA·cm ) 4970 248.5 −2 α-PbO2 (obtained at 4 mA·cm ) 6770 338.5 −2 α-PbO2 (obtained at 5 mA·cm ) 15966 798.3

4 Conclusions

The influences of different current densities on the properties of the Al/conductive coating/alpha lead dioxide electrodes are investigated. The following conclusions are derived from the present study. (1) Applied current density during the deposition of PbO2 has a strong influence on the morphology of the prepared film. A compact and uniform layer of lead dioxide is obtained at the current density of 3 mA·cm−2, further increase in current density resulted in smaller particles with high porosity. (2) It is found by EDS that the PbO2 deposited in alkaline conditions is highly non stoichiometric. XRD spectra of deposited lead dioxide reveal that the PbO impurities are formed on the surface of electrode besides the α-PbO2. Corrosion resistance of α-PbO2 at the low current density is superior to that of the high current density. It can be attributed to a porous surface of deposited films at high current densities. (3) At a fixed current density, the OER overpotential of the Al/conductive coating/α- PbO2 electrodes is lower than that of Pb electrode. Al/conductive coating/α-PbO2 elec- −2 trode with the best electrocatalytic activity is obtained at 1 mA·cm . The lowest RF is obtained at 1 mA·cm−2, while the highest one is obtained at 5 mA·cm−2.

Acknowledgements—This study was ﬁnancially supported by the Author of National Excellent Doctoral Dissertation of China (No.20050053) and Analysis and Measurement Research Fund (2007-21) of Kunming University of Science and Technology. · 382 ·

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