Anti-Corrosion Methods and Materials

Emerald Article: Preparation of non-chromium polymer films on zinc for

corrosion protection due to a compound effect between silane and cerium
salt
Da-jing Fang, Xu-hui Mao, Ye-ming Zhang, Zhi-liang Chen, Min Liu, Fu-xing
Gan

Article information:
To cite this document: Da-jing Fang, Xu-hui Mao, Ye-ming Zhang, Zhi-liang Chen, Min Liu, Fu-xing Gan, (2009),"Preparation of
non-chromium polymer films on zinc for corrosion protection due to a compound effect between silane and cerium salt",
Anti-Corrosion Methods and Materials, Vol. 56 Iss: 4 pp. 226 - 231
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http://dx.doi.org/10.1108/00035590910969356
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 Preparation of non-chromium polymer films
on zinc for corrosion protection
due to a compound effect between
silane and cerium salt
Da-jing Fang and Xu-hui Mao
School of Resource and Environmental Science, Wuhan University, Wuhan, Peoples Republic of China
Ye-ming Zhang
School of Environmental Science and Engineering, Huangshi Institute of Technology,
Huangshi, Peoples Republic of China, and
Zhi-liang Chen, Min Liu and Fu-xing Gan
School of Resource and Environmental Science, Wuhan University, Wuhan, Peoples Republic of China and
State Key Laboratory for Corrosion and Protection of Metals, Shenyang, Peoples Republic of China

Abstract
Purpose The purpose of this paper is to study the compound effect between silane and cerium salts in the passivation process of chemical conversion
treatment of zinc.
Design/methodology/approach Chemical conversion treatment using 3-Glycidoxypropyltrimethoxysilane on zinc is investigated as an alternative
treatment to chromate conversion. The surface chemistry of the silane-treated samples is investigated with mass change measurements, polarization
curves, electrochemical impedance spectroscopy (EIS) and the salt spray tests (SST). The surface morphology of samples was studied using a scanning
electron microscope.
Findings The polarization curves, EIS and SST data are in agreement. On the surface of zinc, the silane formed a compound with the cerium, thus
enhancing the adhesion and corrosion resistance of the polymer film.
Originality/value There have been few reports on the compound effects of silanes and cerium salts in the passivation process. The mechanism of
this compound effect may be due to the ability of Ce3 ions to gain access to the interface through tiny cracks or micropores in the cross-linking
structure of GPS polymer films on zinc, and the subsequent oxidation of Ce3 to Ce4 by H2O2 may result in a barrier effect between the electrolyte
and the metallic substrate.

Keywords Passivation, Zinc, Corrosion protection, Films (states of matter)

Paper type Research paper

Introduction
Zinc is widely used as a metal coating on steel to reduce
corrosion, where the zinc acts as a sacrificial anode providing
high corrosion resistance. In the past, a very popular way to
reduce the corrosion rate of zinc was the use of chemical
conversion layers based on hexavalent chromium ions
(Cr6 ), which can increase the passivation tendency of the
zinc. This procedure is quite effective also for improving the
adhesion of organic coatings deposited on the zinc surface,
but there is a serious environmental problem associated with
the use of Cr6 in the formation of chromate conversion
(CRC) films for galvanized steels because of the high toxicity
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and the strong carcinogensis of the Cr6 ions (Xia and
McCreery, 1998). For these reasons it is desirable to identify
alternative methods for corrosion protection, other than the
use of chromium salts, which are now restricted by
environmental protection legislation all over the world.
Silicate layers have been deposited on aluminum
(Thim et al., 2000), copper (Garcia-Cerda et al., 2002) and
iron alloys (Zwinkels et al., 1996), and as reported, silica
containing layers can also be deposited on zinc from alcoholic
colloidal solutions of silica derived from hydrolyzed
alkoxysilanes (Brinker and Scherer, 1990; Atik et al., 1994).
Moreover, the use of silane coupling agents (SCA), which
containing many organofunctional groups, seems promising
as an environmentally benign alternative for corrosion
protection methods (Veeraraghavan et al., 2003; Hara et al.,
2003). Apparently, SCAs have received the most attention of

Da-jing Fang gratefully acknowledges the support and continuous

Anti-Corrosion Methods and Materials
56/4 (2009) 226 231 encouragement from Prof. Fu-xing Gan, Prof. Lin An and Dr Xu-hui
q Emerald Group Publishing Limited [ISSN 0003-5599] Mao as well as the help of Si-yu Zhang and Yu-jie Qiao for sample
[DOI 10.1108/00035590910969356] preparation.

