Surface and Coatings Technology 174 175 (2003) 107111

Application of plasma deposited organosilicon thin films for the corrosion

protection of metals
F. Fracassia,*, R. dAgostinoa, F. Palumboa, E. Angelinib, S. Grassinib, F. Rosalbinob
a

Dipartimento di Chimica Universita` degli Studi di Bari, IMIP CNR via Orabona, 4 70126 Bari, Italy
b
Dipartimento di Scienza dei Materiali e Ingegneria Chimica, Politecnico di Torino, Italy

Abstract
In this contribution it will be shown that plasma enhanced chemical vapor deposition (PECVD) of silicon containing organic
compounds is a promising approach for the corrosion protection of metals (steel and magnesium alloys). When the deposition
process is preceded by a suitable plasma treatment, which depends on the particular metal under study, a marked increase of the
protective properties measured with electrochemical impedance spectroscopy (EIS) is detected. The highest impedance modulus
obtained for Mg is 450 KVcm2, 8000 times higher than for the bare metal. Highly protective coatings are obtained for inorganic
films, free of sylanols. A marked decrease of the impedance modulus of coated substrates has been registered after immersion in
electrolyte solution due to the presence of pinholes which represents defect points where localized corrosion starts.
2003 Elsevier Science B.V. All rights reserved.
Keywords: Corrosion; PECVD; SiOx

1. Introduction
The protection of metals from corrosion is a very
important problem from the economical point of view
and for its implication on the environment. Corrosion
prevents the wide utilization of some interesting materials such as magnesium alloys in strategic applications,
such as transport and aerospace and therefore many
studies have been carried out in order to develop
successful corrosion prevention strategies. Magnesium
alloys are usually protected by chromate conversion
coatings, anodizing andyor polymer coatings. Unfortunately, despite of their simplicity, these approaches make
use of toxic reactants and produce toxic wastes and
environmental pollutants (e.g. hexavalent chromium ion
is highly toxic and carcinogenic) and therefore alternative technologies should be studied and developed.
Similar problems are encountered also for the protection
of steel manufactures. In this scenario, the plasma
enhanced chemical vapor deposition (PECVD) from
organosilicon precursors appears to be an attractive
approach to increase the corrosion resistance of metallic
*Corresponding author. Tel.: q39-080-544-2009; fax: q39-080544-3405.
E-mail address: fracassi@chimica.uniba.it (F. Fracassi).

materials, since it is a clean environmentally friendly

technique, which does not produce wastes or appreciable
atmospheric emissions.
Among the main technological advantages of PECVD
it is important to mention the possibility of carrying out
substrate pre-treatments, just before the deposition process in the same reactor, in order improve the coatingsubstrate performances.
In this work the evaluation of the corrosion resistance
has been performed by means of electrochemical impedance spectroscopy (EIS), a rapid indirect diagnostic
technique which allows a quantitative evaluation of the
inhibiting effect of the applied coating and to obtain
interesting information on the failure mechanism. The
detailed description of EIS can be found elsewhere w1x,
the measurements are performed by applying an alternating potential to the coated substrate immersed in an
electrolytic solution (Na2SO4 or NaCl). By changing
the frequency of the alternating potential (v), it is
possible to measure the current intensity as a function
of v and therefore to calculate the impedance (Z) at
various frequency values. A convenient way to represent
the experimental data is the Nyquist plot, i.e.ImZ vs.
ReZ (ImZ and ReZ are the imaginary and the real part
of Z, respectively). A suitable equivalent electrical
circuit representing the system under study w2x allows

0257-8972/03/$ - see front matter 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0257-897203.00422-5

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F. Fracassi et al. / Surface and Coatings Technology 174 175 (2003) 107111

