ECS Transactions, 25 (29) 123-133 (2010)

10.1149/1.3327231 © The Electrochemical Society

Silane film obtained from a sol constituted with TMSPMA and TEOS and the
hexavalent chromate conversion film: The comparative performance as a post-
treatment of zinc coating

Marlla Vallerius da Costa a, Tiago Lemos Menezes a, Daniel A. Dalla Corte a, Cláudia
Trindade Oliveira b, Célia de Fraga Malfatti a and Iduvirges Lourdes Muller a
a
Laboratório de Pesquisa em Corrosão - Metallurgy Department, PPGEM, UFRGS, Brazil
b
Feevale – ICET, Novo Hamburgo, Brazil

Silane films obtained by sol-gel process have been proposed as an

alternative to replacement for chromate post-treatment of zinc
coatings. The aim of this work was to study the electrochemical
behavior of electrodeposited zinc coatings post-treated with silane-
cerium film or Cr(VI) conversion coating. Silane-cerium coatings
were obtained by dip-coating from a sol constituted by TMSPMA
and TEOS silanes precursors with the addition of cerium salt.
Electrochemical impedance spectroscopy (EIS) measurements, allied
to potentiostatic polarization curves, demonstrated that the post-
treatment of zinc with hexavalent chromate conversion or silane film
promoted the increase of polarization resistance (Rp) and the
reduction of corrosion current density. However it was verified the
superior performance of silane-cerium coatings associated to the
effect of silane film resistance (Rsi), and the resistance related to the
formation of a corrosion product of zinc and cerium (Rzco).

Introduction

For many years, hexavalent chromate conversion coatings were used as the primary
method to provide the corrosion resistance of zinc and its alloys. The process of chromate
post-treatment is functional and offers a high corrosion protection, however it employs
hexavalent chromium compounds in their formulation. These compounds are considered
mutagenic and carcinogenic agents, which imply environmental restrictions for its use (1).
Due to the Cr (VI) toxicity, non-toxic alternatives have been studied. The development of
new processes free of hexavalent chromium has been investigated, and in that context,
silanes coatings obtained by sol-gel process have been proposed as an alternative to
environmentally acceptable replacement for chromate post-treatment of coatings zinc (2, 3,
4).
The deposits of silanes by sol-gel process are excellent adhesion promoters to painting
when applied to different metals and alloys, and may also promote a good protection
against corrosion by barrier effect. Besides the ease of application on substrates with
various ways, the process of sol-gel is a real candidate for replacement of chemical
conversion coatings, and more specifically for the replacement of treatments based on
hexavalent chromium. The silane film can be obtained by dip-coating method, which is
based on the principle of substrate immersion and withdrawal speed control. In this case,
the film thickness is a function of the withdrawal speed (5).

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 ECS Transactions, 25 (29) 123-133 (2010)

In the sol-gel process, two reactions are responsible for film formation: the hydrolysis
and condensation, leading to the formation of a sol and then a gel (6). The homogeneous
distribution of elements within the sol is stored within the gel. The xerogel film is obtained
by solvent evaporation after the drying process. The molecular precursors used are
generally silicon alkoxides Si(OR)4, which can be used whether or not combined with other
metal alkoxides, that have a role in the interface strengthening between the sol-gel coating
and the metal, and may also contain the corrosion inhibitors (7, 8, 9, 10). Hybrid precursors
such as silanes, for example, have in their structure of organic and inorganic groups, giving
more flexibility, density and functional compatibility. The organic layer acts as a barrier
film, it slows the penetration of aggressive species to the metallic substrate, providing
protection against corrosion. Inorganic groups present characteristics of ceramic materials,
contributing to the strength increased, durability and adhesion to metal substrate (11). The
aim of the present work is to study the electrochemical behavior of electrodeposited zinc
coatings post-treated with silane-cerium film or Cr(VI) conversion coating. The silane-
cerium films were obtained by dip-coating method from a sol constituted with TMSPMA
(3-(Trimethoxysilyl)propyl methacrylate - C10H20O5Si) and TEOS (tetraethoxysilane-
C8H20O4Si) silanes precursors with the addition of cerium salt.

