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Inhibition Effect of Nonionic Surfactant On The Corrosion of Cold Rolled Steel in Hydrochloric Acid
Inhibition Effect of Nonionic Surfactant On The Corrosion of Cold Rolled Steel in Hydrochloric Acid
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Abstract
The inhibition effect of Tween-20 as a nonionic surfactant on the corrosion of cold rolled steel (CRS) in 1.0–8.0 M HCl has been
studied at different temperatures (20–50 °C) by weight loss and potentiodynamic polarization methods. Atomic force microscope
(AFM) provided the CRS surface conditions. The results show that Tween-20 is a good inhibitor in 1.0 M HCl, and the inhibition effi-
ciency (IE) increases with the inhibitor concentration, while decreases with increasing the hydrochloric acid concentration and temper-
ature. Effect of immersion time was also studied and discussed. The adsorption of inhibitor on the CRS surface obeys the Langmuir
adsorption isotherm equation. Both thermodynamic and kinetic parameters have been obtained by adsorption theory and kinetic equa-
tions. The inhibition effect is satisfactorily explained by the parameters. Polarization curves show that Tween-20 is a mixed-type inhibitor
in hydrochloric acid. The results obtained from weight loss and polarization are in good agreement, and Tween-20 inhibition action
could also be evidenced by surface AFM images.
Ó 2007 Elsevier Ltd. All rights reserved.
0010-938X/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2007.08.014
X. Li et al. / Corrosion Science 50 (2008) 420–430 421
2. Experimental method ciency (IE) of Tween-20 on the corrosion of CRS was cal-
culated as follows [35]:
2.1. Materials v0 v
IE% ¼ 100; ð2Þ
v0
Tests were performed on a cold rolled steel (CRS) of the
following composition: 0.07% C, 0.3% Mn, 0.022% P, where v0 and v are the values of the corrosion rate without
0.010% S, 0.01% Si, 0.030% Al, and bal. Fe. and with addition of the inhibitor, respectively.
45
o
40 C
40
o
CH2OH of Tween-20 may attack the CRS surface while
35 50 C the main hydrophobic part CHCH2OCO(CH2)10CH3 may
30 extend to the solution face. Furthermore, Tween-20 may
25 chemisorb at steel/solution interface via hydrogen bond
20 between the –OH groups in Tween-20 molecules and water
15 molecules adsorbed on the surface. When Tween-20 is
10 adsorbed on the metal surface, co-ordinate bond may be
5 formed by partial transference of electrons from the polar
0 atom (O atom) of Tween-20 to the metal surface. Also,
0 10 20 30 40 50 60 70 80 90 100 110
concentration of tween-20 C (mg l )
-1 Tween-20 may be easily protonated in HCl solution, so
there may be a synergism between Cl and Tween-20
Fig. 2. Relationship between corrosion rate (v) and concentration of [34], which improves inhibitive force of inhibitor.
Tween-20 (C) in 1.0 M HCl.
Fig. 3 also gives that the inhibition efficiency decreases
with the experimental temperature, which indicates that
This trend may result from the fact that adsorption amount the higher temperatures might cause the desorption of
and the coverage of surfactant on the CRS increase with Tween-20 from the steel surface.
the inhibitor concentration, thus the CRS surface is effi-
ciently separated from the medium [25,36]. Also, the curves 3.3. Adsorption isotherm
in Fig. 2 show that when the inhibitor concentration
reaches approximately 40 mg l1, the corrosion rate values Assuming the adsorption of Tween-20 on the CRS sur-
reach certain values and do not change obviously. face obeys Langmuir adsorption isothermal equation
[25,34,37]:
3.2. Effect of Tween-20 concentration and temperature on C 1
inhibition efficiency ¼ þ C; ð4Þ
h K
The values of inhibition efficiencies obtained from the where C is the concentration of inhibitor, K the adsorptive
weight loss for different inhibitor concentrations in 1.0 M equilibrium constant and h is the surface coverage. h was
HCl are given in Fig. 3. The results show that inhibition calculated by the Sekine and Hirakawa’s method [38]:
efficiency increases as the concentration of inhibitor v0 v
h¼ ; ð5Þ
increases from 5 to 100 mg l1. The maximum inhibition v0 vm
efficiency was about 94%. The inhibition was estimated to
where vm is the smallest corrosion rate.
be 82% at 20 °C even at very low concentration (5 mg l1),
From the values of surface coverage, the linear regres-
and at 40 mg l1 concentration its protection was >90%
sions between C/h and C were calculated by the computer,
and the parameters are listed in Table 1. Fig. 4 is the rela-
100 tionship between C/h and C at 30 °C. These results show
that all the linear correlation coefficients (r) are almost
90 equal to 1 and all the slopes are very close to 1, which indi-
cates the adsorption of inhibitor onto steel surface accords
80 with the Langmuir adsorption isotherm.
