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Antihypertensive drugs as an inhibitors for corrosion of aluminum and aluminum silicon alloys in aqueous solutions
*Corresponding author. Tel.: +20133245674; fax: +20133222578 metwally555@yahoo.com (M. Abdallah)
-
Received: ,
Accepted: ,
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.
Available online 7 September 2010
Abstract
The corrosion behavior of aluminum and three aluminum–silicon alloys in different concentrations of HCl solutions and its inhibition by antihypertensive drugs was studied using potentiostatic polarization measurements. As the acid concentration increases, the rate of corrosion increases. Aluminum is less susceptible to corrosion than any of Al–Si alloys. The inhibition efficiency of the drug compounds increases with their concentration up to a critical value. At higher additive concentrations the inhibition efficiency starts to decrease. The inhibitive action of these compounds is due to their formation of insoluble complex adsorbed on the metal surface. The adsorption follows Langmuir adsorption isotherms. It was found that the drugs compounds provide protection to Al and Al–Si alloys against pitting corrosion by shifting the pitting potential to more positive direction until critical drug concentrations (250 ppm). After this critical concentration the inhibition against to pitting corrosion starts to decrease.
Keywords
Aluminum
Aluminum–silicon alloy
Inhibitor
Pitting
Antihypertensive drugs
1 Introduction
Aluminum and its alloys exhibit corrosion resistance in many environments and for this reason they find many important industrial applications. The corrosion resistance is due to the initial formation of a compact and adherent passive oxide film on the exposed surfaces. However, in the presence of insidious ions such as chloride ions, the protective oxide film can be locally destroyed, initiating metal dissolution. Again, the oxide film is amphoteric and hence dissolves readily in acidic solutions (Oguzie, 2009).
In an attempt to mitigate electrochemical corrosion of aluminum and its alloys, the main strategy is to effectively isolate the metal from corrosion agents. This can be achieved by the use of corrosion inhibitors. The use of inhibitors is one of the best known methods of corrosion protection. Most of the efficient acid inhibitors are organic compounds that contain mainly nitrogen, sulphur or oxygen atoms in their structure. Organic compounds used as inhibitors act through a process of surface adsorption, So the efficiency of an inhibitor depends not only on the characteristics of the environment in which its acts, the nature of the metal surface and electrochemical potential at the interface but also on the structure of the inhibitor itself, which includes the number of adsorption active centers in the molecule, their charge density, the molecular size, the mode of adsorption, the formation of metallic complexes and the projected area of the inhibitor on the metal surface (Chetouani et al., 2005; Okafor and Zheng, 2009).
Compounds with functional groups containing hetero-atoms which can donate lone pairs of electrons are found to be particularly useful as inhibitors for aluminum corrosion (Khaled and Al-Qahtani, 2009; Obot and Obi-Egbedi, 2008; Lashkari and Arshadi, 2004; Zheludkevich, 2005; Maayta and Al-Rawashdeh, 2004; Amin et al., 2005; Obot et al., 2009). Also, compounds with π-bonds also generally exhibit good inhibitive properties by providing electrons to interact with the metal surface (Yildirim and Cetin, 2008; Hasanov et al., 2007; Umoren and Ebenso, 2008). Both features obviously can be combined within the same molecule such as drugs.
The use of drugs as corrosion inhibitors for metals in different aggressive environments is not widely reported. Few reports exist in the literature to date; these include the use of sulpha drug (El-Naggar, 2007). Some pharmaceutical compounds used for inhibition of Al in 0.5 mol L−1 H3PO4 (Fouda et al., 2009).
In the previous work, rhodanine azo sulpha drugs (Abdallah, 2002) and antibacterial drug (Abdallah, 2004) were used as corrosion inhibitors for corrosion of 304 SS and aluminum in hydrochloric solutions. They inhibit the corrosion by parallel adsorption on the surface of the metal due to the presence of more than one active center in the inhibitor molecule.
The aim of the present paper is to study the inhibiting action of some antihypertensive drugs on the general and pitting corrosion of Al and three alloys of Al–Si in hydrochloric acid solution using potentiostatic and potentiodynamic anodic polarization techniques. The mode of adsorption and the corrosion inhibition mechanism are also discussed.
