RESEARCH NOTE pubs.acs.org/IECR
Effect of Glycine on the Electrochemical and Stress Corrosion Cracking Behavior of Cu10Ni Alloy in Sulfide Polluted Salt Water Ahmed Abdel Nazeer, Nageh K. Allam,* Gehan I. Youssef, and Elsayed A. Ashour Electrochemistry Laboratory, Physical Chemistry Department, National Research Centre, Dokki, Cairo 12622, Egypt ABSTRACT: Corrosion is a natural and inevitable problem that is still a challenge in materials design, with regard to achieving greater operational efficiency. In this study, the electrochemical and stress corrosion cracking (SCC) behavior of Cu10Ni alloy in a 3.5% NaCl solution in the presence of different concentrations of sulfide ions were studied. The presence of sulfide ions has been shown to increase the susceptibility of the material to SCC at different strain rates. The addition of glycine (gly) to the test electrolyte increased the time to failure by changing the mode of failure from brittle transgranular cracking to ductile failure. Therefore, gly can be considered as a potential environmentally friendly corrosion inhibitor. The electrochemical measurements showed that gly acts as a mixed corrosion inhibitor. The synergistic effect of potassium iodide (KI) and gly is also investigated. Electrochemical frequency modulation (EFM) and potentiodynamic polarization data are in good agreement with the SCC results.
1. INTRODUCTION Copper-base alloys are being heavily used as components in systems that are exposed to marine environments, because of their excellent electrical and thermal conductivities, good corrosion resistance, and ease of manufacture.1 However, it is now becoming more widely realized that copper and its alloys face service environments polluted by sulfide ions, which are in the form of hydrosulfide (HS) ions in almost-neutral media. These ions are known to promote the corrosion of copper and its alloys.24 To this end, Alhajji et al. compared the effect of sulfide, urea, and chlorine on the corrosion of Cu10Ni alloy in seawater environments and found that sulfide is the most severe pollutant, causing enormous deterioration of the material.5 Also, Allam et al. showed that the presence of a sulfide ion concentration as low as 2 ppm in salt water could result in significant deterioration of Cu10Ni alloy.3,4 Increasing the sulfide ion concentration from 200 ppm to 3120 ppm was also shown to result in a drastic increase in the corrosion current density of Cu10Ni and Cu30Ni alloys tested in sulfide-polluted seawater.6 Since stress corrosion cracking (SCC) is one of the limiting processes that hinder the use of copper-based alloys in industry, many studies are devoted toward understanding the behavior of such alloys when exposed to stresses in the work environment. For example, Thompson studied the SCC behavior of CuNi alloys and showed that they are practically immune to SCC in seawater.7 Popplewell and Gearing showed that only a few alloys among 25 coppernickel alloys are susceptible to SCC in industrial and marine environments.8 However, Islam et al.9 and La Que10 showed that CuNi alloys are susceptible to SCC, under slow strain-rate conditions, in concentrated sulfide solutions (g0.1 M), but not in dilute sulfide solutions (0.0020.03 M). Because corrosion has a significant impact on the economy, including infrastructure, transportation, utilities, production, and manufacturing, there are many studies that are devoted toward finding efficient procedures and treatments to protect metals and alloys against attack in many industrial environments.1114 In this regard, corrosion inhibitors made of organic compounds are r 2011 American Chemical Society
widely used to protect metals and alloys from corrosion. However, most of these compounds are synthetic chemicals that may be very expensive, toxic, and hazardous to living creatures and the environment. Therefore, the use of environmentally friendly inhibitors becomes one of the necessary protocols that should be adapted to protect metals and alloys against attack in many industrial environments. To this end, amino acids, which are nontoxic, relatively inexpensive, and completely soluble in aqueous media, have been recently tested as corrosion inhibitors in different media; promising results have been published.1520 The objectives of this work were to study the electrochemical and SCC behavior of Cu10Ni alloy in sulfide-polluted salt water and evaluate the effect of glycine (gly) on the susceptibility of Cu10Ni alloy to SCC in such media. Also, the synergistic effect of gly and KI on the corrosion inhibition efficiency was investigated. To the best of our knowledge, this is the first report on the use of amino acids to prevent SCC of Cu10Ni alloy in general and in sulfide-polluted environments in particular.