Experimental
Elaboration of zinc coatings

Zinc coatings were prepared on carbon steel substrates by electrodeposition from a

plating bath containing: ZnCl2 85g.L-1; KCl 210g.L-1, H3BO3 25g.L-1, with the addition of
commercial additives. The electrolyte temperature was between 20 ºC and 35ºC from 4.8
to 5.2. The electrodeposition process of these coatings was carried out at 2 A.dm-2 current
density in a two electrodes cell for 30 minutes, to obtain the zinc coating thickness at about
20μm.

Elaboration of hexavalent chromate conversion coating and silane coating post-treatment

Hexavalent chromate conversion coating was obtained according to technical

specifications reported by suppliers, as shown in Figure 1.
The silane films were obtained on zinc by dip-coating process in a sol constituted by
silane precursors: γ TMSPMA (3-(Trimethoxysilyl)propyl methacrylate - C10H20O5Si) and
TEOS (tetraethoxysilane- C8H20O4Si) and 0.01 mol.L-1 of cerium nitrate (Ce(NO3)3).
Ethanol and water were used as solvent. The withdrawal speed of substrates from the sol
was 20 cm.min-1.

Figure 1: Technical specifications for hexavalent chromate conversion coating elaboration

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 ECS Transactions, 25 (29) 123-133 (2010)

Morphological and electrochemical characterization

Scanning electron microscopy (SEM) was used to evaluate the thickness, by cross
section, and the morphology of silane film/Zn coatings and chromate conversion coatings.
The corrosion performance of the coatings was evaluated by open circuit potentials (OCP)
monitoring, potentiostatic polarization curves and electrochemical impedance spectroscopy
(EIS) measurements in a 5% NaCl solution. The experimental apparatus used for the
electrochemical investigation was a potentiostat (AUTOLAB PGSTAT 30) coupled to a
frequency response analyzer (FRA) system. The EIS measurements were performed in
potentiostatic mode at the OCP. The amplitude of the EIS perturbation signal was 10mV,
and the frequency studied ranged from 100 kHz to 10 mHz.

Results and discussion

Morphological characterization of the films

Figure 2 shows that the two post-treatments applied to zinc coatings presented a
homogeneous coverage. However, the hexavalent chromate conversion coating showed
cracks throughout the film, while on the silane film it was possible to observe the presence
of discontinuities.

Figure 2: SEM: (a) silane film and (b) Cr(VI) conversion coating

From the analysis in cross-section of the coatings (Figure 3) the thickness of the
chromate layer and of the silane film prepared by dip-coating were determined (TABLE I).
It was found that the thickness of the silane film seems to be influenced by surface
roughness, as it can be observed in Figure 4: a peak-to-valley thickness difference, the film
thickness in peak regions is smaller than in valleys regions.

Figure 3: Cross-sectional SEM images: (a) zinc coating; (b) silane film and (c) Cr(VI)
conversion coating
TABLE I. Average thickness of the samples of zinc, Cr (VI)/zinc and silane/zinc
Sample Thickness (µm)

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 ECS Transactions, 25 (29) 123-133 (2010)

Zinc coating 19.3 ± 0.04

Cr (VI) conversion coating 0.26 ± 0.06
Silane film 0.63 ± 0.05

Figure 4: Cross-sectional SEM images: (a) zinc coating and (b) highlight regions with and
without the silane film

Electrochemical behavior

Open Circuit Potential and Potentiostatic Polarization Measurements

Figure 5 (a) shows the open circuit potential values for Zn, Zn/silane and Zn/Cr(VI)
coatings for 1 hour of immersion in a 5% NaCl solution. The values of open circuit
potentials of all the systems studied were close to the one of bare zinc coating. This can be
related, possibly, with the presence of discontinuities in the chromate and silane films, as is
shown in the images obtained by SEM (Figure 2).
From the extrapolation of the Tafel lines, applied to the polarization curves (Figure 5
(b)), corrosion potential (Ecorr), corrosion current (Icorr) and polarization resistance (Rp)
were determined for the systems studied. Zinc post-treated with chromate-chromium film
or silane film presented an increase in polarization resistance (Rp) and a Icorr decrease
(TABLE II) compared to zinc coating without post-treatment. However, it was observed
that silane film cause a shift of corrosion potential (Ecorr) to less active potential values
and a development of less current density (Icorr) values, indicating the best performance of
this coating.