2 Experimental methods
The chemical composition of the three of Al–Si alloys is presented in Table 1.
Sample
Alloy
Si
Fe
Cu
Mn
Mg
Ni
Ti
Zn
Cr
Na
Sr
Al
–
–
–
–
–
–
–
–
–
–
–
–
Alloy I
6063
0.42
0.17
0.001
0.009
0.42
0.001
0.010
0.001
0.000
0.0012
0.000
Alloy II
20556
7.01
0.110
0.000
0.000
0.318
0.001
0.091
0.001
0.000
0.0012
0.000
Alloy III
AlSi11MgSr
10.85
0.110
0.000
0.001
0.176
0.001
0.094
0.001
0.000
0.0016
0.061
These electrodes in the form of a cylindrical rod were fixed to pyrex glass tubing by araldite (exposed surface area is 0.79 cm2 for Al pure, 0.64 cm2 for alloy I, 0.77 cm2 for alloy II and 0.65 cm2 for alloy III). Electrical contacts were made through thick copper wires soldered to the end of the electrodes not exposed to the solution. The electrodes were successively abraded with different grades of emery paper, degreased with acetone and finally washed twice with distilled water; complete wetting of the surface was taken as an indication of its cleanliness. All chemicals used were of A.R. quality. The solutions were prepared using twice distilled water and no trial was made to deaerate them. The electrochemical cell was all Pyrex and described elsewhere (El-Etre, 2007). The experiments were carried out at 25 ± 1 °C using air thermostat.
Potentiostatic and potentiodynamic anodic polarization measurements were carried out using PS remote potentiostat with PS6 software for calculation of some corrosion parameters e.g., corrosion current density (icorr.) corrosion potential (Ecorr.) and rate of corrosion (Rcorr.). The corrosion parameters were calculated from the intercept of the anodic and cathodic Tafel lines. The potentiostatic and potentiodynamic anodic polarization measurements were carried out at scan rate of 10 mV s−1and 1 mV s−1, respectively. A three compartment cell with a saturated calomel reference electrode (SCE) and a platinum foil auxiliary electrode was used.
The inhibition efficiency (I.E.) and the surface coverage (θ) were calculated using the following equations:
Conductance measurements were carried out using YSI model 32 conductance meter of cell constant equal to 1.6.
The inhibitors used in this study were three compounds of antihypertensive drugs. The chemical structure of three compounds is shown in Table 2.
Inhibitor
Name
Structure formula
Molecular formula
Compound I
Enalapril maleate
C20H28N2O5·C4H4O4 M. Wt. = 492.53
Compound II
Atenolol
C14H22N2O3 M. Wt. = 266.3
Compound III
Etilefrine hydrochloride
C10H15NO2, HCl M. Wt = 217.7
3 Results and discussion
3.1 Potentiostatic polarization
3.1.1 Effect of acid concentration
Fig. 1 shows the anodic and cathodic polarization curves of Alloy III in different concentrations of HCl solutions as an example. Similar curves were obtained for the other two alloys and Al pure (not shown) (see Table 3).Anodic and cathodic polarization curves of alloy III in different concentrations of HCl solution.
Electrode sample
Acid Conc. (M)
−Ecorr., mV (SCE)
icorr. × 10−6 (A cm−2)
Rcorr. × 10−2 (mm/y)
Al
1 × 10−3
588
1.65
15.05
5 × 10−3
636
5.60
22.25
1 × 10−2
736
9.00
29.66
5 × 10−2
587
13.90
45.80
1 × 10−1
677
17.30
48.40
2 × 10−1
681
19.60
52.30
Alloy I
1 × 10−3
568
4.20
7.20
5 × 10−3
540
8.00
12.96
1 × 10−2
555
10.90
17.14
5 × 10−2
545
16.72
22.70
1 × 10−1
617
20.00
31.39
2 × 10−1
591
22.38
37.02
Alloy II
1 × 10−3
577
6.42
10.08
5 × 10−3
652
10.95
14.90
1 × 10−2
593
13.57
18.70
5 × 10−2
620
19.68
27.50
1 × 10−1
608
22.60
31.40
2 × 10−1
591
24.48
34.70
Alloy III
1 × 10−3
431
9.60
15.05
5 × 10−3
598
15.60
22.25
1 × 10−2
589
18.90
29.66
5 × 10−2
554
26.18
45.80
1 × 10−1
557
28.98
48.40
2 × 10−1
535
31.43
52.30
The effect of acid concentrations on the corrosion parameters such as Ecorr., icorr. and Rcorr. is summarized in Table 1. Inspection of this table reveals that Ecorr. is dependent of acid concentration. Ecorr. values shifted more negative potentials. The values of icorr. of Al and all the alloys increased with increase of acid concentrations and consequently the corrosion rate Rcorr. increases. At the same acid concentration the value of icorr. decreases in the following order III > II > I > Al. This indicates that alloy III has the highest susceptibility to corrosion and Al is less susceptible to corrosion than any of these alloys in agreement with previous results (Bohni and Uhlig, 1969).
