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Article history:
Received 4 December 2010
Received in revised form 6 March 2011
Accepted 1 April 2011
Keywords:
Inhibition
EIS
SEM
Mild steel
IPMP
a b s t r a c t
Corrosion inhibition of mild steel in H3 PO4 containing chloride or sulphate ions have been studied using different electrochemical techniques. The corrosion and hydrogen evolution of mild steel
alloy in 2 M H3 PO4 acid containing 0.5 M NaCl can be effectively inhibited by addition of natural
product compound, Thymol (IPMP), of different concentrations. However, in 2 M H3 PO4 containing
0.5 M Na2 SO4 corrosion cannot be effectively inhibited. The results of electrochemical impedance
spectroscopy (EIS) and potentiodynamic polarization measurements conrm the synergistic effects
which describe the increase in the effectiveness of a corrosion inhibitor in the presence of Cl ions
in the corrosive medium. At any temperature, an increase in it leads to an increase of the corrosion rate and hydrogen evolution on mild steel. Polarization and EIS results are in good agreement
with each other. The obtained results were conrmed by surface examination using scanning electron
microscope.
2011 Elsevier B.V. All rights reserved.
1. Introduction
The use of inhibitors for the control of corrosion for metals
and alloys which are in contact with aggressive environment is
an accepted practice. Large numbers of organic compounds were
studied to investigate their corrosion inhibition potential. All these
studies reveal that organic compounds especially those with N, S
and O showed signicant inhibition efciency. But, unfortunately
most of these compounds are not only expensive but also toxic to
living beings [1]. It is needless to point out the importance of cheap,
safe inhibitors of corrosion. Plant extracts have become important
as an environmentally acceptable, readily available and renewable
source for wide range of inhibitors. They are the rich sources
of ingredients which have very high inhibition efciency. Acid
solutions are widely used in many industrial processes [2]. Besides
hydrochloric acid, phosphoric acid and sulphuric acid are regular
aggressive solutions for acid cleaning and acid descaling due to
their special chemical properties. The use of corrosion inhibitor is
one of the most practical methods for protecting the corrosion of
metal and decreasing hydrogen evolution. As a result, corrosion
inhibitors for hydrochloric acid, phosphoric acid and sulphuric
acid have attracted increasing attention due to their extended
applications [15]. The protection of metals against corrosion by
H3 PO4 has been the subject of much study since it has been used
in many industrial processes especially in fertilizer production
344
Table 1
The chemical compositions of mild steel (wt%).
Si
Mn
0.31
0.21
0.81
Cu
Cr
Mo
Ni
Sn
0.02
0.01
0.02
0.0
0.002
-4.5
-4.0
0.1
-5.0
0.01
0.5
-5.5
1.0 M
H3PO4
-6.0
-6.5
-7.0
-0.8
-0.7
-0.6
-0.5
-0.4
-0.3
E / mV (SCE)
Fig. 1. Potentiodynamic polarization curves of steel in 2 M H3 PO4 with different
concentrations of SO4 2 .
IPMP
is
2-isopropyl-5-methylphenol,
(IPMP)
(molar
mass = 150.22 g mol1 ) which is a natural monoterpene phenol derivative of cymene, C10 H14 O, isomeric with carvacrol,
found in oil of thyme, and extracted as a white crystalline
substance of a pleasant aromatic odor and strong antiseptic
properties.
The main aim of this research work is to study the electrochemical behavior of mild steel in different concentrations of naturally
aerated NaCl or Na2 SO4 in 2 M H3 PO4 solutions at different temperatures using electrochemical techniques and surface examination.
Also, the effect of adding IPMP as corrosion inhibitor for mild steel
is studied.
