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Corrosion Science 42 (2000) 1379±1388

A study on the ®lming kinetics of corrosion


inhibitors in Fe/Na2SO4 system using EQCM
Fuxing Gan*, Zhongxu Dai, Dihua Wang, Lu-an Yao
Department of Environmental Science, Wuhan University, Wuhan, 430072, People's Republic of China
Received 26 May 1999; accepted 20 November 1999

Abstract

Electrochemical Quartz Crystal Microbalance (EQCM), a new electrochemical technique


developed in recent years, has been employed to study the ®lming kinetics of corrosion
inhibitors in Fe/Na2SO4 neutral system. An equation was deduced to calculate the real
mass change of the electrode surface during the ®lming and some experimental isothermal
curves of ®lming kinetics of corrosion inhibitors were found. It is found that the ®lm
growth on iron in Na2SO4 solution follows the parabolic law in the presence of the
oxidizing inhibitor NaNO2, similar to oxidation kinetics of some metals at high
temperature, or the linear law in the presence of the precipitating inhibitor Na2SiO3. 7 2000
Elsevier Science Ltd. All rights reserved.

Keywords: Electrochemical Quartz Crystal Microbalance; Iron

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 dicult 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 dicult 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

eciency by conventional methods, e.g., weight loss. Microscopically, the


corrosion inhibitor molecule in neutral media may only approach to the surface
®lm, but not to the metal/substrate surface. To study the neutral inhibitor, the
information about the interaction between the inhibitor and the surface ®lm must
be achieved using some new techniques that do not involve traditional
electrochemical methods.
Electrochemical Quartz Crystal Microbalance (EQCM), a new electrochemical
technique developed in recent years, can be employed to get the mass nanogram
grade change on the metal electrode surface in solution. In addition, its
information is point-blank, and the experimental data are handled very easily. So,
EQCM is especially suitable for in situ study of the process of the metal corrosion
and characteristics of corrosion inhibitors in neutral solution.
Previous studies on corrosion inhibition using EQCM do not date too far back.
To date, there is limited literature on this topic. Hager and coworkers [1] studied
the corrosion on the iron surface ®lm. However, in the range of the selected pH
value, the electrochemical behavior on iron was very complex, and only a
qualitative result was given. Moreover, the inhibition eciency of BTA
(benzotriazole) on copper and a positive synergistic e€ect between BTA and Iÿ
ion obtained by EQCM technology has been reported [2].
In this work, a study on ®lming kinetics of corrosion inhibitors in Fe/Na2SO4
neutral system was carried out using EQCM. An equation to calculate the real
mass change of the electrode surface during the ®lming process was deduced and
some experimental isothermal curves of ®lming kinetics of corrosion inhibitors
were developed.

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 di€erent 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 ˆ 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 ˆ 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 di€erence reported in the paper is the change
value of frequency di€erence between the experiment beginning …t ˆ 0† and the
measuring time …t ˆ t). In our laboratory, the frequency di€erence is measured by
subtracting work oscillator frequency …fWork † from the reference oscillator
frequency …fRef †: Then, there is the next formula:
Df ˆ …Df†w, tˆt ÿ…Df†w, tˆ0 ˆ …fRef ÿ fWork †tˆt ÿ…fRef ÿ fWork †tˆ0

ˆ fWork, tˆ0 ÿ fWork, tˆt …2†

Therefore, if the electrode surface mass is increased, the frequency of the work
oscillator …fWork, tˆt † 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:

Dm…t† ˆ Dmf …t† ÿ Dmc …t† …3†

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†
ˆ 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†
ˆ ÿSnc …5†
dt
As a result, the metallic corrosion rate can be determined from with the
measurement of the frequency di€erence.
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

inhibition eciency of corrosion inhibitor is Z ˆ Z…y†, where y is the covering


degree of the inhibiting protective ®lm, which is generally a function of time,
i.e., y ˆ y…t†: Then, the following formula is obtained from the de®nition of the
inhibition eciency:
nc, i ˆ …1 ÿ Z†nc, b …6†

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†  
ˆ S nf ÿ …1 ÿ Z†nc, 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 ˆ 1: On this condition, because the Z value is
constant, nc, i ˆ …1 ÿ Z†nc, b is also constant. Thus, an integrated formula for Eq.
(7) is obtained using the initial condition Df ˆ 0:
Df…t†
Dmf …t† ˆ ‡ …1 ÿ Z†nc, 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 ˆ …1 ÿ Za †nc , b may be supposed as a constant approximately, where Za is
the averaged inhibition eciency 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 eciency (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. 1. Schematic diagram of the EQCM system.

quartz wafer at a current density of 20 mA/cm2 at pH 3.5, 350 g /dm3 ferrous


ammonium sulfate solution [5].
The electrolyte in all experiments was neutral 0.5 mol/dm3 Na2SO4 solution.
The corrosion inhibitors were 2g/dm3 NaNO2 and 0.24 g/dm3 Na2SiO3. Their
inhibition eciency for iron is 63.2 and 6.1%, respectively, as measured with the
linear polarization technique. All experiments were carried out at room
temperature.

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

4. Results and discussion

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 di€erence 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 di€erent media show di€erent 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.

4.1. In the base electrolyte Na2SO4

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 ˆ ÿ 1ÿ ˆ 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 di€usion 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 di€usion, 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 di€usion in neutral Na2SO4 solution.

4.2. In the presence of passive inhibitor NaNO2

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 ˆ Kt ‡ Const:, a simulated curve was ®tted (see Fig. 5) with a correlation
coecient 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 di€usion 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
ˆ …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 ˆ 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.

4.3. In the presence of precipitating inhibitor Na2SiO3

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 eciency of Na2SiO3 is small …Z ˆ 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 ˆ 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 eciency 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

According to the principle of EQCM and experimental conditions used, an


equation (Eq. (8)) was deduced for the calculation of the true mass change of the
metallic electrode surface during the ®lming, and some experimental isotherm
curves for the ®lming kinetics of corrosion inhibitor were obtained. The
experimental results show that the corrosion rate is constant for the
electrodeposited pure iron in the neutral Na2SO4 solution, and the reaction is
controlled by the di€usion of oxygen. After adding the corrosion inhibitors, the
®lming rate exceeds the corrosive rate on the iron electrode. In neutral Na2SO4
solution with the passive inhibitor NaNO2, the isothermal kinetics curve of the
®lm growth follows a parabolic law, similar to the oxidation kinetics of some
metals at high temperature. And with the precipitating inhibitor Na2SiO3, the
curve shows a linear law.

Acknowledgements

This research was supported by the National Natural Science Foundation of


China and the Chinese State Key Laboratory for Corrosion and Protection of
1388 F. Gan et al. / Corrosion Science 42 (2000) 1379±1388

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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[6] J.-Y. Zhuo, Handbook of the Corrosion Data, Chemical Industry Press, (1982) p. 83 (in Chinese).
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