2. EXPERIMENTAL SECTION Tests were performed on a commercial Cu10Ni alloy specimen with the following composition: (in weight percent): 87.57 Cu, 10.68 Ni, 1.2 Fe, and 0.55 Mn. Specimens were provided by Abu-Qeer Power Station, Alexandria, Egypt, with the following mechanical properties: ultimate tensile stress (UTS) = 366.7 MPa, yield stress (YS) = 180 N mm2, elongation = 28%. Experiments were performed at constant strain rates of 1.8 106, 2.5 106, and 5 106 s1. The tensile stress was recorded on a chart recorder (J.J.CR552 - England). The test cell was in the form of a glass cylinder (120 mm in height and 80 mm in diameter). It was closed at the top and bottom by a rubber stopper through which the ends of the specimens protruded. The Received: April 10, 2011 Accepted: June 16, 2011 Revised: June 16, 2011 Published: June 22, 2011 8796
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Figure 1. Stressstrain curves of Cu10Ni alloy at a strain rate of 5 106 s1 in air and in 3.5% NaCl solutions containing different concentrations of sulfide ions.
Figure 2. Effect of sulfide ion concentration on the susceptibility of SCC at different strain rates.
Table 1. Stress Corrosion Cracking (SCC) Parameters of Cu10Ni Alloy in 3.5% NaCl in the Presence of Different Concentrations of Sulfide Ion at Different Strain Rates medium
σ (kg mm2)
Tf (min)
r
τ
S
Strain Rate = 1.8 106 s1 air
44.47
1100
8 ppm S2
43.39
1060
0.98
0.97
0.029
16 ppm S2
42.00
1040
0.94
0.94
0.056
20 ppm S2
41.47
1000
0.93
0.91
0.078
Strain Rate = 2.5 10
6 1
s
air
44.73
740
8 ppm S2
39.19
720
0.88
0.97
0.058
16 ppm S2 20 ppm S2
36.56 36.38
712 660
0.82 0.81
0.96 0.89
0.083 0.142
Strain Rate = 5.0 106 s1 air
49.70
450
8 ppm S2
42.39
410
0.85
0.91
0.114
16 ppm S2
41.33
400
0.83
0.89
0.137
20 ppm S2
39.33
397
0.79
0.88
0.157
lower end of the specimen was sealed to the lower rubber stopper by paraffin wax, to prevent leakage of the solution. The tensile test specimens were designed to have the following dimensions:
Before conducting the tests, the specimens were polished with 320, 600, and 1000 SiC grit papers, degreased with acetone, rinsed with distilled water, and coated with paraffin wax, so that only the gauge length was exposed to the test solution. Solutions were prepared from analar reagent-grade chemicals and doubledistilled water. Na2S was obtained from Riedel-de Haen, while glycine (gly) was obtained from Aldrich Chemical Co., Ltd. All
Figure 3. Stressstrain curves of Cu10Ni alloy at a strain rate of 5 106 s1 in air and in 3.5% NaCl + 20 ppm S2 alone and with different doses of glycine (gly) in the absence and presence of 100 ppm KI.
measurements were performed in a solution containing 3.5% NaCl, which has a salt level that is comparable to that of seawater. The potentiodynamic polarization measurements were performed using a PGZ100 Volta Lab potentiostat (Radiometer Analytical S.A.). A three-electrode electrochemical cell made of Pyrex glass, with a saturated calomel electrode (SCE) as a reference electrode, a platinum foil as a counter electrode, and Cu10Ni specimen as the working electrode, was used. Polarization measurements were performed at potentials in the range from 450 mVSCE to 150 mVSCE, at a scan rate of 0.33 mV s1. The electrochemical frequency modulation (EFM) data have been analyzed using Echem Analyst 5.21. In this work, a potential perturbation signal with an amplitude of 10 mV with two sine waves of 2 and 5 Hz was applied. The intermodulation spectra containing current responses were assigned for harmonical and intermodulation current peaks. The larger peaks were used to calculate the corrosion current density (icorr), the Tafel slopes (βc and βa), and the causality factors CF2 and CF3.