3. Results

2. Experiments

A typical Nyquist plot for a Mg alloy coated with a

1300 nm thick organosilicon film after 1 h of exposure
to a 0.1 M NaCl solution is reported in Fig. 1. The
equivalent circuit model reported in Fig. 2 was considered for an accurate analysis of the impedance diagram.
In this model Rs is the solution resistance, Rct the charge
transfer resistance (electron transfer) of the faradic
process on the metal surface, in parallel with a constantphase element (CPE), Cc is the coating capacitance, in
parallel with the coating resistance Rc, Cdiff (CPE) and
Rdiff are related to a possible diffusion process of
reagents from the bulk solution toward the sample
surface. The impedance of a CPE is represented by the
equation ZsC1y(i v)a.
Notwithstanding the low thickness of the deposited
coating (lower than 1300 nm), a marked inhibiting
action toward the corrosion process occurring at the
metal surface is observed with EIS, when HMDSO or
TEOS are utilized as film precursors, provided a suitable
pre-treatment is performed and the deposition conditions
are optimized. The highest charge transfer resistance
obtained for steel and Mg substrates are summarized in
Table 1. A consistent improvement with respect to the
bare steel is detected (from 250 to 2 200 000 V cm2)
when an oxygen plasma pre-treatment is performed,
while for Mg alloy, the best results are obtained with a
H2 plasma pretreatment (from 60 to 480 000 V cm2)
w4x. These values are indicative of a marked slowing
down of the corrosion process occurring at the metal
surface. When TMOS is utilized as a film precursor, the

Protective SiOx thin films have been deposited on

mild Q panel steel (Fe 99%, Mn-1%) and WE 43 (Mg
94%, Y 3%, Nd 3%) Mg alloy substrates, positioned on
the ground electrode of a home-made parallel plate
reactor (13.56 MHz), at the floating plasma temperature
(T-60 8C) and 100 mTorr of pressure. The feed gas
contained the organosilicon monomer in the mixture
with oxygen and argon. The following organosilicon
monomers have been tested up to now: hexamethyldisiloxane (HMDSO) for steel and Mg, tetraethoxysilane
(TEOS) and tetramethoxysilane (TMOS) for Mg. Pretreatments have been performed in the same reactor,
immediately before the application of the SiOx coating,
in plasma fed with oxygen, hydrogen or CF4 O2 (20%).
Electrochemical impedance measurements have been
performed in aerated 0.1 M Na2SO4 solution for steel
and in aerated 0.1 M NaCl solution for Mg, at 25"1
8C, using a frequency response analyzer EIS300 (Gamry
Instruments). Impedance spectra were recorded at the
open circuit potential with a three-electrode electrochemical configuration (leadlead sulfate electrode as reference and titanium counter electrode).

Fig. 2. Electrical circuit utilized to fit the EIS data obtained with
SiOx coated Mg substrates immersed in aerated 0.1 M NaCl solution.

Fig. 1. Nyquist plot of a Mg alloy sample coated with SiOx film

deposited after a hydrogen plasma pretreatment, in plasma fed with a
3:50 TEOSyO2 mixture after 1 h of immersion in 0.1 M NaCl solution.

to fit the experimental points of Nyquist plot and

therefore to obtain the values of the circuital elements
corresponding to the system and in particular the values
of the charge transfer resistance, Rct. According to the
scientific literature w3x the inhibition capability of the
SiOx coating has been correlated to Rct which is related
to the corrosion process occurring at the metalycoating
interface.

F. Fracassi et al. / Surface and Coatings Technology 174 175 (2003) 107111

109

Table 1
Comparison between the best charge transfer resistance obtained with
EIS on steel and Mg alloy as a function of the pretreatment

Steel
Mg

Untreated

Coated (1300 nm)

Pretreated
and coated

250 V
60 V

1275 V
1150 V

2.2 MV (O2)
125 kV (CF4 O2)
480 KV (H2)

EIS measurements have been performed in 0.1 M Na2SO4 for steel

and 0.1 M Nacl for Mg (1 h immersion).

best charge transfer resistance obtained is orders of

magnitude lower than with HMDSO and TEOS.
The results on steel have been explained by means of
XPS depth profile (Arq ion sputtering) w5x. In agreement with published data, oxygen plasma removes the
surface contamination of adventitious carbon, increases
the surface concentration of oxidized Fe3q and decreases
the density of reduced species (e.g. Fe2q), i.e. the
electron donor species. As a consequence of this modification, the reduction of atmospheric oxygen on the
steel surface, which is responsible for the corrosion
diffusion, slow down w5x. In the case of magnesium
substrates, the effect of the best pretreatment (H2 plasma) is obviously different since it reduces the extent of
surface oxidation. In fact XPS depth profile shows that
when the Mg surface is treated in H2 plasma, a marked
increase of the unoxidized Mg component is revealed
underneath the uppermost layers (Fig. 3), which are
reasonably oxidized during the short time elapsed
between the H2 plasma treatment and XPS analysis. The
comparison of the O 1s XPS region (after 5 min of
Arq sputter cleaning) shows that when the magnesium
surface is treated in H2 plasma a preferential removal of
OH groups occurs, in fact in Fig. 4 it is shown that the
contribution of hydroxyl groups at 533.2 eV becomes
lower than that of the oxide one (531.0 eV) after H2
plasma treatment w6x. A contribution of preferential
sputtering and surface rearrangement due to the sputter
cleaning procedure, however, cannot be ruled out. The
improvement of corrosion resistance reported in Table 1

Fig. 3. Mg surface depth profile (Auger KLL transition). Without (a)

and with (b) hydrogen plasma treatment.