Figure 5: (a) OCP measurements in a 5% NaCl solution and (b) potentiodynamic

polarization curves (1mV/s).

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 ECS Transactions, 25 (29) 123-133 (2010)

TABLE II. Electrochemical parameters obtained from potentiodynamic polarization curves

Zn Zn/Cr(VI) Zn/silane
icorr (A/cm²) 1.3E-5 6.2E-7 2.6E-7
Ecorr (mV) -1069 -1198 -1032
Rp (Ω.cm2) 8.7E+2 6.4E+3 2.5E+4

The SEM images obtained for samples after the polarization test (Figure 6) showed
that the zinc coating presents a generalized corrosion (Figure 6 (a)), while the zinc coating
post-treated with silane film (Figure 6 (b)) showed a localized attack in discrete regions of
the surface. Zinc coating post-treated with hexavalent chromate conversion film (Figure 6
(c)) presented regions of film detachment and the zinc coating attack.

Figure 6: SEM after potentiostatic polarization: (a) zinc coating; (a1) zoom in a attacked
region of zinc coating; (b) zinc /silane coating; (b1) zoom in a attacked region of zinc/silane
coating; (c) zinc/Cr(VI) coating; (c1) zoom in a attacked region of zinc/Cr(VI) coating

Electrochemical Impedance Spectroscopy Measurements

Models of equivalent electrical circuits were proposed to simulate the

electrochemical behavior of the coatings studied from the analysis of electrochemical
impedance. These models are based on the combination of resistances, capacitances and
other elements that should have a physical meaning, probably related to the electrochemical
response of the system. TABLE III, TABLE IV and

TABLE V present the values of electrical parameters obtained by fitting the

equivalent electrical circuit diagrams to the experimental EIS data obtained for zinc,
zinc/silane and zinc/Cr(VI) coatings for 168 hours of immersion in a 5 % NaCl solution.

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 ECS Transactions, 25 (29) 123-133 (2010)

Figure 7 shows the Bode diagrams obtained for 1, 24, 72 and 168 hours of immersion in
5% NaCl solution for zinc, zinc/silane and zinc/Cr(VI) coatings.
TABLE III. Values of parameters obtained from the simulation of the equivalent electrical
circuit to experimental impedance diagrams for zinc coatings without post-treatment with
silane film along of 168 hours of immersion in a 5% NaCl solution.
Zinc 1h 24h 48h 72h 168h
2
Rs [Ω.cm ] 3.4 3.9 2.9 3.7 4.7
-2 (n-1)
CPEdcp [Fcm s ] 0.100E-4 0.7058E-3 0.5839E-3 0.1700E-3
n 1.0 0.57 0.56 0.61
2
Rdcp [Ω.cm ] 6.26 32.2 62.7 70.9
CPEct [Fcm-2s(n-1)] 0.3770E-4 0.3871E-3 0.3886E-3 0.42860E-3 0.2748E-3
n 0.84 0.71 0.81 0.89 0.66
2
Rct [Ω.cm ] 305 506 495 415 443
-2 (n-1)
CPEcp [Fcm s ] 0.249E-02 0.73E-1 0.228E-1 0.69E-1 ***
n 1.0 1.0 1.0 1.0 ***
2
Rcp [Ω.cm ] 250 77.3 234.6 225.2 ***
(*)Time constant was not simulated because of the insufficient number of experimental
data