3. RESULTS AND DISCUSSION 3.1. Stress Corrosion Cracking (SCC) Behavior. 3.1.1. Effect of Sulfide Ions and Strain Rates. To determine the most severe 8797
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Table 2. Stress Corrosion Cracking (SCC) Parameters of Cu10Ni Alloy in 3.5% NaCl + 20 ppm S2 with Different Concentrations of Glycine at Strain Rate of 5 106 s1 σ (kg mm2)
Tf (min)
air
49.70
450
20 ppm S2 20 ppm S2 + 100 ppm gly
39.33 43.70
20 ppm S2 + 500 ppm gly 20 ppm S2 + 500 ppm gly +100 ppm KI
medium
toughness (MJ m3)
r
τ
S
397 420
0.79 0.88
0.88 0.93
0.157 0.090
213.2 269.8
46.62
420
0.94
0.93
0.064
282.8
48.02
430
0.97
0.96
0.039
298.2
321.2
Figure 5. Polarization curves of Cu10Ni alloy in 3.5% NaCl + 20 ppm sulfide (blank), blank + different concentrations of gly, and blank + 500 ppm gly + 100 ppm KI.
Figure 4. SEM fractographs of Cu10Ni alloy in (a) air, (b) 3.5% NaCl + 20 ppm S2 (blank) at a strain rate of 2.5 106, (c) blank at a strain rate of 5 106, (d) blank + 500 ppm glycine (gly), and (e) blank + 500 ppm gly + 100 ppm KI.
tested in sulfide-polluted media, compared to that tested in air (i.e., in the absence of sulfide). The susceptibility of the alloy to SCC (S)21,22 was estimated by the ratios of both the time to failure (τ) and the maximum stress (r) as S = [(1 r)(1 τ)]0.5 and summarized in Table 1, where tf ðsolÞ tf ðairÞ
ð1aÞ
σ max ðsolÞ σ max ðairÞ
ð1bÞ
τ¼ and
conditions under which Cu10Ni alloy will be susceptible to SCC, the stressstrain behavior was investigated in a 3.5% NaCl solution that was polluted with different concentrations of sulfide ions (8, 16, and 20 ppm) at different strain rates (1.8 106, 2.5 106, and 5 106 s1). Those sulfide ion concentrations were specifically chosen based on our previous study,19 which showed that those concentrations represent a severe and harsh testing environment. Figure 1 shows the stressstrain curves obtained at a strain rate of 5.0 106 s1. In general, the curves are characterized by an initial rapid increase of stress with increasing strain up to the yield stress, followed by a slight gradual increase (in the form of a plateau) to reach a maximum, after which the stress begins to decline to reach the point of failure. The corresponding data obtained in air are also included for comparison. It is noted that similar behavior was obtained upon the use of the other strain rates (1.8 106 and 2.5 106 s1 (not shown)). A considerable decrease in both ultimate tensile stress and the amount of strain was observed for the samples
r ¼
Although both r and τ slightly decrease as the concentration of sulfide ions added to the test solution increases, the susceptibility to SCC significantly increases with increasing sulfide ion concentration. It is noted that the increase in the value of S varies with the applied strain rate. For example, the increase in the value of S, at different sulfide concentrations, is more significant when using a strain rate of 5 106 s1, compared to lower strain rates (1.8 106 or 2.5 106 s1). Figure 2 summarizes those findings, where the susceptibility of Cu10Ni alloy to SCC increases as the concentration of sulfide ion, as well as the applied strain rate, each increase. At a sulfide ion concentration of 20 ppm, for example, the value of S doubles (from 0.078 to 0.157) upon increasing the applied strain rate from 1.8 106 to 5 106 s1. This is consistent with the results reported by Habib and Husain.23 Based on the obtained results (Table 1 and 8798
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Table 3. Effect of Glycine on the Free Corrosion Potential (Ecorr), Corrosion Current Density (icorr), Tafel Slopes (βa and βc), Percentage Inhibition Efficiency (IE%), Polarization Resistance (Rp), and Corrosion Rate (CR) of Cu10Ni Alloy in 3.5% NaCl + 20 ppm Sulfide Tafel Slopes (mV decade1) concentration (ppm) blank
icorr (μA cm2)
Ecorr (mV)
βc
βa
IE%
Rp
corrosion rate, CR (mm/yr)
2.27
127.7
10.92
328
166.0
87.0
blank + 100 ppm gly
6.26
321
165.0
123.1
42.67
4.90
73.21
blank + 250 ppm gly
4.90
316
147.2
134.8
55.13
6.24
57.30
blank + 500 ppm gly
2.87
309
139.9
122.2
73.72
9.88
33.56
blank + 500 ppm gly + 100 ppm KI
1.38
303
112.3
105.0
87.36
17.09
16.14
