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Abstract
1. Introduction
The metallic corrosion process is much more complex in neutral media than in
acidic media. The basic reason is that the corrosion product is not soluble
normally and forms an extremely complex ®lm. So, the study of neutral corrosion
inhibitors is more dicult than that of acidic corrosion inhibitors.
Macroscopically, because the corrosion rate of metal in neutral media with
corrosion inhibitors is very slow, it is very dicult to evaluate the inhibition
* Corresponding author.
0010-938X/00/$ - see front matter 7 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 0 0 ) 0 0 0 0 7 - X
1380 F. Gan et al. / Corrosion Science 42 (2000) 1379±1388
2. Theory
EQCM is mainly composed of a quartz wafer. Both sides of the quartz wafer
were coated by gold. One side of the quartz wafer is immersed in the solution as a
work electrode, meanwhile, the other side is exposed in air. By keeping two sides
of the quartz wafer in dierent media one can achieve resonance in an
appropriately designed oscillator circuit, from which the relevant information can
be obtained.
For many conditions, surface mass changes originate changes in the oscillation
frequency of the EQCM through the Sauerbrey equation: [3]
Dm
Df ÿS
1
A
where Df is the change in the oscillation frequency, Dm is the change in the
interfacial mass, A is the electrode apparent area, S is the mass sensitivity
determined by the oscillation fundamental frequency f0 (for f0 10 MHz, S is
0.226 Hz cm2/ng correspondingly). In the Sauerbrey equation, there is a simple
linear relationship between Df and Dm:
F. Gan et al. / Corrosion Science 42 (2000) 1379±1388 1381
In fact, the mass change value in the electrode surface is more signi®cant than
the mass absolute value in practical work. In order to minimize systematic error
from the equipment, the frequency dierence reported in the paper is the change
value of frequency dierence between the experiment beginning
t 0 and the
measuring time
t t). In our laboratory, the frequency dierence is measured by
subtracting work oscillator frequency
fWork from the reference oscillator
frequency
fRef : Then, there is the next formula:
Df
Dfw, tt ÿ
Dfw, t0
fRef ÿ fWork tt ÿ
fRef ÿ fWork t0
Therefore, if the electrode surface mass is increased, the frequency of the work
oscillator
fWork, tt would decrease, and Df would increase. In other words, the
change orientation of Df is identical with the change direction of electrode surface
mass. Naturally, it is not contrary to the Sauerbrey equation. Without considering
the speci®c mechanism and the detailed process in the electrode reaction, the mass
equilibrium on the electrode surface should be suitable for the next equation as
follows:
where Dm, Dmf and Dmc are the total mass change, ®lm adding weight and
corrosion losing weight in the electrode surface, respectively. According to Eqs.
(1) and (2), it can be expressed as:
d
Df
S
nf ÿ nc
4
dt
where nf is ®lming rate and nc the corrosive rate. On the basis of Eq. (4), the
metallic corrosion and ®lming kinetics could be studied.
To simplify Eq. (4), two special cases have been discussed for metallic corrosion
and ®lming kinetics in neutral solution as follows:
1. In the absence of corrosion inhibitor: In natural corrosive conditions, there is
already an oxidized ®lm on the metal surface before the experiment. If the ®lm
has no protection or the protective performance is very poor, in comparison
with the corrosion rate, the ®lm growth rate can be neglected, i.e., nc nf , and
Eq. (4) may be simpli®ed to:
d
Df
ÿSnc
5
dt
As a result, the metallic corrosion rate can be determined from with the
measurement of the frequency dierence.
2. In the presence of corrosion inhibitors: Because of the ®lming promoting action
of corrosion inhibitors, the ®lm growth rate will increase, whereas, the metallic
corrosive rate will decrease. Then nf will be close to nc : It is given that the
1382 F. Gan et al. / Corrosion Science 42 (2000) 1379±1388
where nc, i and nc, b are the corrosion rate with and without corrosion inhibitor
in neutral solution. According to Eqs. (6) and (4), the next equation is
obtained:
d
Df
S nf ÿ
1 ÿ Znc, b
7
dt
where the parameters used have been de®ned above.
