Rapid method for corrosion protection

determination of VCI films

S.B. Valdez, R.K. Zlatev, W.M. Schorr and G.N. Rosas
Engineering Institute, Autonomus University of Baja California, Mexicali, Mexico, and
Ts. Dobrev, M. Monev and I. Krastev
Institute of Physical Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria

Abstract
Purpose – To develop and test a rapid method for evaluation of the corrosion protection (CP) of carbon steel (CS) by vapour corrosion inhibitors
(VCI) films.
Design/methodology/approach – The determination of the CP by VCI on CSs is commonly carried out in a chamber applying neutral salt spray (NSS)
and usually it takes many days. The common disadvantage of the various rapid methods created until now is the need of special laboratory equipment
making their application complicated and inconvenient for field tests. The method for CP measurement of VCI films on CS described in this study is
based on measurement of the height of the anodic peak under galvanostatic condition applied earlier on other types of films and coatings. By means of
a calibration plot: peak height (V) vs NSS protection time (s), CP of VCI films on CS specimens expressed in hours NSS is determined in a few seconds
without using an NSS chamber. Measurements of CP by VCI films under field conditions are performed applying a hand held tester.
Findings – Two groups of CS UNS G10180 steel specimens with increasing thickness of VCI films were studied – one in an NSS chamber and the
second by the application of a corrosion tester. The correlation between the results obtained for the two groups of specimens was found and a
calibration plot was made.
Practical implications – Based on this method, a special corrosion tester was developed, able to measure under field conditions as well.
Originality/value – The method subject of the paper is a further development of a galvanostatic method developed by the authors for CP evaluation of
chromate films of Zn and Cd coatings. The method was modified according to the properties of VCI films

Keywords Vapour pressure, Corrosion inhibitors, Corrosion protection, Steel, Tests and testing

Paper type Research paper

Introduction 2 to 8 wt%, while the pH is normally 7 to 10 for the amine salt

Application of corrosion inhibitors for corrosion protection
(CP) of carbon steel (CS) is simpler than galvanic coatings,
oxidation, painting, etc. The main advantage of the vapour
corrosion inhibitors (VCI) is that no contamination occurs on
the protected surface. The use of the VCI aqueous solutions
avoids the oiling process done by steel producers and the
consequent problems for cleaning, shipping, low CP and
particularly to eliminate safety related problems.
VCI’s are salts of organic, chemical compounds and
inorganic acids, commonly supplied as crystals contained in
plastic foam supports (Valdez et al., 2003). They volatize
easily forming protective films of adsorbed ions on the
metallic surface in closed wet environments; they are also
known as volatile corrosion inhibitors. The VCI’s are used to
diminish the atmospheric corrosion in closed environments
where free air flow is limited. Water-based formulations are
applied as wet films that form uniform thickness after drying.
These formulations normally contain tensoactive substances
to improve a complete wetting of CS surfaces by the aqueous
solution. The usual concentration of VCI in water varies from
The current issue and full text archive of this journal is available at
www.emeraldinsight.com/0003-5599.htm
Anti-Corrosion Methods and Materials
53/6 (2006) 362– 366
q Emerald Group Publishing Limited [ISSN 0003-5599]
[DOI 10.1108/00035590610711705]
and 3 or 4 when there is an excess of mineral or organic acid
in the solution or condensate.
Amine salt based VCI aqueous solutions have a diminishing
effect on the anodic reaction, more pronounced in the
presence of free amines. The anodic ionization of a metal
surface is slowed due to the direct contact of the amine salt
solution. The effective wetting that improves the formation of
a stronger hydrophobic barrier is due to the surfactant content
which increases the contact angle of the liquid with the metal
surface. After the ions create the protective barrier, corrosion
accelerators such as oxygen and aggressive anions, cannot
reach the metal surface and corrosion is inhibited.
Dicyclohexylamine (DCHA) is one of the most effective VCI’s.
Nitrite, carbonate or organic acid salts are commonly employed
to formulate oil, foam impregnated or aqueous volatile corrosion
inhibitors. In this work, the dicyclohexylamine carbonate salt
(DCHAC) was selected for its ability to protect ferrous alloys
from atmospheric corrosion.
The evaluation of the CP of any film is usually carried out in a
chamber with neutral salt spray (NSS). The application of this
classic method however takes a long time: days, weeks or even
months which is unsatisfactory in most of the cases. Therefore,
the development of a rapid method for evaluation of the CP of
protection films will contribute to solve this problem.
Diverse methods for fast evaluation of CP were developed
and applied, mainly based on potentiostatic polarization
(DIN 50021, DIN 50960), electrochemical spectroscopic
impedance ESI (Zeller and Savinell, 1986), films breakdown
voltage (Kudzene and Bikulchius, 1989), the Faradic