Figure 2), it seems that the most severe conditions needed for the SCC of Cu10Ni to occur are 20 ppm S2 at a strain rate of 5 106 s1. Based on the above results, the presence of sulfide ions can seriously promote the corrosion of Cu10Ni alloy. The first step is believed to be an initial adsorption process: HS ðaqÞ + Cu ¼ HS : Cu
ð2Þ
where HS:Cu refers to the adsorbed sulfide species on the bare copper surface. This adsorbed species catalyzes the anodic dissolution reaction: HS : Cu ¼ CuS + H+ + 2e
ð3Þ
The resulting sulfide scale (CuS and Cu2S), as well as dissolved sulfide,3,4 catalyzes the partial anodic (eq 3) and cathodic (eq 4) reactions: 1 O2 + H2 O + 2e ¼ 2OH 2
ð4Þ
The overall corrosion reaction is the sum of the two partial reactions (eqs 3 and 4), which can be represented as 1 HS : Cu + O2 ¼ CuS + OH 2
ð5Þ
Consequently, the rates of reactions 35 are affected by the sulfide ions that are adsorbed on the metal surface. 3.1.2. Effect of Glycine and KI. The possibility of using glycine (gly) as an environmentally friendly corrosion inhibitor was investigated for the SCC of Cu10Ni under the most severe conditions identified above (20 ppm S2 at a strain rate of 5 106 s1). Since KI was shown to act as a healing material for the ruptured passive films caused by the stress or strain of various surfaces,24,25 we aimed at studying the possible effects of combining KI and gly on the SCC of Cu10Ni alloy. Figure 3 shows the stressstrain curves obtained for Cu10Ni alloy samples tested in air as well as in electrolytes containing 3.5% NaCl + 20 ppm S2 in the presence of glycine alone and with 100 ppm KI. It is noted that the addition of glycine increases both the ultimate stress and strain values, compared to glycine-free electrolytes. Consequently, it decreases the susceptibility of the alloy to SCC (from 0.157 to 0.064) and improves the toughness (the area under the stressstrain curve) of the material (from 213 MJ m3 to 283 MJ m3), as shown in Table 2. Although increasing the gly concentration from 100 ppm to 500 ppm increases the ultimate stress, the strain remains almost constant. On the other hand, the addition of 100 ppm KI to the electrolyte containing 500 ppm of glycine resulted in a further increase in the ultimate stress and strain values, with an ∼50% decrease in
the susceptibility to SCC (0.039) than in the presence of glycine alone (0.064). Also note that the toughness increases from 282.8 MJ m3 to 298.2 MJ m3. This indicates the synergistic effect of KI and gly on improving the resistance of the alloy toward SCC in sulfide-polluted salt water. To gain insight into the surface morphology of the fractured surfaces, SEM investigation was performed. Figure 4 displays the obtained SEM micrographs of the fractured surfaces obtained in air and in 3.5% NaCl + 20 ppm S2 (blank) in the absence and presence of 500 ppm gly alone and with 100 ppm KI. It can be seen that the mode of failure in air (Figure 4a) is mainly ductile. However, in the presence of sulfide at a strain rate of 2.5 106 s1, the fracture mode was found to be mixed (brittle transgranular with few intergranular) (see Figure 4b). Upon increasing the strain rate to 5 106 s1, the fracture mode becomes brittle transgranular with the appearance of microcracks on the surface (Figure 4c). In the presence of gly alone (Figure 4d) and with KI (Figure 4e), the mode of failure changes from brittle transgranular to ductile failure, which is the same mode of failure obtained upon testing the material in air. The obtained results indicate that gly can act as a potential environmentally friendly corrosion inhibitor for the SCC of Cu10Ni alloy in a 3.5% NaCl solution containing sulfide ions. Also note the absence of cracks on the alloy surface when KI is added (see Figure 4e), which confirms the fact that KI can act a sealing compound for the ruptured passive film that exists on the alloy surface, because of stress or strain.24,25 However, it is important to note that the absence of cracking is not the only factor determining the immunity of the material to SCC.26 The inhibition effect of gly can be attributed to the adsorption of gly on the alloy surface, which inhibits of the anodic dissolution of the alloy by blocking the active sites on the alloy surface and subsequently the SCC. To gain further insight into the mode of inhibition (anodic, cathodic, or mixed) and to quantify the inhibition efficiency, we performed an electrochemical study of the alloy behavior in similar electrolytes used to study the SCC behavior. 