Table 1 also gives that the adsorptive equilibrium con-
IE (%)
120 0.5
100 0
80
ln K (l mg )
-0.5
-1
C/θ
60
-1
40
-1.5
20
-2
0.00295 0.00305 0.00315 0.00325 0.00335 0.00345 0.00355
-1
0 1/T (K )
0 20 40 60 80 100 120
-1 Fig. 5. The relationship between ln K and 1/T in 1.0 M HCl.
C (mg l )
tion heat (DH) can be approximately regarded as the stan- 20 0.82 103Mw 26.14–2.44 35.81 32.99 + 8.32
dard adsorption heat (DH0) under experimental conditions ln Mw ln Mw
30 0.86 103Mw 27.15–2.52 35.81 28.56 + 8.31
[25,40,41].
ln Mw ln Mw
The adsorption of organic inhibitor molecules from the 40 0.31 103Mw 25.39–2.60 35.81 33.27 + 8.30
aqueous solution can be regarded as a quasi-substitution ln Mw ln Mw
process between the organic compound in the aqueous 50 0.28 103Mw 25.93–2.69 35.81 30.57 + 8.32
phase [Org(sol)] and water molecules at the electrode surface ln Mw ln Mw
[42]. Mw – the molecular weight of Tween-20, 1159–1250 g mol1.
424 X. Li et al. / Corrosion Science 50 (2008) 420–430
DH 0 DG0 4.5
DS 0 ¼ : ð9Þ
T 4
ln v (g m h )
-1
cates that inhibition efficiency decreases with increasing the
2
-2
temperature. This conclusion agrees with the values of IE
(Fig. 3). Such behaviour can be interpreted on the basis 1.5
that an increase in temperature resulted in the desorption 1
of some adsorbed inhibitor molecules from the metal
0.5
surface. The negative values of DG0 suggest that the
adsorption of inhibitor molecule onto steel surface is a 0
90 90
95
80 80
ln A (g m h )
Ea (kJ mol )
Ea
-1
70 70
-1
90
ln A
-2
60 60
IE (%)
85
50 50
40 40 80
-1
30 30 10 mg l
-1
20 75 50 mg l
20
0 10 20 30 40 50 60 70 80 90 100 110 -1
-1 100 mg l
C (mg l )
70
0 12 24 36 48 60 72 84 96 108 120 132 144 156
Fig. 7. The relationship of Ea and ln A with the concentration of Tween-
immersion time t (h)
20 in 1.0 M HCl.
Fig. 9. Effect of immersion time on IE of Tween-20 for CRS at 20 °C in
1.0 M HCl.
3.6. Effect of immersion time on corrosion inhibition
Effect of immersion time (3–144 h) on corrosion inhibi- Fig. 9 shows the effect of changing immersion time (3–
tion of Tween-20 at different concentrations on the corro- 144 h) at 20 °C on the inhibition efficiency of Tween-20
sion of CRS in 1.0 M HCl at 20 °C was also studied. at 10, 50 and 100 mg l1. It can be seen from Fig. 9 that
Fig. 8 shows the corrosion rates obtained in the absence the inhibition efficiency is higher than 75% when the
and presence of Tween-20 act as a function of time. In immersion time is only 3 h, which indicates the adsorption
the absence of Tween-20, the corrosion rate was about rate of Tween-20 adsorbing on the steel surface is relatively
5.5 g m2 h1 when the immersion time was only 3 h, then high. Fig. 9 shows that Tween-20 inhibits the corrosion of
immediately increased with the increase of immersion time, CRS for all immersion time at all concentrations. At rela-
then fluctuated around 7.0 g m2 h1. That is to say, the tively lower concentrations of Tween-20 (10 and
corrosion rate of steel is dependent on the immersion time, 50 mg l1), increasing time resulted in increasing IE in 3–
so it is very important to study the effect of immersion time 24 h, then IE began to decrease with the immersion time.
on corrosion inhibition. Fig. 8 also shows that the corro- On the other hand, in the presence of 100 mg l1, increas-
sion rate does not change obviously with the immersion ing immersion time resulted in increasing IE, and the maxi-
time in the presence of Tween-20, which may be ascribed mum IE was about 98% when the immersion time was
to the adsorption film formed on the steel surface. higher than 24 h and the corrosion inhibition was steady.
It is noted that the corrosion rate decreased with The high inhibition efficiency with longer immersion time
increasing the immersion time in the presence of 100 mg l1 can be attributed to the formation of a protective film is
Tween-20 and the corrosion rate was only 0.07 g m2 h1 time-dependent on the CRS surface. It has been stated that
when the immersion time was 144 h, which may be ascribed stable, two-dimensional layers of inhibitor molecules are
to the heteroatom (oxygen atom) of the inhibitor molecule formed on metal surfaces after longer immersion time [63].
