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Corrosion Science 50 (2008) 420–430

www.elsevier.com/locate/corsci

Inhibition effect of nonionic surfactant on the corrosion of cold

rolled steel in hydrochloric acid
Xianghong Li a,*, Shuduan Deng b, Guannan Mu c, Hui Fu a, Fazhong Yang a
a
Department of Fundamental Courses, Southwest Forestry University, Kunming 650224, PR China
b
Department of Wood Science and Technology, Southwest Forestry University, Kunming 650224, PR China
c
Department of Chemistry, Yunnan University, Kunming 650091, PR China

Received 25 January 2007; accepted 19 August 2007

Available online 7 September 2007

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.

Keywords: A. Steel; B. AFM; B. Polarization; B. Weight loss; C. Acid inhibition

1. Introduction adsorption of the surfactant on the metal surface can

The use of hydrochloric acid in pickling of metals, aci-
dization of oil wells and in cleaning of scales is more eco-
nomical, efficient and trouble-free, compared to other
mineral acids [1,2]. Inhibitors are used to prevent metal
dissolution as well as acid consumption [3,4]. Most well-
known acid inhibitors are organic compounds containing
nitrogen, sulfur, and oxygen atoms. The surfactant inhibi-
tor has many advantages such as high inhibition efficiency,
low price, low toxicity and easy production [5–10]. The
*
Corresponding author.
E-mail address: xianghong-li@163.com (X. Li).
markedly change the corrosion-resisting property of
the metal [11,12], and so the study of the relationship
between the adsorption and corrosion inhibition is of great
importance.
Ionic surfactants have been used for the corrosion inhi-
bition of iron [13–20], copper [21–24], aluminum [25–28]
and other metals [29,30] in different corroding media.
Recently, many nonionic surfactants have been widely used
as corrosion inhibitors for iron in acidic media [31–33].
However, as a nonionic surfactant, Tween-20 was rarely
studied as an inhibitor for cold rolled steel in hydrochloric
acid. For the reason, based on the proceeding papers, the
objective of the present work is to investigate the corrosion
inhibition by Tween-20 in 1.0–8.0 M HCl, so as to further
study the inhibitive mechanism of Tween-20 for cold rolled
steel in hydrochloric acid.