3.2. Electrochemical Characterization. 3.2.1. Potentiodynamic Polarization. Figure 5 shows the polarization curves of Cu10Ni alloy in sulfide-polluted salt water (3.5% NaCl + 20 ppm S2) in the presence and absence of different concentrations of gly. In the presence of gly, the cathodic and anodic curves were shifted toward more-positive potentials, compared to that in the absence of gly. It is noted that the shift in free corrosion potential (Ecorr) also increases by increasing the gly concentration. Consequently, the corrosion current density (icorr) decreases as the gly concentration increases. For example, icorr decreases from 10.92 μA cm2 to 2.87 μA cm2 and Ecorr 8799
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Figure 6. Intermodulation spectra for (a) 3.5% NaCl + 20 ppm S2 (blank), (b) blank + 100 ppm glycine, (c) blank + 250 ppm glycine, (d) blank + 500 ppm glycine, and (e) blank + 500 ppm glycine + 100 ppm KI.
goes from 328 mV to 309 mV upon the addition of 500 ppm of gly to the test electrolyte (see Table 3). Note that the combination of KI and gly leads to a greater decrease in icorr, down to 1.38 μA cm2. The corrosion rate (CR), expressed in terms of mm yr1, and the inhibition efficiency (IE) in the presence of gly were calculated from the polarization curves using the following
equations:27,28
3:27 103 icorr EW CR ¼ D IE% ¼
8800
icorr icorr ðinhÞ 100 icorr
ð6Þ ð7Þ
dx.doi.org/10.1021/ie200763b |Ind. Eng. Chem. Res. 2011, 50, 8796–8802
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Table 4. Electrochemical Kinetic Parameters Obtained by EFM Technique for Cu10Ni Alloy in 3.5% NaCl + 20 ppm S2 (Blank) in the Absence and Presence of Different Concentrations of Glycine Alone and with KI Tafel slopes (mV decade1) concentration blank
icorr (μA cm2)
βa
βc
CF-2
CF-3
IE%
Rp
15.06
79
122
2.03
2.76
100 ppm gly
7.05
90
104
1.88
2.81
53.19
2.98
250 ppm gly 500 ppm gly
5.34 2.93
71 69
86 74
1.93 1.87
2.92 2.93
64.54 80.54
3.16 5.29
500 ppm gly + 100 ppm KI
1.91
59
63
1.91
2.95
87.32
6.94
where EW is the equivalent weight of the specimen, D is the density (g cm3), and icorr(inh) and icorr are the corrosion current density (μA cm2) in the presence and absence of gly, respectively. The values of different electrochemical parameters are summarized in Table 3. The addition of glycine resulted in the change of the slopes of cathodic (βc) and anodic (βa) Tafel lines (i.e., gly acts as a mixed-type inhibitor for Cu10Ni in sulfidepolluted salt water). Upon the addition of 500 ppm gly, it was possible to attain a maximum inhibition efficiency of 73.7% which is accompanied by a significant decrease in the corrosion rate from 127 mm/yr to 33 mm/yr. However, upon the addition of 100 ppm KI, the efficiency goes up to 87.4% and the corrosion rate decreases to 16 mm/yr. It is believed that the presence of negative ions, such as iodide, may enhance the adsorption of amino acids on the alloy surface29 and, thus, may be held responsible for the observed increase in the inhibition efficiency. 3.2.2. Electrochemical Frequency Modulation. Electrochemical frequency modulation (EFM) is an electrochemical technique in which two sinusoidal potential signals are summed and applied to a test sample through a potentiostat. The great strength of the EFM is the causality factors, which serve as an internal check on the validity of the EFM measurement.30 The results of EFM experiments are a spectrum of current response as a function of frequency. The spectrum is called the intermodulation spectrum. The spectra contain current responses assigned for harmonical and intermodulation current peaks. Figure 6 shows the intermodulation spectra obtained for Cu10Ni alloy in sulfide-polluted saltwater (3.5% NaCl + 20 ppm S2) in the absence and presence of different concentrations of gly alone or with 100 ppm KI. The larger peaks were used to calculate the electrochemical parameters (the corrosion current density (icorr), the Tafel slopes (βa and βc), and the causality factors (CF-2 and CF-3); see Table 4). Note that the corrosion current density decreases as the concentration of gly increases. The addition of KI resulted in greater diminishment of the current. The results obtained from the EFM measurements are in good agreement with those obtained from the potentiodynamic measurements. The inhibition efficiency (IEEFM (%)) was calculated from the EFM data, using the following equation:30