[61,62].
8
3.7. Effect of hydrochloric acid concentration on corrosion
inhibition
7
6
Fig. 10 shows the relationship between corrosion rate (v)
corrosion rate v (g m h )
blank
-2
5
10 mg l
-1 (immersion time is 6 h). The corrosion rates obtained both
50 mg l
-1 in the absence and presence of Tween-20 increase with the
4
-1 increase of HCl concentration, and the trend is obvious
100 mg l
3 when the HCl concentration ranging from 5.0 to 8.0 M.
However, the corrosion rates decrease in the presence of
2
Tween-20 in the whole HCl concentration, especially the
1 corrosion rate is lower than 40 g m2 h1 in the presence
of 100 mg l1 Tween-20 even when acid concentration is
0
0 12 24 36 48 60 72 84 96 108 120 132 144 156 8.0 M.
immersion time t (h) Fig. 11 shows the effect of changing HCl concentra-
Fig. 8. Effect of immersion time on the corrosion rate of CRS in 1.0 M tion at 20 °C on the inhibition efficiency of Tween-20
HCl at 20 °C. at 10, 50 and 100 mg l1. In all cases, increasing acid
426 X. Li et al. / Corrosion Science 50 (2008) 420–430
100 5
90 blank
-1
10 mg l 4
80
-1
corrosion rate v (g m h )
50 mg l
-1
70
-1 3
-2
100 mg l
60
ln v (g m h )
-2 -1
50 2
40 blank
1 -1
30 10 mg l
-1
20 50 mg l
0 -1
100 mg l
10
0 -1
0 1 2 3 4 5 6 7 8 9 0 1 2 3 4 5 6 7 8 9
concentration of HCl CHCl(M) concentration of HCl CHCl (M)
Fig. 10. Relationship between corrosion rate (v) and hydrochloric acid Fig. 12. Variation of ln v with CHCl at 20 °C.
concentration(CHCl) at 20 °C.
3.0 M and 2.0 M HCl in the absence and presence of inhib-
100
itor, respectively. The steel surface was observed that there
10 mg l
-1 was a dark corrosion product layer on the steel surface in
90 -1 1.0–3.0 M uninhibited HCl after immersion, while there
50 mg l
80 -1 was no insoluble corrosion product in 3.0–8.0 M uninhib-
100 mg l
ited HCl after immersion. Thus, the break point in 3.0 M
70 uninhibited HCl may be ascribed to the corrosion product.
In accordance, the break point in 2.0 M inhibited HCl
IE (%)
60
might be ascribed to the adsorption film of inhibitor.
50 Namely, the adsorption film in 1.0–2.0 M HCl was more
closely and uniform than that in 2.0–8.0 M HCl. The
40
straight lines show that the kinetic parameters could be
30 calculated by Eq. (11), and listed in Table 4.
Eq. (10) shows that k can be regarded as a commencing
20 rate at zero acid concentration, so k means the ability of
0 1 2 3 4 5 6 7 8 9
concentration of HCl CHCl (M) corrosion of HCl for steel [64–66]. Table 4 clearly shows
that k decreases obviously after adding Tween-20 in HCl
Fig. 11. Effect of change in HCl concentration on IE of Tween-20 for the solution, which indicates Tween-20 is a good inhibitor
steel at 20 °C.
in HCl. Furthermore, the values of k in 1.0–2.0 M HCl
inhibited solution are lower than those in 2.0–8.0 M HCl
concentration resulted in decreasing IE. It is worth noting inhibited solution, which indicates that the values of IE
that when the acid concentration reaches 5.0 M, the IEs in 1.0–2.0 M HCl are more superior to those in 2.0–
reach certain values and do not change obviously with 8.0 M HCl (Fig. 11). According to Eq. (11), B is the slope
the acid concentration. Fig. 11 also show that inhibition of the line ln v–C, so B indicates the changed extent of v
efficiency increased with the increase of inhibitor concen- with the acid concentration [67,68]. The values of B in
tration in whole HCl solutions, and IE was about 65% of inhibited HCl are higher than that in uninhibited HCl,
5.0–8.0 M HCl for 100 mg l1 Tween-20, thus it is possible which indicates that the changed extent of v with C in
to add higher concentration of inhibitor in relatively higher
HCl concentration solutions. Table 4
Calculated values of kinetic parameters for the corrosion of steel in HCl
3.8. Rate constant (k) and reaction constant (B) containing Tween-20 at 20 °C
C B (g m2 h1 M1) k (g m2 h1)
Assuming the corrosion rate against the molar concen- (mg l1) 1.0–2.0 M 2.0–8.0 M 1.0–2.0 M 2.0–8.0 M
tration of HCl (CHCl) obeys the expression proposed by HCl HCl HCl HCl
Mathur and Vasudevan [64]: 0 0.22a 0.44b 5.68a 2.67b
ln v ¼ ln k þ BC HCl ; ð11Þ 10 1.08 0.47 0.38 1.47
50 1.48 0.51 0.13 1.06
where k is the rate constant, and B is the reaction constant. 100 1.26 0.52 0.12 0.59
Fig. 12 is the curve of ln v vs. CHCl in different conditions. a
1.0–3.0 M HCl.
b
As can be seen from Fig. 12, the break points appear at 3.0–8.0 M HCl.