2. Material and methods
The steel rod was tested in the present study with its crosssectional area of 0.47 cm2 . The chemical composition of the steel,
as given by the supplier, is listed in Table 1. The test aqueous solutions contained H3 PO4 , NaCl (Aldrich), Na2 SO4 (BDH) and IPMP
with different concentrations. Triple distilled water was used for
preparing all solutions. In all measurements, mechanically polished
Table 2
Equivalent circuit and corrosion parameters of mild steel after 1 h immersion for different concentrations of Na2 SO4 , NaCl or 0.5 M NaCl containing different concentrations
of IPMP, in 2.0 M H3 PO4 at 298 K.
[conc.] (M)
R0 ( cm2 )
R1 (k cm2 )
[H3 PO4 ]
2.0
6.6
3.11
[NaCl]
0.01
3.6
16.83
0.10
3.0
3.84
0.50
3.1
3.29
1.00
2.6
20.63
[Na2 SO4 ]
0.01
11.2
16.11
0.10
1.8
15.23
0.50
1.2
9.09
1.00
1.2
5.75
[IPMP] (mM) in presence of 2 M H3 PO4 + 0.5 M Cl
0.1
15.3
9.49
0.1
8.6
9.30
5.0
5.5
21.50
10.0
3.3
29.80
Q1 (1 s cm2 )
icorr (A cm2 )
Ecorr (V)
17.2
0.99
0.23
0.46
0.164
0.097
0.090
0.276
278.8
342.5
952.2
38.2
0.99
0.84
0.83
0.81
0.35
2.06
2.75
0.27
0.65
0.72
0.81
0.49
0.81
0.86
0.84
0.84
0.170
0.123
0.098
0.063
152.2
321.1
322.4
370.1
0.96
0.99
0.99
0.96
0.28
0.41
0.56
0.90
0.48
0.53
0.66
0.69
0.89
0.89
0.89
0.95
2.045
0.723
5.114
8.608
515.1
541.3
552.4
570.1
0.97
0.96
0.98
0.99
1.09
0.852
0.475
0.264
0.78
0.76
0.74
0.69
R2 (k cm2 )
6.5
0.93
0.341
35.0
100.4
480.8
36.5
0.83
0.83
0.89
0.91
18.0
27.3
33.5
34.1
115.1
117.1
119.6
214.2
Q2 (1 s cm2 )
-0.45
Table 3
Inhibition efciencies of mild steel alloy at different concentrations of IPMP at 298 K.
-4
H3PO4 + SO
-0.50
-0.55
Ess / mV (SCE)
345
-0.60
Cinhibitor (mM)
IE% Tafel
IE% EIS
0.1
1.0
5.0
10
60.2
69.0
82.7
90.4
70.7
66.2
87.3
91.2
H3PO4 + Cl
-0.65
-0.70
-0.75
-0.80
-0.85
0.0
0.2
0.4
0.6
0.8
1.0
1.2
C/ M
Fig. 2. Variation of ESS of the steel with the concentration of Cl or SO4 2 in 2 M
H3 PO4 .
H 3 PO 4 + Cl
icorr / A cm
-2
2.5
2.0
1.5
1.0
0.5
H 3 P O 4 + S O --4
0.0
0.0
0.2
0.4
0.6
0.8
1.0
C/M
Fig. 3. Variation of icorr of the steel with the concentration of Cl or SO4 2 in 2 M
H3 PO4 .
IE% = 1
iinh
100
icorr
(1)
where icorr and iinh are the uninhibited and inhibited corrosion
current densities, respectively. It can be seen from the experimental results derived from polarization curves that increasing
IPMP concentration in presence of 0.5 M Cl decreased icorr and
hydrogen evolution at all of the studied concentrations. The
change of cathodic and anodic Tafel slopes alters unremarkably in the presence of the inhibitor. This is indicative that
the inhibitor acts by merely blocking the reaction sites of the
metal surface without changing the anodic and cathodic reaction
mechanisms [2]. Both the anodic and cathodic current densities were decreased indicating that IPMP suppressed both the
anodic and cathodic reactions. Also it was found that the IE
increases till 81.5% at 10 mM IPMP concentration in presence
of Cl as shown in Fig. 4. The order of IE increases as follows: H3 PO4 + IPMP + Cl > H3 PO4 + IPMP > H3 PO4 + IPMP + SO4 2 . It
is apparent that sulphate ions hinder IPMP adsorption, thus IE is
less than that in phosphoric acid only. This may be due to that in
presence of sulphate ions the salts formed in the pits are somewhat
more soluble than in its absence.