226
 A compound effect between silane and cerium salt
Da-jing Fang et al.
the various organic conversion coatings being developed, for
the reason that SCAs are capable of forming strong bonds to
metal substrates and, additionally, of forming cross-linking
polymers on the zinc surface. Both of these abilities contribute
to the formation of strong conversion films. Recent
publications have reported that the chrome-free conversion
coatings formed by SCA were comparable to or better than
CRC films (Tang and van Ooij, 1997; van Ooij and Child,
1998). Additionally, more than half of the methods associated
with the applications of SCA for conversion coating are
protected by patents (van Ooij, 1996a; van Ooij, 1996b; van
Ooij et al., 1998; van Ooij and Yuan, 1998). Another
environmentally benign inhibitor, cerous nitrate, is also
known to be effective for corrosion resistance of zinc or
galvanized steel in acidic solutions. This kind of inhibitor
suppresses the cathodic process of zinc corrosion by the
formation of a hydrated or hydroxylated cerium oxide layer on
the surface (van Ooij et al., 2001; Aramaki, 2001). This layer
is constructed by adsorption of hydrated or hydroxylated
Ce3 ions on the hydroxylated zinc surface, therefore,
protecting zinc from corrosion.
In this paper, a characterization of a compound conversion
film of silane and cerium on zinc surface is reported in
comparison with traditional chromate treatments. An
improved method to form a dense cross-linking polymer
film containing silica and cerium onto zinc is proposed that is
based on the use of GPS and cerium salts. The central aim of
this study is to investigate the possibility and feasibility of
the composition of silane and cerium salt as well as the
anticorrosion effectiveness of the GPS-Cerium conversion
(GCC) polymer films in comparison with CRC films on zinc.
Experimental
In all experiments, pure zinc specimens (99.95 per cent purity,
2.5 mm thickness), provided by Wuhan Research Institute of
Materials Protection, were prepared by dividing the pure zinc
plate into 35 55 mm (for SST) and 8 12 mm (for making
electrodes) sheets. The smaller zinc sheets were fixed with epoxy
adhesive to the end of special plastic tube holders and the
outside of the zinc sheet was used as an electrode. Every zinc
sample was degreased at about 325 K for 5 min in an aqueous
alkaline degreaser after its surface was polished with emery
paper and rinsed with distilled water. After these steps, the
sample was rinsed with distilled water again before use.
A high grade reagent of Ce(NO3)3 6H2O, CoSO4 7H2O,
H2O2 (30 per cent), and nanometric colloidal silicate were
used in this experiment. The silane, GPS, is a commercial
product of the Debang Chemical Industries, Ltd, Hubei, PR
China.
An example of the GCC polymer film preparation is
described as follows: cerium salt, hydrogen peroxide and
nanometric colloidal silicate were added into an aqueous
solution containing GPS and methanol (hydrolyzed for
several hours, 298 K, with agitation) after the pH value of
the aqueous solution had been adjusted to about 1.5. The
specimens then were rinsed thoroughly with distilled water
and treated in the foregoing solution immediately after they
were acid activated in 3 mass% HNO3 at 298 K for 5 s.
Immediately after the passivation process, the specimens with
wet films were placed into a convection oven at 423 K for
40 min. The specimens then were taken out from the oven for
natural aging for two days.
227
Anti-Corrosion Methods and Materials
Volume 56 Number 4 2009 226 231
For the sake of comparative study, a GPS film was prepared
on zinc in an aqueous solution containing only GPS and
methanol following the foregoing method, with a cerium
conversion (CEC) film on zinc in aqueous solution containing
cerous nitrate, hydrogen peroxide and boric acid. Table I
shows the operation conditions of CEC, CRC, GPS, GCC
films for all experiments.
A Sartorius BS 124S balance (made in Germany) with an
accuracy of 102 4 g was used to record mass changes. The
mass gain of the zinc sheet specimen was measured before
and after the aforementioned passivation process at room
temperature. After the passivation process, the corrosion
process was carried out by immersing the zinc sheet into a
solution containing 1.3 M lead acetate (5.8 pH, adjusted by
acetic acid) at room temperature for 1 min. Subsequently, the
zinc sheets were brushed free of corrosion products, rinsed
and dried. Finally, the weight losses of the zinc sheet
specimens were measured immediately before and after the
corrosion process.
A zinc electrode with an exposed area of 0.896 cm2 was
immersed in an aerated 0.5 M NaCl solution at 303 K for 4 h.
With a saturated calomel reference electrode and a platinum
counter electrode, the anodic and cathodic polarization curves
of the bare and film-covered electrodes were measured
potentiodynamically in the NaCl solution at room
temperature at a sweep rate of 5 mV/min in the positive and
negative directions starting from open-circuit potential. Data
obtained from electrochemical impedance spectra (EIS) were
recorded at the corrosion potential in a frequency range
between 105 and 10 102 3 Hz by Parstat 2273 (Ametek Inc).
Surface morphologies of the films were analyzed using a
Stereoscan 440 (Leo) scanning electron microscope (SEM).
And the corrosion behavior was evaluated by neutral SST
carried out employing a humidified NaCl spray in accordance
with the ASTM B117 standard. The deterioration of the
coated surfaces was monitored over time by simple visual
observation of the white rust coverage.
Results
Mass change tests
The mass changes of the bare zinc, CEC, GPS, GCC and
CRC films on zinc recorded at room temperature are
presented in Figure 1.
Tafel studies
Figure 2 shows the polarization curves of the zinc electrode
coated with films in the aerated 0.5 M NaCl solution at about
298 K. Both the cathodic and the anodic processes of zinc
corrosion were suppressed to some extent by covering the
surface with the CEC, GPS or GCC films. The Ecorr values of
these films on electrodes were changed to some extent toward
a more positive potential from the value of uninhibited
electrode, E 0corr 21:076 V(SCE) The Ecorr values of inhibited
electrodes were 2 1.065, 2 1.042, 2 1.025 and 2 1.021
V (SCE) for the CEC, GPS, GCC and CRC films,
respectively. These small shifts were attributed to inhibition
of both anodic and cathodic processes by these inhibitors.
The corrosion current density was determined by
extrapolation of the cathodic and anodic Tafel lines in the
curves and the protective efficiency, P(%) of a film on an
electrode in an aerated NaCl solution can be obtained by the
following equation:
 A compound effect between silane and cerium salt Anti-Corrosion Methods and Materials
Da-jing Fang et al. Volume 56 Number 4 2009 226 231