1.38
presence of KI is 87.32%, which is almost the same value obtained from the potentiodynamic measurements (87.36%), confirming the high accuracy of the results. Moreover, the calculated causality factors (CF-2 and CF-3) are very close to their theoretical values of 2 and 3, respectively, indicating that the measured data are of good quality.31 There clearly is a good agreement between the data obtained using EFM and potentiodynamic polarization techniques for the corrosion of Cu10Ni alloy in sulfide-polluted saltwater in the presence of gly alone or with KI. 3.2.3. Polarization Resistance. The polarization resistance (Rp) values can help to assess the relative ability of a material to resist corrosion, as indicated by the SternGeary equation:32 Icorr ¼
B Rp
ð9Þ
where Icorr is the corrosion current and B is the proportionality constant for a particular system, which can be calculated from βa and βc: B¼
βa βc 2:3ðβa + βc Þ
ð10Þ
ð8Þ
Note that the polarization resistance is inversely proportional to the corrosion current (i.e., the material with the highest Rp (and thus the lowest corrosion current) has the highest corrosion resistance and vice versa). From the calculated values of polarization resistance using the Tafel plots and EFM measurements (Tables 3 and 4, respectively), it can be seen that Rp increases as the gly concentration increases, as well as in the presence of KI. The low value of Rp in the absence of gly can be ascribed to the dissolution of copper, which is due to the formation of CuCl2 and Cu2S.19 In the presence of gly, a competitive surface adsorption between aggressive Cl and S2 ions, as well as gly molecules, is expected to occur,33 which decreases the alloy dissolution and, consequently, results in higher Rp values. Also, the synergistic effect between gly and I ions helps to stabilize the adsorption of gly molecules on the alloy surface through the negatively charged I ions. The I ions adsorbed on the metal surface form interconnecting bridges between the metal atoms and the positively charged glycine molecules, thus facilitating the adsorption process.34
where i0corr and icorr are the corrosion current densities in the absence and presence of gly, respectively. Note that IEEFM increases as the gly concentration increases in the same way as that observed from the potentiodynamic measurements. The addition of KI again resulted in a further enhancement in the protection efficiency. The maximum efficiency obtained in the
’ CONCLUSIONS The stress corrosion cracking (SCC) study, along with the metallographic observations, reveal that Cu10Ni alloys are susceptible to SCC in sulfide-polluted saltwater. The SCC increases as both the sulfide ion concentration and the applied strain rate increase. The addition of glycine (gly) to the test
IEEFM ð%Þ ¼
i0corr icorr 100 i0corr
8801
dx.doi.org/10.1021/ie200763b |Ind. Eng. Chem. Res. 2011, 50, 8796–8802
Industrial & Engineering Chemistry Research electrolyte resulted in the inhibition of the SCC of the alloy by increasing the time to failure and changing the mode of fracture from brittle transgranular cracking to ductile failure. This was also confirmed using electrochemical measurements such as potentiodynamic polarization and electrochemical frequency modulation (EFM). The study also reveals that gly acts as a mixed-type inhibitor. The synergistic effect between gly and I ions leads to a stabilized adsorption of gly molecules on the metal surface. Consequently, the inhibition efficiency increases from 73% to 87%.
’ AUTHOR INFORMATION Corresponding Author
*E-mail:
[email protected].
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