362
 Rapid method for corrosion protection determination of VCI films Anti-Corrosion Methods and Materials
S.B. Valdez et al. Volume 53 · Number 6 · 2006 · 362 –366

distortion of the conversion film (Pirnat et al., 1994), Instrumentation

isopotential contour mapping (Kalantary, 1994), etc. but Perkin Elmer Fourier Transform Infrared Spectrometer
none of these methods has been applied for the CP evaluation (FTIR) with an attenuated total reflection (ATR) device
of VCI. was utilized to analyze the composition of the VCI film. The
A rapid method for the evaluation of CP of protection films thickness of the dry VCI film was measured by Panametrics-
on CS, based on galvanostatic anodic polarization was NDT TM Model 37DL PLUS hand-held ultrasonic
developed and reported earlier by the authors as well as its thickness gauge, used with Software V1.02.
various applications (Dobrev et al., 1986, 1992, 1995, 1996, A corrosion tester, special electronic device (Figure 1) was
2000). Further development of the method and results of its developed for CP measurement. This instrument consisted of
application on VCI protection films are the subject of the
a special electrochemical cell and a galvanostat (300 V,
present work.
100 mA) equipped with a peak detector measuring unit and
two LED displays, for the current and for the anodic potential
Methodology maximum. The tester measured and displayed the anodic
Measurement method peak height under galvanostatic conditions and the magnitude
The measurement method was based on the anodic peak height of the current. The results of the measurement of anodic peak
determination during a galvanostatic anodic polarization of the height were transferred to a PC for additional treatment and
protected specimen carried out in a proper electrolyte. A storage through an RS 232 port. The measuring
controlled current flowed through the pores of the protection electrochemical cell consisted of an acrylic plastic cylindrical
film towards the CS specimen surface. If the pores size is small, body with a 3.5 mm in diameter soft polyurethane ring at its
the resulting electrical resistance of the protection film is high. bottom. By a screw mechanism the electrochemical cell could
Thus, in order to maintain the current constant, the galvanostat be moved up and down and the polyurethane ring was pressed
will increase the output voltage in order to overcome the pores to the specimen preventing electrolyte leakages. The
resistance. As a result of the potential rising, a breakthrough of electrochemical cell contained two electrodes: a stainless
the protection films takes place and the current of the steel tube used as counter electrode and a silver-silver chloride
galvanostat reaches its preview constant value. After the
(Ag/AgCl) as the reference electrode, while the CS specimen
destruction of the protection film, a clean metal surface
covered with a VCI film played the role of the working
contacts the electrolyte and the galvanostat voltage decreases in
order to maintain the current value constant, so a peak will electrode.
appear in the potential/time plot. Since, the breakdown voltage
is a function of the pore size, which determines the CP Figure 1 Corrosion tester
properties of the film, the height of the peak will correspond to
the CP of the protection film.
In general, the peak height/time relationship (Dobrev et al.,
1996, 2000) shows that potential maximum in most of the
cases is reached during 0.05-0.5 s and that the peak width
depends on its height. Also, the rising edge of the peak
corresponding to the breakthrough of the protection film is
shorter (measured in ms) than the falling edge that
corresponds to the complete destruction of the protection
film (measured in s).
CS specimens coated by VCI were inserted in an NSS
chamber for two weeks and the anodic peak potential was
measured under galvanostatic conditions every day applying
the corrosion tester. The measured specimen was placed on
the stainless steel support of the corrosion tester and the
plastic electrochemical cell was pressed on the specimen
surface and filled with the electrolyte. The current was
applied during 10 s and the resulting peak potential was
measured. Data of peak heights from measurements at
different sites of the steel surface were collected and
compared with the results of corrosion tests in NSS chamber.

Specimens
Test specimens were prepared from 1 mm thick sheet CS
UNS G10180 steel. VCI was applied as an aqueous solution
of DCHAC with a pH of 8.2, containing non ionic
surfactants: alkyl phenol ethoxylated type, to get a high
wetting effect on the metal surface. The wet VCI film on the
CS surface was dried under indoor conditions. The final
uniform VCI film was obtained by a multiply covering of the
specimens followed by drying and thickness control. The
conditions of NSS tests conformed to ASTM standard B117.