Fig. 4. O 1s region of Mg substrates after 5 min of Arq sputtering

(3 KeV). (A) as received; (B) after hydrogen plasma treatment.

for the pretreatment in CF4 O2 (20%) plasma has been

ascribed to the formation of MgF2; w6x the presence of
oxygen in the feed gas avoids the massive formation of
fluorocarbon polymer contamination. The reasons of the
beneficial effect of the pretreatment on the properties of
SiOx coatings is not completely understood, at present
the following factors appear to play a key role: elimination of surface contamination (i.e. hydrocarbon layer);
modification of the chemical composition and consequent passivation of the metal surface at the metalcoating interface; improvement of the coating-metal
adhesion and reduction of film defectiveness.

Fig. 5. FT-IR of a SiOx thin film (TEOSyO2 yArs3y30y36, 100 mTorr,

100 W) immersed in 0.1 M NaCl : (A) as deposited; (B) after 24 h;
(C) after 720 h.

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F. Fracassi et al. / Surface and Coatings Technology 174 175 (2003) 107111

Fig. 6. SEM photograph of a SiOx coating; (a) as deposited; (b) after 24 h of immersion in NaCl 0.1 M.

The exploitation of various experimental conditions

and film composition has shown that the best corrosion
protections are obtained for inorganic SiOx-like coating,
when any organic and SiOH (silanol) groups are
detected by infrared spectroscopy. This is in agreement
with what was recently reported on the utilization of
SiOx thin film as a barrier to oxygen and water vapor
on PET for food packaging w7x. Inorganic films are
more compact, more cross-linked and therefore they are
a good barrier to the permeation of liquids and gases.
Silanol groups decrease the crosslinking of the coating
and represent reactive points where the degradation of
the film immersed in water or exposed to humidity
starts. This can be appreciated in Fig. 5, where it is
shown that, for SiOH-containing coatings, the IR absorption of silanol groups increases with the time of immersion in NaCl solution. If the SiOx film does not contain
silanols, the FT-IR spectrum is not modified during
immersion in the electrolytic solution. The best approach
to obtain inorganic deposits from organosilicon precursors is to increase the oxygen content of the feed gas;
oxygen atoms generated by plasma activation burns
the organic groups and leaves an inorganic SiOx-like

film. Unfortunately this can result in a contemporaneous

increase of silanol concentration w8x which reduces the
chemical stability of the coating and therefore its corrosion resistance. This inconvenience can be solved by
rising the input power, which decreases the SiOH concentration as well as that of the residual organic groups.
In order to study the stability of the film, EIS
measurements have been performed on substrates coated
under the best conditions as a function of the time of
immersion in the electrolyte solution. A decrease of the
corrosion protection with time has been registered. In
fact the Rct of a steel sample immersed for 870 h in
Na2SO4 0.1 M is reduced to 16 KV cm2 (from 2.2 MV
cm2), that of a Mg after 192 h immersion in NaCl
passes from 480 to 2 KV cm2. Fig. 6 shows that this
effect can be ascribed to a localized corrosion that starts
at a few defect points (not present on the as deposited
coating) representing preferential electrolyte penetration
path. The corrosion process remains localized at these
defect points also after long immersion times, in fact
the SiOx coating is stable, its chemical composition is
not affected by the interaction with the electrolyte since
any variation is detected, even after long immersion
time by FT-IR. The chemical stability of deposited films
is also confirmed by the trend of the coating capacitance,
Cc (see Fig. 2), as a function of exposure time, reported
in Fig. 7. As a matter of fact, some authors relate the
coating degradation to a progressive increase of Cc
values, w9x while in our case an opposite trend is
observed.
Acknowledgments
This research has been partially supported by the
Italian Ministero dellUniversita` e della Ricerca Scientifica e Tecnologica (DM n. 10 del 23 gennaio 2001).
References

Fig. 7. Trend of the coating capacitance, Cc , as a function of exposure

time in 0.1 M NaCl solution.

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