3.1.2 Effect of antihypertensive drugs
The effect of addition of increasing concentration of three compounds of antihypertensive drugs (I–III) on the anodic and cathodic polarization curves of aluminum electrode and three of Al–Si alloys in 0.01 M HCl solution was studied. Similar curves to Fig. 1 were obtained (not shown). The corrosion parameters of Al and three Al–Si alloys such as Ecorr., icorr. and Rcorr. were calculated and listed in Tables 4–6, respectively. By the inspection of these tables, it is clear that the values of Ecorr. are changed by increasing the concentration of drugs. It is clear from Table 4 in presence of compound I. The values of Ecorr. are shifted to more positive potential. This indicates that this compound acted as an anodic inhibitor for Al, alloy I, alloy II and alloy III. In Table 5 compound II generally acted as cathodic inhibitors (except Al and alloy II, 1000 ppm compound II) On the other hand in Table 6 compound III generally acted cathodic inhibitor (except Al 1000 ppm compound III). When the additive concentrations increase from 50 up to 250 ppm the values of icorr. and hence Rcorr. decrease. Then at concentrations more than 250 ppm the values of icorr. and Rcorr. increase; consequently, the value of inhibition efficiency (IE) increases at concentrations up to 250 ppm. But at higher concentrations more than 250 ppm of drugs, the values of I.E. decrease. This indicates that the resistance to corrosion starts to decrease. At one and the same inhibitor concentrations the values of I.E. decrease according to the following sequence:
Alloy
Inhibitor Conc. (ppm)
Ecorr. mV (S.C.E)
icorr. × 10−6 (A cm−2)
Rcorr. × 10−2 (mm/y)
I.E. (%)
θ
Al
0
−736
9.00
12.78
–
–
50
−713
3.80
5.400
57.70
0.5770
100
−640
3.10
4.400
65.6
0.6560
150
−570
2.10
3.200
76.83
0.76.83
250
−518
1.70
2.500
80.33
0.8033
500
−494
2.04
2.900
77.00
0.7700
1000
−466
2.40
3.400
73.39
0.7339
Alloy I
0
−555
10.9
17.14
–
–
50
−556
3.30
5.100
69.72
0.6972
100
−642
2.40
3.820
77.98
0.7798
150
−602
2.20
3.400
79.75
0.7975
250
−535
1.70
2.700
81.10
0.8110
500
−510
2.20
3.460
79.82
0.7982
1000
−449
2.70
4.250
75.23
0.7523
Alloy II
0
−593
13.5
18.7
–
–
50
−632
2.30
3.24
82.96
0.8296
100
−569
1.60
2.23
88.15
0.8815
150
−490
1.48
1.18
89.07
0.8907
250
−440
1.20
1.59
91.11
0.9111
500
−448
2.10
2.90
84.44
0.8444
1000
−432
2.90
4.01
78.52
0.7852
Alloy III
0
−589
18.9
29.66
–
–
50
−587
2.00
2.950
89.40
0.8940
100
−474
1.50
2.400
92.06
0.9206
150
−433
1.38
2.100
92.80
0.9280
250
−436
1.20
1.870
93.70
0.9370
500
−476
2.50
4.290
86.77