X. Li et al. / Corrosion Science 50 (2008) 420–430 427
inhibited HCl is bigger than that in uninhibited HCl. inhibitor in HCl. The same results have been reported with
Namely, the IE decreases obviously with the acid concen- other organic compounds in HCl [11,34,70].
tration (Fig. 11). In addition, the values of B in 1.0– It is worth noting that when Tween-20 concentration is
2.0 M HCl inhibited solution are higher than those in 100 mg l1, the corrosion potential (Ecorr) shifts slightly to
2.0–8.0 M HCl inhibited solution, which indicates that more negative potentials, both anodic and cathodic reac-
the changed degree of IE in 1.0–2.0 M HCl is greater than tions of electrode are drastically inhibited, probably being
that in 2.0–8.0 M HCl. caused by a strong adsorption layer which covers both ano-
dic and cathodic reactive sites on the steel surface.
From Table 5, it can be concluded that inhibition effi-
3.9. Polarization studies ciencies obtained from weight loss and electrochemical
polarization curves are in good agreement.
Both anodic and cathodic polarization curves for cold
rolled steel in HCl at various concentrations of Tween-20 3.10. Atomic force microscope (AFM) surface examination
are shown in Fig. 13. It is clear that the presence of inhib-
itor causes a markedly decrease in the corrosion rate, i.e. The atomic force microscope (AFM) provides a power-
shifts the anodic curves to more positive potentials and ful means of characterizing the microstructure [71–74]. The
the cathodic curves to more negative potentials. This may three-dimensional AFM images of cold rolled steel (CRS)
be ascribed to adsorption of inhibitor over the corroded surface in 1.0 M HCl are shown in Fig. 14. Fig. 15 illus-
surface [69]. The values of corrosion current densities trates the corresponding two-dimensional AFM images.
(Icorr), corrosion potential (Ecorr), the cathodic Tafel slope As can be seen from Fig. 14a, that the corrosion of CRS
(bc), anodic Tafel slope (ba), and the inhibition efficiency steel samples in the absence of inhibitor appeared to be rel-
(IE) as functions of Tween-20 concentration, were calcu- atively uniform in general and some parts to a low-mound-
lated from the curves of Fig. 13 and given in Table 5. Table like structure. The image is quite different from the pitting
5 reveals that the corrosion current decreases obviously corrosion image [73] or the corrosion in HClO4–
and IE increases with the inhibitor concentration. The CH3COOH solution [75]. However, in the presence of
presence of Tween-20 does not remarkably shift the corro- 100 mg l1 Tween-20, the surface becomes more smooth
sion potential, while the anodic and cathodic Tafel slopes and homogeneous (Fig. 14b).
change upon addition of increasing inhibitor concentra- Fig. 15 clearly shows the corrosion degree of CRS
tion. Therefore, Tween-20 can be arranged as mixed-type decreases in the presence of Tween-20. Fig. 15b shows
some spherical or bread-like particles appear the surface,
-0.2
blank which do not exist in Fig. 15a. Therefore, it may be con-
10 mg l
-1
cluded that these particles are the adsorption film of the
-0.3
50 mg l
-1
inhibitor [67,68], which efficiently inhibits the corrosion
100 mg l
-1
of CRS. In addition, Fig. 15a shows that the corrosion of
-0.4
steel in the absence of inhibitor appears some ‘‘curves-net-
E (V vs. SCE)
Fig. 14. AFM three-dimensional images of the cold rolled steel (CRS) surface in 1.0 M HCl: (a) in the absence of Tween-20; (b) in the presence of
100 mg l1 Tween-20.
Fig. 15. AFM two-dimensional images of the cold rolled steel (CRS) surface in 1.0 M HCl: (a) in the absence of Tween-20; (b) in the presence of
100 mg l1 Tween-20.
Fig. 16. AFM images of the cold rolled steel (CRS) surface topography in 1.0 M HCl: (a) in the absence of Tween-20; (b) in the presence of 100 mg l1
Tween-20.
X. Li et al. / Corrosion Science 50 (2008) 420–430 429
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