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
2. Experimental method
2.1. Materials
Tests were performed on a cold rolled steel (CRS) of the
following composition: 0.07% C, 0.3% Mn, 0.022% P,
0.010% S, 0.01% Si, 0.030% Al, and bal. Fe.
2.2. Inhibitor
The nonionic surfactant of Tween-20 was obtained from
Shanghai Chemical Reagent Company of China. Fig. 1
shows the molecular structure of the Tween-20. It is obvi-
ous that Tween-20 is an O-heterocyclic compound. The
main functional group is hydroxyl, which may be easily
protonated in acidic solution.
2.3. Solutions
The aggressive solutions, 1.0–8.0 M HCl, were prepared
by dilution of analytical grade 37% HCl with distilled
water. The concentration range of Tween-20 used was 5–
100 mg l1.
2.4. Weight loss measurements
The cold rolled steel (CRS) sheets of 2.5 cm  2.0 cm 
0.06 cm were abraded with a series of emery paper (grade
320-500-800) and then washed with distilled water and ace-
tone. After weighing accurately, the specimens were
immersed in 250 ml beaker, which contained 250 ml hydro-
chloric acid with and without addition of different concen-
trations of Tween-20. All the aggressive acid solutions were
open to air. After 6 h, the specimens were taken out,
washed, dried, and weighed accurately. Experiments were
carried out in triplicate. The average weight loss of three
parallel CRS sheets could be obtained. Then the tests were
repeated at different temperatures and HCl concentration.
The corrosion rate (v) was calculated from the following
equation [34]:
W a cold air blaster, and then used for a Japan instrument
v¼ ; ð1Þ
St
where W is the average weight loss of three parallel CRS
sheets, S the total area of the specimen, and t is immersion
time. With the calculated corrosion rate, the inhibition effi-
O
H 2C CHCH2OCO(CH2)10CH3
HOHC CHO(CH2CH2O)nCH2CH2OH
OH
Fig. 1. Chemical molecular structure of the Tween-20.
421
ciency (IE) of Tween-20 on the corrosion of CRS was cal-
culated as follows [35]:
v0  v
IE% ¼  100; ð2Þ
v0
where v0 and v are the values of the corrosion rate without
and with addition of the inhibitor, respectively.
2.5. Polarization measurements
Polarization experiments were carried out in a conven-
tional three-electrode cell with a platinum counter elec-
trode (CE) and a saturated calomel electrode (SCE)
coupled to a fine Luggin capillary as the reference elec-
trode. The working electrode (WE) was in the form of a
square cut from CRS embedded in epoxy resin of polytet-
rafluoroethylene (PTFE) so that the flat surface was the
only surface in the electrode. The working surface area
was 1.0 cm  1.0 cm.
Before measurement, the electrode was immersed in test
solution at natural potential for 2 h until a steady state was
reached. All polarization curves were recorded by a PAR-
STAT 2263 potentiostat (Perkin ElmerTM Company, USA)
at 20 °C. The potential increased with a speed of
30 mV min1 and started from potential of 250 mV to
+250 mV vs. corrosion potential (Ecorr). IE% was defined
as
I corr  I corrðinhÞ
IE% ¼  100; ð3Þ
I corr
where Icorr and Icorr(inh) are the corrosion current density
values without and with inhibitor, respectively, determined
by extrapolation of Tafel lines to the corrosion potential.
2.6. Atomic force microscope (AFM)
The CRS specimens of size 1.0 cm  1.0 cm  0.06 cm
were abraded with emery paper (grade 320-500-800) and
gave a mirror surface, then washed with distilled water
and acetone. After immersion in 1.0 M HCl without and
with addition of 100 mg l1 Tween-20 at 20 °C for 6 h,
the specimen was cleaned with distilled water, dried with
model SPA-400 SPM Unit atomic force microscope
(AFM) examinations.
3. Experimental results and discussion
3.1. Effect of Tween-20 on the corrosion rate
The corrosion rate curves of cold rolled steel (CRS) with
the addition of Tween-20 in 1.0 M HCl at various temper-
atures are shown in Fig. 2. The curves in Fig. 2 show that
the corrosion rate values (g m2 h1) of CRS in 1.0 M HCl
solution containing Tween-20 decrease as the concentra-
tions of the inhibitor increase, i.e. the corrosion inhibition
strengthens with the nonionic surfactant concentration.
422 X. Li et al. / Corrosion Science 50 (2008) 420–430

65 (20–30 °C). These better performances can be explained

60 as follows: Fig. 1 shows that the molecular weight of
55 o Tween-20 is high, thus Tween-20 can relatively easily
20 C
50 o
adsorb on the CRS surface by van der Waals force. In addi-
30 C
corrosion rate v (g m h )

tion, the main hydrophilic part CHO(CH2CH2O)nCH2-

-2 -1

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 (%)

70 stant (K) decreases with increasing temperature, which

indicates that it is easily adsorbed strongly onto the steel
o
20 C
60 o
30 C
o Table 1
40 C
50 o
Parameters of the linear regression between C/h and C
50 C
Temperature Slope K (l mg1) Linear correlation
40 (°C) coefficient (r)
0 20 40 60 80 100 120
-1 20 0.9923 0.82 0.9999
concentration of tween-20 C (mg l ) 30 0.9881 0.86 1.0000
Fig. 3. Relationship between inhibition efficiency (IE) and concentration 40 0.9822 0.31 0.9995
of Tween-20 (C) in 1.0 M HCl. 50 0.9718 0.28 0.9996
 X. Li et al. / Corrosion Science 50 (2008) 420–430 423

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 )

Fig. 4. The relationship between C/h and C at 30 °C in 1.0 M HCl.

OrgðsolÞ + xH2 OðadsÞ $ OrgðadsÞ + xH2 OðsolÞ ð7Þ
surface for the inhibitor at relatively lower temperature.
But when the temperature was relatively higher, the where x is the size ratio, that is, the number of water mol-
adsorbed inhibitors tended to desorb from the steel surface. ecules replaced by one organic inhibitor.
Thus, the standard adsorption free energy (DG0) could
be obtained according to [43–47]:
3.4. Thermodynamic parameters
 