TABLE IV. Values of parameters obtained from the simulation of the equivalent electrical
circuit to experimental impedance diagrams for zinc coatings with post-treatment with
silane film, along 168 hours of immersion in a 5% NaCl solution.
Zinc/silane 1h 24h 48h 72h 168h
2
Rs [Ω.cm ] 8.6 8.7 5.0 6.6 4.7
-2 (n-1)
CPEhf [Fcm s ] 0.4541E-5 0.1421E-4 71.1E-9 77.1E-9 82.5E-9
n 0.64 0.57 1.0 1.0 1.0
2
Rhf [Ω.cm ] 272.2 136.0 36.9 30.97 24.61
-2 (n-1)
CPEzco [Fcm s ] 0.2208E-4 0.4059E-4 0.1077E-3 0.1779E-3 0.2414E-3
n 0.65 0.62 0.53 0.49 0.48
2
Rzco [Ω.cm ] 2990 1839 5390 6070 6700
-2 (n-1)
CPEsi [Fcm s ] 0.1070E-4 0.10e-4 0.1972E-4 0.1848E-4 0.1939E-4
n 0.89 0.94 1.0 1.0 1.0
2
Rsi [Ω.cm ] 26170 9970 4800 5340 4810

TABLE V. Values of parameters obtained from the simulation of the equivalent electrical
circuit to experimental impedance diagrams for zinc coatings with post-treatment with
Cr(VI), along 168 hours of immersion in a 5% NaCl solution.
Zinc/Cr (VI) 1h 24h 48h 72h 168h
2
Rs [Ω.cm ] 4.2 4.8 4.0 3.7 3.5
-2 (n-1)
CPEpo [Fcm s ] 11.93E-6
n 1.0
2
Rpo [Ω.cm ] 19.87
CPEcp [Fcm-2s(n-1)] 0.2871E-4

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 ECS Transactions, 25 (29) 123-133 (2010)

n 1.0
2
Rcp [Ω.cm ] 64.3
-2 (n-1)
CPEcc [Fcm s ] 20.11E-3 0.8133E-5
n 1.0 0.90
2
Rcc [Ω.cm ] 4760 5960
CPEct [Fcm-2s(n-1)] 0.1358E-3 0.1260E-3 0.3765E-4
n 0.74 0.71 0.77
2
Rct [Ω.cm ] 330 350 663
-1
W (Ω ) 0.8940E-3 0.5289E-3
-2 (n-1)
CPEdf [Fcm s ] 0.2731E-2 0.1341E-2 0.1048E-3
n 0.45 0.62 0.50
2
Rdf [Ω.cm ] 796 91300 158900

Figure 7: Bode diagrams for zinc, zinc/silane and zinc/Cr(VI) in a 5% NaCl solution

It was observed for the zinc coating, from the electrochemical impedance diagrams
(Figure 7 and TABLE III), the presence of two capacitive loops along the first hour of
immersion. These loops were associated to two distinct phenomena: the formation of a
corrosion product of zinc and the charge transfer of zinc. For the following hours of
immersion (between 24 and 168 hours), a third capacitive loop shows up at high frequency
referent to the diffusion through the corrosion product formed on the surface of zinc.
The equivalent circuit of Figure 8 is a proposed model for the simulation of
electrochemical behavior of zinc coating from 24 hours of immersion on, where Rs
represents the electrolyte resistance, Rdcp and CPEdcp represent the resistance and a

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 ECS Transactions, 25 (29) 123-133 (2010)

constant phase element associated to the capacitance diffusion through a corrosion product
formed. Additionally, Rct and CPEct represent the resistance of charge transfer and a
constant phase element associated to the double layer capacitance, while Rcp and CPEcp
represent, are respectively the corrosion product resistance and a constant phase element
associated to the capacitance of the same one.

Figure 8: Equivalent electrical circuit used to adjust the experimental impedance diagrams
obtained for zinc coating for 24 hours of immersion in a 5% NaCl solution.