If the corrosion inhibitor is a passive one and its concentration is higher than
the critical concentration, all the metallic surface should transform active state
into passivity immediately [4], i.e., y 1: On this condition, because the Z value is
constant, nc, i
1 ÿ Znc, b is also constant. Thus, an integrated formula for Eq.
(7) is obtained using the initial condition Df 0:
Df
t
Dmf
t
1 ÿ Znc, b t
8
S
According to Eq. (8) the ``true'' mass change of the metallic electrode surface
during the ®lming can be calculated, and the isothermal curves of the ®lming
kinetics for corrosion inhibitor may be obtained. Generally, to measure the real
curve of the ®lming kinetics Z and nc, b must be constant in the system, e.g., in a
self-passivation system mentioned above. However, if the Z value is small and
changes only slightly during the experiment period, e.g., in a system with a
precipitating corrosion inhibitor, it may be considered that the metallic corrosion
rate is a contant that is little lower than nc, b after adding the corrosion inhibitor,
i.e., nc , i
1 ÿ Za nc , b may be supposed as a constant approximately, where Za is
the averaged inhibition eciency of the corrosion inhibitor. Similarly, the ®lming
kinetics curve can be obtained according to Eq. (8).
3. Experimental method
The EQCM used in this work was developed by the Electrochemical Research
Institute of Wuhan University (Fig. 1). The fundamental frequency of the quartz
wafer with a gold coating deposited by Chemical Vapor Deposition (CVD) is 102
0.04 MHz and the theorical mass eciency (S ) is 0.226 Hz cm2/ng. The working
electrode diameter is 0.5 cm.
The iron electrode was produced by electroplating the gold electrode of the
F. Gan et al. / Corrosion Science 42 (2000) 1379±1388 1383
Fig. 2. The Df±t curve for an iron electrode in 0.5 mol/dm3 neutral Na2SO4 solution at the open circuit
potential.
1384 F. Gan et al. / Corrosion Science 42 (2000) 1379±1388
Figs. 2±4, show the Df vs. t curves of an iron electrode determined at the open
circuit potential in the neutral Na2SO4 base solution, and containing 2 g/dm3
NaNO2 and 0.24 g/dm3 Na2SiO3, respectively. All the three curves are regular and
smooth. The magnitude of the frequency dierence change was singi®cantly more
than hundreds of Hertz, exceeding the instrumental resolution (1 Hz). It implies
that some useful information could be obtained in the experimental system. The
three curves measured in dierent media show dierent characteristics. In the base
electrolyte (without corrosion inhibitor), Df decreases with time t almost linearly
(see Fig. 2). After adding the passive inhibitor NaNO2, Df increases linearly with
time and slows down gradually (Fig. 3). However, on adding precipitating
inhibitor Na2SiO3, Df increases initially and decreases slowly after 40 min. These
characteristics are discussed below.
Fig. 2 shows that Df vs. t curve is a straight line with a negative slope, i.e.,
d
Df =dt= constant. If the electrode/solution system (Fe/Na2SO4 without
corrosion inhibitor) satis®es Eq. (5), the result indicates that the corrosion rate of
iron in neural Na2SO4 solution is constant and can be calculated from Eq. (5):
d
Df D
Df
nc ÿ 1ÿ 0:38 mm=a
S dt SDt
This nc value is in conformity with 0.05±0.5 mm/a reported in [6]. It is well known
that the metallic corrosion process is often controlled by the oxygen diusion in
neutral solution. When the dissolving oxygen concentration, and the mass-transfer
Fig. 3. The Df±t curve for an iron electrode in 0.5 mol/dm3 neutral Na2SO4 and 2 g/dm3 NaNO2
solution at the open circuit potential.
F. Gan et al. / Corrosion Science 42 (2000) 1379±1388 1385
condition in the solution are basically stable, the rate of the oxygen diusion, and
the metallic corrosive rate, should be constant according to Fick's law. It is
proved from the experimental results that corrosion on iron is controlled by the
oxygen diusion in neutral Na2SO4 solution.