1 DG0
It is generally accepted that organic molecules inhibit K¼ exp ; ð8Þ
55:5 RT
corrosion by adsorption at the metal–solution interface
and that the adsorption depends on the molecule’s chemi-
cal composition, the temperature and the electrochemical where R is the gas constant (8.314 J K1 mol1), T the
potential at the metal/solution interface [39]. Thermody- absolute temperature (K), and the value 55.5 is the concen-
namic parameters play an important role in understanding tration of water in solution expressed in M (mol l1 or
the inhibitive mechanism. The adsorption heat could be mol dm3) [43–47]. The unit of DG0 is J mol1 (or
calculated according to the Van’t Hoff equation [25,34]: kJ mol1). Obviously, the adsorptive equilibrium constant
K unit is l mol1 in Eq. (8) [41,45,46]. Thus, the adsorptive
DH
ln K ¼ þ constant; ð6Þ equilibrium constant K unit l mg1 (Table 1) should be
RT changed into l mol1 [48]. Because Tween-20 is also a poly-
where DH and K are the adsorption heat and adsorptive mer, it is difficult to know the exact molecular weight.
equilibrium constant, respectively. Assuming the molecular weight of Tween-20 is Mw
It should be noted that DH/R is the slope of the g mol1. The changed adsorption equilibrium constant in
straight line ln K–1/T according to Eq. (6) and the molecu- unit l mol1 is listed in Table 2.
lar weight of inhibitor is also a positive constant, so the Then the standard adsorption entropy (DS0) can be
value of adsorption heat value does not change with the obtained by the basic thermodynamic equation:
unit of adsorptive equilibrium constant. The straight line
ln K–1/T is shown in Fig. 5. Because the experiment is pro- Table 2
ceeded at the standard pressure (101,325 Pa) and the solu- The thermodynamic parameters of adsorption of Tween-20 on CRS
tion concentration is so low that it is close to standard surface
condition, the adsorption heat DH can be approximately Temperature K DG0 DH0 DS0
regarded as the standard adsorption heat DH0. The adsorp- (°C) (l mol1) (kJ mol1) (kJ mol ) (J mol1 K1)
1

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

All the calculated thermodynamic parameters are listed in 3.5

Table 2. The negative value of DH0 shows that the adsorp- 3
tion of inhibitor is an exothermic process [49], which indi- 2.5

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

spontaneous process. Generally, values of DG0 up to -0.5

20 kJ mol1 are consistent with the electrostatic interac- -1
tion between the charged molecules and the charged metal 0.00295 0.00305 0.00315 0.00325 0.00335 0.00345 0.00355
-1
(physical adsorption) while those more negative than 1/T (K )
40 kJ mol1 involve sharing or transfer of electrons from Fig. 6. Arrhenius plots related to the corrosion rate of cold rolled steel for
the inhibitor molecules to the metal surface to form a co- various concentrations of Tween-20 in 1.0 M HCl: (j) blank; (s)
ordinate type of bond (chemisorption) [50–52]. Because 5 mg l1; (d) 10 mg l1; (M) 50 mg l1; (N) 100 mg l1.
the molecular weight (Mw) of Tween-20 is about 1159–
1250 g mol1 [53], it can be seen from Table 2 that the
value of DG0 is around 43 kJ mol1, which indicates the and given in Table 3. It is clear that the value of Ea in
adsorption of Tween-20 is mainly the chemisorption. As the presence of the Tween-20 are higher than that in the
for the value of DS0 in Table 2, the sign of DS0 is positive. uninhibited acid solution. These results are according with
This is opposite to what would be expected, since adsorp- the reported studies [31,59]. The increase of Ea in the pres-
tion is an exothermic process and is always accompanied ence of the inhibitor indicates that physical adsorption or
by a decrease of entropy. Ateya et al. [54] described this sit- weak chemical bonding between the Tween-20 molecules
uation as the adsorption of the organic compound which is and the steel surface might occur [60].
accompanied by the desorption of water molecules from According to Eq. (10), it can be seen that the lower pre-
the surface. Thus, while the adsorption process is believed exponential factor A and the higher Ea lead to the lower
to be exothermic and associated with a decrease in entropy corrosion rate (v). For the present study, the value of A
of the solute, the opposite is true for the solvent. Therefore, in the presence of Tween-20 is higher than that of in the
the gain in entropy accompanied by the substantial adsorp- absence of Tween-20. Therefore, the decrease in steel cor-
tion process is attributed to the increase in solvent entropy rosion rate is mostly decided by the apparent activation
[41,55]. The positive values of DS0 mean that the process of energy.
adsorption is the process accompanied by an increase in en- The relationship of Ea and ln A with the inhibitor con-
tropy, which is the driving force for the adsorption of centration is shown in Fig. 7. It is clear that both Ea and
inhibitor onto the CRS surface [56,57]. ln A increase in the presence of Tween-20. But when the
inhibitor concentrations reach 40 mg l1, the values do
3.5. Apparent activation energy (Ea) and pre-exponential not change obviously. That is to say, according to Eq.
factor (A) (10), the corrosion rate (v) does not change obviously after
40 mg l1. The results obey Figs. 2 and 3.
It has been reported by a number of authors that for the
acid corrosion of steel, the natural logarithm of the corro-
sion rate (in g m2 h1) is a linear function with 1/T Table 3
(following Arrhenius equation) [31,34,40,58,59]: Parameters of the regression between ln v and 1/T
C Ea A Linear regression
Ea
ln v ¼ þ ln A; ð10Þ (mg l1) (kJ mol1) (g m2 h1) coefficient (r)
RT
0 58.22 1.89  1011 0.9974
where Ea represents the apparent activation energy, R the 5 86.07 2.55  1015 0.9947
gas constant, T the absolute temperature, A the pre-expo- 10 86.93 3.15  1015 0.9944
20 94.73 5.18  1016 0.9927
nential factor, and v is the corrosion rate. 30 92.69 2.12  1016 0.9871
The regression between ln v and 1/T was calculated by 40 94.68 4.04  1016 0.9856
computer. Arrhenius plots of ln v vs. 1/T for the blank 50 96.12 6.70  1016 0.9877
and different concentrations of the nonionic surfactant 70 95.71 5.27  1016 0.9893
are shown in Fig. 6. All the parameters were calculated 100 97.28 8.64  1016 0.9936
 X. Li et al. / Corrosion Science 50 (2008) 420–430 425