Some studies [20,21] show Thyme, which contains the powerful
anticeptic thymol has the active ingredient, offers excellent protection for steel and decrease hydrogen evolution. NaCl has been used
to improve the inhibition efciency of inhibitor; this phenomenon
has been frequently used in practice due to its efciency and low
effective cost [22,23].
346
80
60
IE%
H 3PO 4 + IPMP
H 3PO 4 + IPMP + SO--4
40
20
0
0
10
12
C / mM
Fig. 4. Variation of IE% with the concentration of IPMP.
Fig. 6. Equivalent circuit model representing two time constants for an electrode/electrolyte solution interface.
R1
R2
+
1 + R1 Q1 (j) 1
1 + R2 Q2 (j) 2
(2)
with 0 1 , 2 1.
The passive lm can be considered as the dielectric plates
capacitor formed between the metallic substrate and the counter
electrode. Fitting procedures have shown that good agreement
between the theoretical and experimental data is obtained if a
frequency-dependent constant phase element (CPE) is introduced
instead of pure capacitor, where Q, with the units of 1 s , is a general admittance function has a combination of properties related
to both the surface and electroactive species and is independent of
the frequency (f). The equivalent circuit parameters are tabulated
in Table 2. This EEC consists of two circuits in series from R1 Q1 and
R2 Q2 parallel combination and the two are in series with the solution resistance (R0 ). By this way Q1 is related to combinations from
the capacitance of the porous (outer) layer and Q2 of the barrier
inner layer while R1 is the resistance of the sealed pores by the corrosion products in the outer layer and R2 of the barrier layer [24,25].
For this model, the relation gives the reciprocal capacitance of the
surface lm that is directly proportional to its thickness [26]:
C 1 = Q11 + Q21
Fig. 5. Bode plots of steel in different concentrations of (a) Cl or (b) SO4 2 solution
in 2 M H3 PO4 .
(3)
347
50
40
RT / k cm2
30
H3PO4+ IPMP
--
20
H3PO4+ IPMP+SO4
10
0
10
12
C / mM
Fig. 7. Variation of RT values of steel with concentration of IPMP in 2 M H3 PO4
solutions without and with 0.5 M Cl or 0.5 M SO4 2 .
explaining the behavior of the steel in phosphoric acid with chloride or sulphate solutions over the concentration range studied. The
equivalent circuit parameters are presented in Table 2. In our study
the values of 1 and 2 are from 0.81 to 0.99. Fig. 7 represents the
variation of RT (R1 + R2 ) values of steel with concentration of IPMP
in 2 M H3 PO4 solutions without and with 0.5 M Cl or 0.5 M SO4 2 .
The data indicates that RT values for steel in H3 PO4 containing Cl
increase with increasing IPMP concentrations but in case of absence
and presence of SO4 2 , the relation shows a limited increase. As far
as the present results are concerned, a possible concomitant hydrolysis reaction cannot be also excluded which generates insoluble
salts or hydroxides that hinder contact between the metallic surface
and the electrolyte solution in the pit with a consequent decrease
in the corrosion rate associated with an increase in RT value [27,28].
The effect of IPMP concentration (0.110 mM) as inhibitor is studied in 2 M H3 PO4 solution containing 0.5 M chloride solution and
shown in Fig. 8 as Nyquist plots. The diameter of the depressed
uncompleted circles increases with increasing IPMP concentration
which suggests that the formed surface lm increased in its stability with increasing inhibitor concentration. It is well known that
chloride ions have a smaller degree of hydration, and they can bring
excess negative charges in the vicinity of the interface due to specic adsorption, then, positively charged ions may adsorb onto the
surface. In the present study, IPMP may be protonated in the acid
solution. Since steel surface contains positive charges in the acid
Fig. 9. SEM graphs for the steel in (a) 2 M H3 PO4 containing 0.5 M Cl , (b) 2 M
H3 PO4 containing 0.5 M Cl + 0.1 mM IPMP and (c) 2.0 M H3 PO4 containing 0.5M
Cl + 10 mM IPMP.