0.8677
1000
−434
3.50
5.540
81.50
0.8150
Alloy
Inhibitor Conc. (ppm)
Ecom mV (S.C.E)
icorr. × 10−6 (A cm−2)
Rcorr. × 10−2 (mm/y)
I.E. (%)
θ
Al
0
−736
9.00
12.78
–
–
50
−682
4.80
6.900
46.34
0.4634
100
−730
4.00
5.900
55.37
0.5537
150
−715
3.37
4.790
62.50
0.6250
250
−725
2.90
4.130
67.69
0.6769
500
−733
3.40
4.770
62.22
0.6222
1000
−731
4.20
5.850
53.33
0.5333
Alloy I
0
−555
10.9
17.14
–
–
50
−690
4.90
7.400
55.43
0.5543
100
−702
3.88
6.100
64.39
0.6439
150
−685
3.20
4.990
70.36
0.7085
250
−691
2.89
4.390
74.36
0.7436
500
−674
3.50
5.600
67.90
0.6790
1000
−656
4.30
6.800
60.50
0.6050
Alloy II
0
−593
13.5
18.7
–
–
50
−640
6.60
9.16
51.11
0.5111
100
−661
4.60
6.30
65.93
0.6593
150
−630
3.90
5.14
71.25
0.7125
250
−678
3.16
4.90
76.60
0.7660
500
−666
4.75
6.61
64.80
0.6480
1000
−517
6.40
8.90
52.60
0.5260
Alloy III
0
−589
18.9
29.66
–
–
50
−623
5.00
7.850
73.50
0.7350
100
−627
4.20
6.550
77.78
0.7778
150
−640
3.90
5.900
78.79
0.7879
250
−676
3.40
5.320
82.00
0.8200
500
−622
4.10
6.480
78.30
0.7830
1000
−622
4.70
7.340
75.13
0.7513
Alloy
Inhibitor Conc. (ppm)
Ecorr. mV (S.C.E)
icorr. × 10−6 (A cm−2)
Rcorr. × 10−2 (mm/y)
I.E. (%)
θ
Al
0
−736
9.00
12.78
–
–
50
−750
5.40
7.690
39.80
0.3980
100
−788
4.40
6.260
51.00
0.5100
150
−790
3.90
5.530
56.75
0.5675
250
−752
3.60
5.160
59.64
0.5964
500
−836
4.40
6.170
51.11
0.5110
1000
−609
5.40
7.570
40.00
0.4000
Alloy I
0
−555
10.9
17.14
–
–
50
−716
5.70
8.980
47.61
0.4761
100
−702
4.30
6.750
60.60
0.6060
150
−710
3.90
6.080
64.53
0.6453
250
−737
3.60
5.700
66.97
0.6697
500
−675
4.10
6.500
62.38
0.6238
1000
−658
5.20
8.210
52.23
0.5223
Alloy II
0
−593
13.5
18.7
–
–
50
−654
7.00
9.70
48.15
0.4815
100
−710
5.00
7.12
62.96
0.6296
150
−745
4.85
6.70
64.04
0.6404
250
−768
4.34
6.50
67.86
0.6786
500
−662
5.70
7.95
57.78
0.5778
1000
−656
7.00
9.70
84.15
0.8415
Alloy III
0
−589
18.9
29.66
–
–
50
−695
6.80
10.80
64.00
0.6400
100
−658
5.30
8.350
71.96
0.7196
150
−668
4.50
6.700
74.30
0.7430
250
−697
3.75
5.900
80.16
0.8016
500
−756
4.70
7.340
75.13
0.7513
1000
−604
5.50
8.600
70.90
0.7090
3.1.3 Adsorption isotherm
The adsorption of antihypertensive drugs on the surface of aluminum and its alloys can be interpreted by finding a suitable isotherm which describes the variation of experimentally obtained values of the amount of adsorbed substance by unit area of the metal surface with its concentration in bulk solution at constant temperature. The degree of surface coverage (θ) which represents the part of metal surface covered by drug molecules was calculated using the following Eq. (2).