100 100 100

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 )

and hydrochloric acid concentration (CHCl) at 20 °C

-1

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.
Namely, the IE decreases obviously with the acid concen-
tration (Fig. 11). In addition, the values of B in 1.0–
2.0 M HCl inhibited solution are higher than those in
2.0–8.0 M HCl inhibited solution, which indicates that
the changed degree of IE in 1.0–2.0 M HCl is greater than
that in 2.0–8.0 M HCl.
3.9. Polarization studies
Both anodic and cathodic polarization curves for cold
rolled steel in HCl at various concentrations of Tween-20
are shown in Fig. 13. It is clear that the presence of inhib-
itor causes a markedly decrease in the corrosion rate, i.e.
shifts the anodic curves to more positive potentials and
the cathodic curves to more negative potentials. This may
be ascribed to adsorption of inhibitor over the corroded
surface [69]. The values of corrosion current densities
(Icorr), corrosion potential (Ecorr), the cathodic Tafel slope
(bc), anodic Tafel slope (ba), and the inhibition efficiency
(IE) as functions of Tween-20 concentration, were calcu-
lated from the curves of Fig. 13 and given in Table 5. Table
5 reveals that the corrosion current decreases obviously
and IE increases with the inhibitor concentration. The
presence of Tween-20 does not remarkably shift the corro-
sion potential, while the anodic and cathodic Tafel slopes
change upon addition of increasing inhibitor concentra-
tion. Therefore, Tween-20 can be arranged as mixed-type
-0.2
blank
10 mg l
-1
-0.3
50 mg l
-1
100 mg l
-1
-0.4
E (V vs. SCE)
inhibitor in HCl. The same results have been reported with
other organic compounds in HCl [11,34,70].
It is worth noting that when Tween-20 concentration is
100 mg l1, the corrosion potential (Ecorr) shifts slightly to
more negative potentials, both anodic and cathodic reac-
tions of electrode are drastically inhibited, probably being
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-
ciencies obtained from weight loss and electrochemical
polarization curves are in good agreement.
3.10. Atomic force microscope (AFM) surface examination
The atomic force microscope (AFM) provides a power-
ful means of characterizing the microstructure [71–74]. The
three-dimensional AFM images of cold rolled steel (CRS)
surface in 1.0 M HCl are shown in Fig. 14. Fig. 15 illus-
trates the corresponding two-dimensional AFM images.
As can be seen from Fig. 14a, that the corrosion of CRS
steel samples in the absence of inhibitor appeared to be rel-
atively uniform in general and some parts to a low-mound-
like structure. The image is quite different from the pitting
corrosion image [73] or the corrosion in HClO4–
CH3COOH solution [75]. However, in the presence of
100 mg l1 Tween-20, the surface becomes more smooth
and homogeneous (Fig. 14b).
Fig. 15 clearly shows the corrosion degree of CRS
decreases in the presence of Tween-20. Fig. 15b shows
some spherical or bread-like particles appear the surface,
which do not exist in Fig. 15a. Therefore, it may be con-
cluded that these particles are the adsorption film of the
inhibitor [67,68], which efficiently inhibits the corrosion
of CRS. In addition, Fig. 15a shows that the corrosion of
steel in the absence of inhibitor appears some ‘‘curves-net-