363
 Rapid method for corrosion protection determination of VCI films
S.B. Valdez et al.
Reagents
The electrolyte was inserted into the cell using a plastic
syringe through the stainless steel tube employed also as a
counter electrode (Dobrev et al., 1996). The electrolyte was
prepared using analytical grade chemicals and deionised
water. The optimized electrolyte contained 0.5 M NaCl and
0.5 M Na2SO4.
Results
FTIR-ATR characterization of VCI films
The IR spectra of the aqueous solution and the dry VCI film
formed under conditions described below were recorded by
FTIR spectrometer using an ATR plate, Figures 2 and 3.
The concentration range of DCHAC in VCI aqueous
solutions was in the range: 2-5 per cent, to get a homogeneous
solution, containing surfactants as well.
The aqueous formulation of VCI based on DCHA formed
a protection film within 30 min. The wet VCI film on the CS
Figure 2 IR spectra of aqueous VCI based on DCHAC
Figure 3 IR spectra of dry VCI film based on DCHAC
364
Anti-Corrosion Methods and Materials
Volume 53 · Number 6 · 2006 · 362 –366
surface was dried under indoor conditions. The covering
procedure was repeated while VCI films with a thickness
between 1 and 3 mm were achieved.
Anodic peak height measurement
A group of ten CS specimens covered by 3 mm thick VCI film
were kept under indoor conditions at 258C. Another group of
ten were tested in the NSS chamber at 37 ^ 18C. The anodic
peak potentials of the two specimen groups were measured
every 24 h applying the corrosion tester according to the
procedure described above.
Keeping the specimens under indoor conditions lead to an
increase in the density of the VCI film along the time
increasing the CR of the VCI film. As a consequence, the
anodic peak height slightly increased (Figure 4).
The results for the CS specimens exposed to NSS chamber
are shown in Figure 5, where the flat plateau corresponds
to the degree of CP along the time. The change in the trend to
fall is due to the VCI film destruction.
 Rapid method for corrosion protection determination of VCI films Anti-Corrosion Methods and Materials
S.B. Valdez et al. Volume 53 · Number 6 · 2006 · 362 –366

Figure 4 Calibration plot for 3 mm VCI film on CS under indoor air Figure 6 Anodic peak height – time in NSS plot for different VCI film
conditions and 258C thicknesses

Figure 5 Anodic peaks height – time plot for VCI film on CS in NSS at
378C

Figure 7 Calibration plot under NSS chamber conditions

At the same time, the specimens not covered or partially covered

by VCY were inserted in the NSS chamber and observed
microscopically daily; the results are shown in Figure 6.
Figure 8 Covered (left) and not covered steel surface after 288 h in NSS
Calibration plot at 378C (dVCI ¼ 3 mm)
Two calibration plots in coordinates: anodic peak heights vs
time are presented. One is related to VCI films under indoor
conditions, shown in Figure 4. The second, shown in Figure 7,
relates to NSS chamber conditions. Abscise for both is the time
of the beginning of destruction of the VCI films, i.e. the end of
the plateau and the first points of the falling part of the curve.
The ordinate values of the two plots are the corresponding
anodic peak heights measured by the corrosion tester where
higher anodic peaks correspond to longer time of protection.

Microscopic observation
The CS specimen partly covered by a 3 mm thick VCI film
after 288 h exposition in NSS chamber shows that the two
parts of the specimen surface – the treated and the untreated
with VCI are well distinguishable (Figure 8). The untreated
surface is completely covered by corrosion products, while the
treated is unchanged – the formation of corrosion products
has just begun on very small separate areas.