The values of (θ) for different concentrations of the studied drug compounds have been used to explain the best isotherm for adsorption of drug compounds on the metal surface. It is regarded as substitutional adsorption process between the drug compound in the aqueous phase (drug aq.) and water molecules adsorbed on the metal surface (H2O)ads (Moretti et al., 1999).
Langmuir adsorption isotherm for alloy III.
3.2 Potentiodynamic anodic polarization
3.2.1 Susceptibility of Al and its Alloys to pitting corrosion by chloride ions
Fig. 3 represents the potentiodynamic anodic polarization curves of Al electrode in different concentrations of NaCl solution at scan rate of 1 mV s−1. Similar curves (not shown) were obtained for other three alloys.Potentiodynamic anodic polarization curves of pure Al in different concentrations of NaCl solutions.
Inspection of the curves of this figure reveals that:
-
There is no any active dissolution oxidation peak was observed during the anodic scan. This reflects the stability of the air-formed oxide film on surface of aluminum or its alloys.
-
Increasing the sodium chloride concentrations causes the current flowing along the passive region to increase suddenly and markedly at some definite potential denoting the destruction of the passivating oxide film and the initiation of visible pits. The effect of increasing the chloride ions concentrations is the shift of the pitting potential into the active (negative) direction.
The dependence of Epitt. with the concentration of Cl− ion is shown in Fig. 4. The relation presents sigmoid S-shaped curve that indicates a higher Epitt. value at the lower chloride ion concentrations. In this case, the rate of passive film formation prevails over that the film breakdown, which is clear from the small change of Epitt. into the negative direction of potential. Thus, the metal surface may undergo a repassivation (Abdallah, 2004; Abd El-Haleem, 1979). However, at relatively higher Cl− ion concentrations, Epitt varies with Cl− ion concentration according to a straight-line relationship in the following forms (Abdallah and Al-Karanee, 2009):
The relationship between pitting potential and logarithm of the concentrations of NaCl solution.
Further inspection of the curves of Fig. 4 reveals that at one and the same Cl− ion concentration the shift of pitting potential (Epitt) to active (negative) values decreases in the following order:
This sequence differs from that sequence obtained by general corrosion of Al and its alloys, where Al is more resistant to corrosion in HCl solution than Al–Si alloys. In general corrosion the oxide film formed by Al is thick, adherent and non porous. The addition of Si as an alloying element increases the rate of corrosion. Since Al is trivalent and Si is tetravalent, the excess of electron d delocalized throughout the lattice producing point defect. The point defect increases with increasing Si content. This led to the decrease of the resistance of Al.
In the localized attack (pitting) by chloride ions, the presence of Si as an alloying element increases the pitting corrosion resistance of Al (Abd El-Rehim et al., 2004). This can be attributed to the incorporation of Si atoms in the passive film (Mzhar et al., 2001). This incorporation repairs the film defect and renders it more stable (Strehblow and Doherty, 1978). The above sequence may be attributed to that the chloride ions attack the passive film which contains mainly Al2O3 and SiO2. The increase of Si content in the alloy led to form solid solutions consequently increases the resistance to pitting attack.
This sequence shows that pure Al has the highest susceptibility to pitting corrosion and alloy III is the less susceptible to pitting corrosion than any of other two alloys.
3.2.2 Inhibition of pitting corrosion
The effect of increasing addition of the studied drug compounds on the potentiodynamic anodic polarization curves of Al and its alloys in 1 × 10−2 M NaCl solution was studied. Similar curves (not shown) to those of Fig. 3 were obtained in the presence of these compounds. In their presence, the pitting potential was shifted toward a more positive direction until concentration of drug was up to 250 ppm. This indicates that inhibitive effect of these compounds for pitting corrosion. At higher concentrations (more than 250 ppm) of drugs, there is a shift of Epitt., into the active (negative) direction. This shift indicates that the resistance to pitting corrosion is decreased.
Fig. 5 represents the relationship between Epitt and log Cinh. From the curves of this figure, it is clear that the increase of the concentration of the antihypertensive drugs until a critical concentration (250 ppm) causes a shift of pitting corrosion potential into the noble (positive) direction, in accordance with the following equation:
The relationship between pitting potential and logarithm of the concentrations of inhibitor compounds in 1 × 102 M NaCl solution for alloy III.