Table I Operation conditions of CEC, CRC, GPS, GCC films

The Immersion
Films Composition of the conversion solution pH value Temperature/K time/s Subsequent processing
CEC cerous nitrate, hydrogen peroxide and boric acid 1.5 318 120 Rinsed with distilled water,
hot blast dried and natural aging for 5 days
CRC chromium trioxide, nitric acid, sulfuric acid and acetic acid 1.8 298 30 Rinsed with distilled water, hot blast
dried and natural aging for 2 days
GPS GPS, methanol, acetic acid and nitric acid 2.0 298 130 Heated in convection oven at 423 K
for 30 min with wet film and natural
aging for 2 days
GCC GPS, methanol, acetic acid, cerous nitrate, 1.7 298 130 Heated in convection oven at 423 K
hydrogen peroxide, nanometric colloidal silicate, for 40 min with wet film and natural
cobaltous sulfate and nitric acid aging for 2 days

Figure 1 Average results of the mass gain and weight loss P% 1001 2 i cor =i 0cor
measurements for different conversion coatings in passivation process
(treated in conversion solution) and corrosion process (treated in where i 0corr and icorr denote the corrosion current densities of
solution of lead acetate), respectively the electrode bare and coated with the film, respectively. The P
Blank CEC GPS GCC CRC values of different films on the electrodes are also shown in
Figure 2.
Mass gain (gm2)

2
1 EIS tests
Figure 3 shows the Nyquist plots from the EIS study in 5 M
0
NaCl solution at room temperature. In the case of CRC film,
1 the EIS response showed in Figure 4(a) was modeled by a
Randles-type equivalent circuit consisted of polarization
2
Figure 3 Nyquist diagrams obtained for the bare electrode and
3
electrodes coated with CEC, GPS, GCC and CRC films in 0.5 M NaCl
Weight loss (gm2)