For the zinc sample post-treated with silane film (Figure 7 and TABLE IV), it was
observed the existence of three capacitive loops along the 168 hours of immersion. The
capacitive loops at middle and low frequency are associated respectively to the diffusion
through a zinc and cerium corrosion product and the silane film.
The resistances related to the presence of the silane film (Rsi), and the formation of
a corrosion product of zinc and cerium (Rzco) acted jointly to protect the zinc coating,
inserting a resistance Rt, the sum of both, which stifles the corrosion of zinc; Rt remained
similar along the immersion time (Figure 9), indicating the efficiency of the silane film and
the corrosion inhibitor. For the first 24 hours of immersion (Figure 7 and TABLE IV), the
capacitive loop at high frequency is associated to the resistance to charge transfer of zinc,
indicating that the silane film is permeable or presents discontinuities, and therefore does
not constitute an effective barrier between the zinc coating and the environment. For the
following hours of immersion (between 48 and 168 hours), a new phenomenon emerges in
high frequency associated to the decreased resistance of the silane film and the increased
resistance of the film of zinc oxide/cerium.

Figure 9: Rt values x immersion time

The equivalent circuit presented on Figure 10 is a proposed model for the simulation
of the zinc electrochemical behavior after treatment with the silane film from 48 hours of
immersion on, where, Rs represents the electrolyte resistance, and Rhf and CPEhf represent
respectively the resistance and a constant phase element associated to the capacitance of the
phenomenon at high frequency; Rzco and CPEzco represent the resistance and a constant
phase element associated to the diffusion phenomenon through a corrosion product of zinc
and cerium, formed during the corrosion process. The Rsi and CPEs represent the silane
film resistance and a constant phase element associated to this film.

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 ECS Transactions, 25 (29) 123-133 (2010)

Figure 10: Equivalent electrical circuit used to adjust the experimental impedance diagrams
obtained for zinc with silane film for more than 48 hours of immersion in a 5% NaCl
solution

For the zinc/Cr(VI) (Figure 7 and TABLE V), the results showed the existence of
four capacitive loops after the first hour of immersion. The phenomenon at the highest
frequencies is probably related to the presence of pores in a zinc corrosion product formed
on the surface of the coating. The phenomenon at high frequency is associated to the zinc
corrosion product, while the middle frequency phenomenon is associated to the chemical
conversion layer and the phenomenon at low frequency is associated to the diffusion effect
through the chemical conversion layer. For 24 hours of immersion it was no longer spotted
the existence of a porous layer of the zinc corrosion product and it was possible to observe
the existence of only two capacitive loops related to the chemical conversion layer and
diffusion through this layer. Between 48 and 72 hours of immersion two phenomena were
observed: the zinc charge transfer and the replacement of the capacitive loop (associated to
the phenomenon of diffusion through the conversion layer) by a Warburg component. For
168 hours of immersion, the system returns to present two capacitive loops, as in 24 hours
of immersion, indicating that a recovery of the conversion (chromium oxide) occurs.
The equivalent circuit of Figure 11 is the model proposed for the simulation of the
zinc coating electrochemical behavior, after treatment with hexavalent chromate, for 168
hours of immersion, where Rs represents the electrolyte resistance, Rcc and CPEcc
represent the resistance and a constant phase element associated to the chemical conversion
layer. On the same circuit, Rdf and CPEdf represent the resistance and a constant phase
element associated to the diffusion through the conversion layer, respectively.

Figure 11: Equivalent electrical circuit used to adjust the experimental impedance diagrams
obtained for zinc/Cr(VI) for 168 hours of immersion in a 5% NaCl solution.

Figure 12 shows the experimental impedance diagrams and the fitted curves for the
zinc, zinc/Cr(VI) and zinc/silane systems, obtained after 72 hours of immersion in a 5%
NaCl solution.

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 ECS Transactions, 25 (29) 123-133 (2010)

Figure 12: Nyquist diagrams obtained for a) untreated zinc, b) hexavalent chromate
conversion and c) zinc post-treated with silane film, in a 5% NaCl solution

Conclusions

The results showed that the silane film presented a leveling effect on the zinc
coating surface, however, discontinuities (pores) on the silane film were observed. The EIS
results and potentiostatic polarization curves showed that the silane films with cerium salts
post-treatment improve the characteristics of the protective zinc coating, thus being an
effective alternative for the replacement of chemical chromating conversion process.

Acknowledgments

Partners of this project are strongly acknowledged: CNPq, Finep and CAPES.

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