Some authors (Shams El-Din et al., 1977; Abd El Haleem et al., 1995) attributed the above observation to the hydrolysis of inhibitor to produce corrosion promoting species. However, one may attribute the lose of inhibiting effect toward pitting aluminum and its alloys in presence of high concentrations of antihypertensive sites drugs (more than 250 ppm) due to the competition for adsorption sites on the metal surface. The accumulation of the inhibitors molecules on the metal surface which creates a steric hindrance effect (Schweinsberg et al., 1988). Such effect leads to loosely attack the layer which stimulates corrosion rather than inhibition.
4 Mechanism of inhibition
The inhibition of the general and the pitting corrosion of pure aluminum and aluminum silicon alloys in hydrochloric acid solutions by some antihypertensive drugs as measured by potentiostatic polarization and potentiodynamic anodic polarization were found to depend on both the concentration and the nature of the inhibitors. As the concentration of the inhibitors increases the observed corrosion parameters led to:
-
Decrease of corrosion density.
-
Increase of inhibition efficiency.
-
Increase of surface coverage.
-
Shift of pitting potential to positive direction.
The inhibition efficiency of antihypertensive drugs against the corrosion of Al and Al–Si alloys in 1 × 10−2 M HCl was explained on the basis of the adsorption of the inhibitors at the electrode-solution interface (Mohmoud et al., 1996). Since the drug compounds contain more than one active center in their chemical structures, they will improve the adsorption process, and consequently inhibit the metals against corrosion. However, the inhibition efficiency of the studied compounds depends on many factors, which include the number of adsorption active centers in the molecule, charge density, molecular size, structure and mode of interaction with metal surface and ability to form complexes (Fouda et al., 1986).
To illustrate the mechanism of interaction of antihypertensive drugs with metal ions, the stoichiometry of the expected Al-drugs complexes was estimated by conductance measurements. Conductometric titration curves were obtained by titrating 50 ml of 1 × 10−3 M Al3+ with a solution of 1 × 10−4 M drugs compound as a titrant. The conductance ml-added curves (Fig. 6) are characterized by breaks at molar ratio of 1.0 metal cation: 1.0 drugs additives for compounds I, II and III (cation-ligand).Conductometric titration of 50 ml of 1 × 10−4 M antihypertensive drugs (R) against 1 × 10−3 M AlCl3 (M).
It is known that (Amin, 1995) the shape of the conductometric curve depends on the concentrations of all the species present during the titration process as well as on some other factors such as viscosity, dielectric constant, solvation, complexation and proton transfer.
The inhibition process of antihypertensive drugs can be attributed to the formation of insoluble complexes. The three compounds of antihypertensive drugs can react with Al3+ ion according to the following reaction:
Compound I (high molecular weight) which gives the highest inhibition efficiency, can react with Al3+ ion via one of three routes to give structures I, II or III.Structure (I)
Structure I contains one covalent bond (O–Al) and one coordination bond (O → Al). Structure II contains two coordination bonds (O → Al). On the other hand, structure III contains two covalent bonds. Since the covalent bond (O-Al) is stronger than the coordination bond (O → Al), thus, structure III is the most expected complex to be formed.
Compound II interacts with the metal ion to give the following structure.
Compound III reacts with the metal ions and the following structure may be obtained.
The last structure contains two bonds; one of them is coordination bond (N → Al), while the other bond (O–Al) is covalent.
In view of the above observations, one can conclude that the inhibition efficiencies (I.Es) of antihypertensive drugs (I–III) decrease in the order:
This sequence is in a good agreement with the results obtained experimentally from the two techniques.
5 Conclusion
Antihypertensive drugs act as inhibitors for general and pitting corrosion of Al and Al–Si alloys.
The inhibition efficiency increases with increasing drug concentrations up to a critical value and starts to decrease in presence of higher additives’ concentrations due to steric hindrance effect.
The drug compound acts as corrosion inhibitor due to the formation of insoluble complex adsorbed on the metal surface.
The adsorption process follows Langmuir adsorption isotherm.
Al–Si alloys are more resistant to pitting corrosion than Al in chloride-containing solution.
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