365
 Rapid method for corrosion protection determination of VCI films
S.B. Valdez et al.
Discussions
VCI’s are substances used to protect metallic components
against corrosion exposed to wet close environments. The
evaluation of their CP ability in simulation chambers usually
takes several days and the impossibility to be used in field
conditions.
In the present work, a rapid electrochemical galvanostatic
method was adapted to evaluate the CP performance of
different thicknesses in the range from 1 to 3 mm VCI films on
CS surfaces. The films were deposited using a DCHAC
(2-5%w/w) and less than 1 per cent of surfactant wetting
agents aqueous solution with a pH of 8.2.
The presence of the VCI components in the film was
corroborated by FTIR-ATR analysis. The presence of free
amine in the solution is clear (Figure 2) and show the
presence of a peak at 1,638.69 cm2 1, while the carbonate salt
predominated in the dry film (Figure 3) as is shown by the
transmittance peak at 1,735.5 cm2 1. The peak of water at
3,308 cm2 1 has negligible height in the IR spectra of the dry
film while it has significant height in Figure 2.
The IR spectra results proved the protection mechanism of
VCI films as well as the peak height vs time curve shape.
Along the time, a conversion process occurred inside the VCI
film with the free amine and the air humidity participation
resulting in a protective barrier forming on the metal surface.
This result explains the diminishing of the free amine
concentration in dry VCI film. Under indoor conditions, the
process rate was slow leading to a slight increase in the
protecting properties of the VCI film, resulting in an increase
of the anodic peak height (Figure 4).
On the other hand, the extremely high humidity under the
NSS chamber conditions provoked film degradation after a
period of stable protection. That is why the curve: peak height/
time for CS specimens kept in an NSS chamber (Figure 5) has a
completely different shape compared with the one obtained
under indoor conditions. Two well defined parts appears: a
plateau followed by a rapid fall. The plateau height corresponds
to the degree of the CP by the VCI film and its length
corresponds to the time of CP. The falling part of the curve
corresponds to destruction of the VCI films and lost of CP.
The higher plateau is related to longer time of protection as
well. Both parameters: height and length of the plateau
depend on the VCI film thickness and increased thickness of
the VCI film lead to increased CP (Figure 5). The VCI film of
3 mm was unchanged after 240 h in the NSS chamber, while
1 mm thick film was completely destroyed within this time.
The calibration plots under indoor and NSS chamber
conditions are used for rapid CP determination of VCI films
expressed as time under indoor conditions or time in NSS.
The results obtained for the height of the anodic peak within a
few seconds with the corrosion tester are converted in time
applying the calibration plot.
The microscopic observation results are in good agreement
with the data shown in Figure 5 and proved the reliability of
the calibration plot. The time value of 288 h corresponds to
the end of the plateau zone and the beginning of the corrosion
products formation for the surface zone which was treated
with the VCI solution.
To purchase reprints of this article please e-mail: reprints@emeraldinsight.com
Or visit our web site for further details: www.emeraldinsight.com/reprints
366
Anti-Corrosion Methods and Materials
Volume 53 · Number 6 · 2006 · 362 –366
Conclusion
A rapid method for CP determination of the VCI protection
films on CS specimens is described. Measuring the height of
the anodic peak under galvanostatic conditions, the CP
expressed in hours NSS can be determined in a few seconds
without the use of NSS chambers. The determination is based
on a previously build calibration plot: anodic peak height vs
protection time in NSS. Measurements of CP of VCI
protection films, in field conditions are performed applying
hand held corrosion tester.
References
Dobrev, Ts., Monev, M., Krastev, I., Richtering, W.,
Zlatev, R. and Rashkov, St. (1996), “Electrochemical
determination of corrosion protection properties of
chromated zinc, zinc alloy and cadmium electroplated
coatings”, Trans. I.M.F. (UK), Vol. 74 No. 2, p. 45.
Dobrev, Ts., Monev, M., Krastev, I., Richtering, W.,
Zlatev, R. and Rashkov, St. (2000), “An electrochemical
method for determination for corrosion protection
properties of chromate films onto zinc, zinc alloys and
cadmium electroplated coatings”, VII Intern. Corr. Symp.
Proceedings, pp. 442-9.
Dobrev, Ts., Monev, M., Krastev, W., Zlatev, R. and
Rashkov, St. (1995), “A method for express test of
protective layers on metal surfaces”, Bulg. Pat. No. 61538.
Dobrev, Ts., Monev, M., Nikolova, S. and Rashkov, St.
(1986), “Evaluation of the corrosion protection properties
of multilayer copper-nickel-chromium deposits, surface
technology”, Surf. Coat. Technol., Vol. 29, p. 27.
Dobrev, Ts., Monev, M. and Rashkov, St. (1992), “A method
for the evaluation and forecasting of the corrosion
protection properties of multilayer Ni-Cr and Cu-Ni-Cr
electrodeposited coatings”, Bulg. Chem. Comm., Vol. 25
No. 1, p. 49.
Kalantary, M.R. (1994), “Zinc alloy electrodeposition for
corrosion protection”, Plat. Surf. Finish., Vol. 81, p. 80.
Kudzene, B. and Bikulchius, H. (1989), “Prognozirovanija
korozionnoj stoykosti hromatnih pleonak na Zn pokritiah
metodom Fritinga”, Trudi Acad. Sci. Lit. SSR, B, Vol. 175,
p. 15.
Pirnat, A., Meszaros, L., Meszaros, G. and Lengyel, B.
(1994), “A measuring method and instrument for the
evaluation of corrosion resistance of chromate layers”, Corr.
Sci., Vol. 34, p. 1147.
Valdez, B., Flores, J., Cheng, J., Schorr, M. and Veleva, L.
(2003), “Application of vapour phase corrosion inhibitors
for silver corrosion control in the electronic industry”,
Corrosion Reviews, Vol. 21 Nos 5/6, pp. 445-57.
Zeller, R. and Savinell, R.F. (1986), “Interpretation of AC
impedance response of chromated electrogalvanized steel”,
Corr. Sci., Vol. 26, p. 389.
Further reading
Paatsch, W. (1978), “Korrosionsschutz Testmöglichkeiten
und Erläuterungen”, Galvanotechnik, Vol. 69, p. 3.