Fig. 3 shows the Df vs. t curves on iron electrode in neutral Na2SO4 solution
with passive inhibitor NaNO2 in a concentration of 2 g/dm3. For this self-passive
system, the simpli®ed Eq. (8) may be satis®ed. Therefore, from Eq. (8) and taking
the data in Fig. 3 and the values for nc, b (0.38 mm/a, see Section 4.1) and Z
(63.2%, see Section 3), the curve of the real ®lming mass change Dm vs. time t on
iron electrode in neutral Na2SO4 solution with NaNO2 was calculated as shown in
Fig. 5. The curve is similar to the parabola. According to the parabolic equation
Dmf 2 Kt Const:, a simulated curve was ®tted (see Fig. 5) with a correlation
coecient 0.994.
In many cases of metallic oxidation at high temperature, the oxide ®lm growth,
i.e., oxidation kinetics, follows the parabolic law [7]. Because the continuous ®lm
growth is controlled by the diusion step of metallic or oxygen ion in the ®lm
when the growing oxide ®lm is protective, the growth rate is inversely
proportional to the ®lm thickness, that is:
dX K
9
dt X
where X is the ®lm thickness, K is a constant. Integrating Eq. (9), a parabolic
equation is obtained:
Fig. 4. The Df±t curve for an iron electrode in 0.5 mol/dm3 neutral Na2SO4 and 0.24 g/dm3 Na2SiO3
solution at the open circuit potential.
1386 F. Gan et al. / Corrosion Science 42 (2000) 1379±1388
X 2 Kt C 10
where C is a constant.
From the parabola curve in Fig. 5, it is found that the ®lming kinetics of
passive inhibitor NaNO2 on iron in Na2SO4 solution is similar to the oxidation
kinetics of some metals at high temperature.
Fig. 4 shows the Df±t curve on iron electrode in neutral 0.5 mol/dm3 Na2SO4
solution with precipitating inhibitor Na2SiO3 at a concentration of 0.24 g/dm3.
Because the inhibition eciency of Na2SiO3 is small
Z 6:1%, see Section 3) and
may be assumed as a constant approximately, the Dm±t of the real ®lming kinetics
curve should still be obtained from Eq. (8) and the data in Fig. 4. The
experimental curve and a regression curve are shown together in Fig. 6. The linear
kinetics curve shows that the growth rate of the silicate deposit ®lm is constant.
According to the slope, the rate is 50 ng minÿ1cmÿ2. If the ®lm thickness is
uniform and the deposit density is equal to that of SiO2
r 2:32 g/cm3), the
®lming rate is 0.2 nm/min. According to the kinetics there are only two cases in
which the ®lming rate may be a constant and independent of the ®lm thickness:
either the ®lming reaction is only dependent of a chemical process and
independent of the mass transfer through the ®lm; or although the reaction
includes the transfer step, the ®lm is loose and porous and has no barrier
characteristics for the transfer process.
In this experimental system, the two cases may co-exist. If the precipitate ®lm
essentially consists of SiO2 gel from the hydrolysis of Na2SiO3, the ®lming rate is
only determined by the ¯occulation process and is independent of mass-transfer.
Although Na2SiO3 may react chemically with the corrosion products to deposit
Fig. 5. The isotherm curve of iron surface passive ®lm growth in the NaNO2 containing system.
F. Gan et al. / Corrosion Science 42 (2000) 1379±1388 1387
Fig. 6. The isotherm curve of iron surface sendimental ®lm growth in the Na2SiO3 containing system.
ferrous silicate and a mass-transfer of the metallic ion through the deposit layer
should take place, the resistance of mass-transfer could be ignored when the ®lm
is loose and porous. The low inhibition eciency of Na2SiO3 for iron may be
caused by the latter. Upon the results in Fig. 6, a supposition is made that the
inhibition ®lm on the iron electrode in neutral Na2SO4 solution with Na2SiO3 may
consist of SiO2 gel and has a poor protection.
5. Conclusion
Acknowledgements
Metals. The authors would like to thank Prof. B.L. Wu and Dr. S.L. Chen, of
Department of Chemistry at Wuhan University, for their help with the
experimental instrumentation.
References
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