348
NaCl (Fig. 9a), in 0.1 mM IPMP (Fig. 9b) and in 10 mM IPMP (Fig. 9c).
Fig. 9a is corroded and contain a lot of pits suggesting that a chloride
ion is so aggressive at this concentration. However, for 0.1 mM IPMP
in 2 M H3 PO4 with 0.5 M NaCl the image is smoother than blank.
Also, Fig. 9c is for 10 mM IPMP in 2 M H3 PO4 with 0.5 M NaCl; it
shows that the lm is much more improved at high concentration
forming a lm in the form of a net.
-0.2
-0.6
Fe + H2 O Fe H2 Oads
(4a)
+
Fe H2 Oads + inh Fe inh
ads + H + inh
(4b)
(4c)
rds
FeOHads + e
FeOH
ads
Fe inhads Fe
FeOHads + Fe
+
inh+
ads
inh+
ads
FeOH + H Fe
(4d)
+e
(4e)
+
Fe inhads + FeOH
2+
+ H2 O
(4f)
(4g)
(5)
(6)
log ( / C)
The inhibition efciency of Thymol could be due to the substitution of terminal hydrogen of phenyl ring by alkyl group that
contain higher number of carbon atom, in addition to the aromatic
phenyl ring donating higher electron density group. It is well known
that chloride ions have a smaller degree of hydration, thus they
could bring excess negative charges in the vicinity of the interface,
and then, positively charged ions might adsorb onto the surface. In
the present study, IPMP might be protonated in the acid solution
according to the mechanism which involving two adsorbed intermediates has been used to account for the retardation of Fe anodic
dissolution in the presence of an inhibitor [30,31]:
-0.4
EIS
R 2 = 0.98
-0.8
Tafel
R2 = 0.97
-1
-1.2
-1.2
-1
-0.8
-0.6
-0.4
log (1-)
Fig. 10. Curve tting of EIS and Tafel data of steel in 2 M H3 PO4 + 0.5 M Cl containing
different concentrations of IPMP to FloryHuggins isotherm at 303 K.
one imply the formation of multilayer of inhibitor on the metal surface. However, values of x less than one mean that a given inhibitor
molecule would occupy more than one active site. K is the binding
constant of the adsorption reaction and C is the inhibitor concentration in the bulk solution. K can be related to the standard free
K=
Gads
1
exp
55.5
RT
(7)
Ea
+ const.
RT
(8)
349
cal data indicating the validity of the proposed model (two time
constants) in explaining the experimental data.
The
order
of
IE
(calculated
from
polarization
and
EIS
data)
increases
as
follows:
H3 PO4 + IPMP + Cl > H3 PO4 + IPMP > H3 PO4 + IPMP + SO4 .
The total resistance RT values increase with increasing IPMP concentration in Cl than in SO4 2 . It is possible to assume that Cl
can concomitantly hydrolysis reaction which generates insoluble
salts or hydroxides that hinder contact between the metallic surface and the electrolyte solution with a consequent decrease in
the corrosion rate associated with RT value increase.
At different temperatures, the results indicate that increasing
temperature leads to a decrease of the total resistance value,
RT , hence increasing the corrosion rate of the mild steel even in
presence of Cl ions.
SEM suggesting that addition of chloride ions to IPMP inhibitor
in the H3 PO4 improves the inhibition process while addition of
sulphate retards the inhibition process and this conrms the
impedance and polarization results.
References
Fig. 12. Variation of ln icorr with T1 for steel in 2 M H3 PO4 + 10 mM IPMP without/with 0.5 M Cl or 0.5 M SO4 2 at different temperatures.