work-like” image, which is caused by the corrosion of HCl.

-0.5
On the other hand, Fig. 15b shows that the ‘‘curves-net-
work-like” image disappears, and the corrosion of steel
-0.6
appears the more flat and uniform film, which may be
ascribed to the adsorption of Tween-20 onto the steel sur-
-0.7 face, thus efficiently protects the steel from corrosion.
Fig. 16 shows the CRS surface topography in 1.0 M
-0.8 HCl. Fig. 17 illustrates the height profiles, which is made
-6.5 -6.0 -5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5
log I (A cm )
-2
along the line marked in corresponding Fig. 16. It can be
seen from Fig. 16a that the micrograph of CRS surface
Fig. 13. Potentiodynamic polarization curves for CRS in 1.0 M HCl
after immersion in uninhibited 1.0 HCl shows the main
containing Tween-20 at 20 °C.
characteristic of uniform corrosion in acidic media [76].
Fig. 16b shows that some spherical particles decorating
Table 5
the steel surface and the retention of surface grinding
Potentiodynamic polarization parameters for the corrosion of CRS in marks, which indicate a macroscopically thin film [67,68].
1.0 M HCl containing different concentrations of Tween-20 at 20 °C Fig. 16 also shows that the particles on the steel surface
C Ecorr Icorr bc ba IE become smaller after adding Tween-20 in 1.0 M HCl.
(mg l1) (mV) (lA cm2) (mV dec1) (mV dec1) (%) Fig. 17a shows that the surface roughness of the CRS in
0 448.4 172.0 98 61 – uninhibited 1.0 HCl is about 28.03 nm, while in the pres-
10 457.2 33.7 107 76 80.4 ence of Tween-20, the roughness decreases to 8.54 nm
50 455.0 20.7 111 81 88.0 (Fig. 17b). Thus, the roughness is consistent with the
100 492.9 11.6 175 122 93.3 results shown in Figs. 14 and 15.
428 X. Li et al. / Corrosion Science 50 (2008) 420–430

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
Fig. 17. Height profiles of the CRS surface in 1.0 M HCl: (a) in the
absence of Tween-20; (b) in the presence of 100 mg l1 Tween-20.
4. Conclusions
(1) Tween-20 acts as a good inhibitor for the corrosion
of cold rolled steel in 1.0 M HCl, and the maximum
inhibition efficiency is about 94%. The inhibition effi-
ciency values increase with the inhibitor concentra-
tion, but decrease with the acid concentration and
the temperature.
(2) The adsorption of the Tween-20 on the cold rolled
steel surface obeys the Langmuir adsorption iso-
therm. The adsorption process is a spontaneous
and exothermic process accompanied by an increase
in entropy.
(3) The corrosion rate of steel in the presence and absence
of Tween-20 acts as a function of immersion time. The
inhibition efficiency was dependent on the immersion
time, and the highest IE was about 98% for 100 mg l1
Tween-20 when the immersion time was 24–144 h.
(4) The rate constant (k) decreases obviously after add-
ing Tween-20 in 1.0–8.0 M HCl solution, while the
reaction constant (B) increases, especially in 1.0–
2.0 M HCl. The values of both apparent activation
energy (Ea) and pre-exponential factor (A) also
increase after adding Tween-20 in 1.0 M HCl. The
inhibitive mechanism is mostly decided by the appar-
ent activation energy.
(5) Tween-20 acts as a mixed-type inhibitor in 1.0 M
HCl. The weight loss and polarization curves are
in good agreement.
(6) The introduction of Tween-20 into 1.0 M HCl solu-
tion results in the formation of a film on the CRS
surface, which causes the decrease of the steel sur-
face roughness and effectively protects steel from
corrosion.
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