4 solution at about 298 K

5 10,000
Passivation process
6
Corrosion process Blank
7 8,000 CEC
GCC
8 GPS
Zim (ohmscm2)

6,000 CRC

Figure 2 Polarization curves (the potential, E and the current density, i)

of a zinc electrode in an aerated 0.5 M NaCl solution and the electrode 4,000
covered with a CRC, CEC, GPS and GCC film. The protective efficiency, P
of different films on the electrodes was also expressed in the diagram
2,000
100 Blank CEC
3.0 80 GPS
60 GCC 0
P(%)

2.5 40
0 2,000 4,000 6,000 8,000 10,000 12,000 14,000
20 CRC Zre (ohmscm2)
log[i(A/cm2)]

2.0 0
Blank CEC GPS GCC CRC
Blank
Figure 4 Equivalent electrical circuits for the samples
1.5 CEC
GPS Cf
GCC
1.0 CRC Cf

Rs Rs Cdl
0.5
Rp
Rf
0.0
Rct
1.30 1.25 1.20 1.15 1.10 1.05 1.00 0.95
E (V/SCE) (a) (b)

228
 A compound effect between silane and cerium salt
Da-jing Fang et al.
resistance (Rp) and film capacitance (Cf) in parallel, in which the
Rp represented the electrical resistance of the chromate film
coated on electrode at open circuit potential. The equivalent
electrical circuit able to model the impedance values of CEC,
GPS and GCC films is shown in Figure 4(b), which is based on a
previous proposal by Michailovskii et al., (Hinton and Wilson,
1989). This circuit is based on the solution resistance (Rs), film
resistance (R f ), film capacitance (Cf ) and other two
contributions: the impedance of the interface, the charge
transfer resistance (Rct) in parallel with the double layer
capacitance (Cdl).
SEM microanalysis
The microscopic observation of the samples shown in Figure 5
revealed that uniform films were formed on the electrodes.
Salt spray tests
Figure 6 shows the surface ratio of white rust for the four kinds
of specimens in a salt spray atmosphere of NaCl solution. It was
found that the time for white rust to initiation on samples coated
with silica-based polymer films increased significantly
compared to untreated samples, as shown in Figure 6.
Discussion
The zinc electrodes lose their weight during the passivation
process of forming CEC or CRC films, owing to the low pH
Figure 5 Surface morphology (SEM) of the electrodes coated with different films
(a) CEC
(c) GCC
229
Anti-Corrosion Methods and Materials
Volume 56 Number 4 2009 226 231
value of the conversion solution. However, in the case of GPS
or GCC films, the weight of zinc electrodes increased during
the passivation process and the mass gain of GCC film was a
little larger than GPS film, indicating a possibility that silane
compounded with cerium. By contrast, the GCC film lost
more weight than did the CEC or GPS films during the
corrosion process, so it is not easy to determine whether this
film composition occurred or (on the assumption it
happened) that it enhanced the corrosion resistance of
conversion films on zinc surface.
In general, the corrosion potentials did not vary
significantly from CEC/GPS to the GCC film, but on the
other hand, the corrosion current varied more, due to the
cathodic process, which was stimulated by the addition of
cerium salt into the GPS conversion solution, implying a
compound effect between silane and cerium that enhanced
the corrosion resisting property of the GPS film. However, the
composite film of silane and cerium was inferior to the CRC
film, and research on the composition between them is almost
non-existent. No pit was observed on the electrode surface
after the polarization measurement in the NaCl solution,
though severe pitting corrosion occurred on the uninhibited
electrode. The p value of the compound film was higher than
for the CEC or GPS films. It was concluded, therefore, that
the corrosion resisting property of the GCC polymer film
containing both silicates and cerium salts was better than the
(b) GPS
(d) CRC
 A compound effect between silane and cerium salt
Da-jing Fang et al.
Figure 6 The ratio of white rust in the SST for bare zinc and sheets
coated with different films
100
80
Ratio of white rust (%)
60
40
20
0
0 50 100 150 200 250
Immersion time (h)
CEC or GPS films, hence indicating the compound effect
between silane and cerium had occurred.
The values of Rf and Rct give information on the barrier
properties of the films and the kinetics of the corrosive
processes, respectively. The compound polymer film (GCC)
of silane and cerium salt seemed to offer a higher corrosion
resisting property than did the single and simple films.
The curve of the GCC film on the Nyquist diagram shows
two capacitive loops and a relatively larger value of charge
transfer resistance Rct. This indicates a more highly resistant
corrosion interface, as compared to the CEC or GPS films.
This enhancement in its corrosion resisting property could be
attributed to the dielectric properties of the insulating silica-
based cross-linking structure polymer film, i.e. a corrosion
protection mechanism by a barrier effect between the
electrolyte and the metallic substrate. The existence of
Ce3 ions enhances the barrier effect by forming of insoluble
CeO2 at the interface.
However, the mechanism of corrosion protection of the
GCC polymer film is not a self-healing process, as in the case
of CRC film, for the reason that the GCC film is not
impermeable, so that the incipient barrier effect of the GCC
film is not present as the electrolyte was absorbed by the
polymer layer, though the absorption process was
comparatively slow. The charge transfer resistance, as shown
by the impedance diagram of the GCC file, will be reduced to
some extent after days of immersion in 0.5 M NaCl solution.
The Rct value decreased after 24-60 h of immersion, and the
diagram of GCC film in Figure 3 was obtained after it had
been immersed in 0.5 M NaCl solution for 36 h. After days of
immersion, the interface of the GCC film changed from an
unstable dielectric barrier during the first stage of the
immersion in the NaCl solution to another mechanism of
corrosion protection, probably associated with the penetration
of electrolyte through the film and to the accumulation and
diffusion of corrosion products inside the silica-based polymer
layer. This means that although stemming from a different
protective mechanism, the silica-based cross-linking polymer
layer introduced in the present paper generally could be
expected to provide an equivalent degree of corrosion
protection to classical chromate coatings if the composite
mode of silane and cerium salt can be modified.
Anti-Corrosion Methods and Materials
Volume 56 Number 4 2009 226 231
It was verified that the morphology of the CEC film was
light golden, brownish and had a finely cracked structure,
whilst some brownish powder could be found on its surface,
which was confirmed later to be cerium oxide. The silica-
based baths usually led to semitransparent, grayish, relatively
thicker and homogeneously cracked layers (treated at 423 K
for 30 min), but the GCC film was dissimilar to GPS film, the
main differences between them being their color and
microstructure. Pits were distributed on the GCC film
instead of cracks, and both pits and cracks on the silica-based
films were adverse to the anti-corrosion capability of the silica-
based film. Additionally, the addition of CoSO4 and colloidal
Blank silicate to the GPS solution enhanced adhesion between zinc
CEC and the silica-based polymer film. By contrast, the classic
GPS CRC film was light green, iridescent, thin and was more
GCC compact than were the other coatings.
CRC The proportion of white rust formation on sheet coated
300 350 400 with GCC film increased at a relatively low speed, compared
to sheets coated with GPS or CEC films, indicating an
improvement in corrosion resistance stemming from the
synergistic effect between the silane and the cerium salt. The
results of mass change measurements and electrochemical
measurements also supported the observations of the salt
spray test.
Conclusions
It has been shown clearly from the analysis of the
aforementioned data that the formation of GCC film
improved the anticorrosion abilities of GPS or CEC films
through a synergistic effect. The mechanism of forming of the
GCC film may be due to the ability of aggressive ions (Ce3 )
to gain access to the interface through cracks or microspores
in the cross-linking structure of the GPS polymer film on the
zinc surface, and the subsequent dehydration process
(forming of CeO2) of the hydrated film at 423 K for 30 min
may result in a barrier effect between the electrolyte and the
metallic substrate.
The GCC film was produced as a new chemical conversion
treatment for pure zinc or galvanized steel, and was
characterized as an alternative to the traditional CRC
coating. Further, work has to be carried out in order to
understand better the composite mode of silane and cerium
salt on the existence of CoSO4 and colloidal silicate.
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Anti-Corrosion Methods and Materials
Volume 56 Number 4 2009 226 231
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(British Lending Library Translation).
van Ooij, W.J., Subramanian, V. and Zhang, C. (1998),
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US Patent No. 5,750,197, US Patents Office, Alexandria,
VA, May 12.
Corresponding author
Fu-xing Gan can be contacted at: fxgan@whu.edu.cn