Corrosion Protection Properties of Organofunctional Silanes-Main

TSINGHUA SCIENCE AND TECHNOLOGY
I SSN 1007- 0214 01/ 11 pp639-664

Volume 10, Number 6, December 2005
Corrosion Protection Properties of Organofunctional Silanes
An Overview
W. J . van Ooij
**
, D. Zhu, M. Stacy, A. Seth, T. Mugada, J . Gandhi, P. Puomi

Department of Chemical and Materials Engineering, University of Cincinnati, Cincinnati, Ohio, USA;
Salo Business and Health Care College, Karjalankatu 2-6, FIN-24130, Salo, Finland

Abstract: The aim of this paper is to review the development and state of the art in the application of cer-
tain organosilicon compounds known as trialkoxysilanes (or simply silanes) to the problems of the metal
finishing industry. The ultimate goal of this work is the replacement of chromate passivation and paint
pretreatments, as well as overcoming the shortcomings of organic coatings formulated in the modern
environmentally friendly world, thus without chromate or chromated pigments, volatile organic carbon (VOC)
containing compounds or harazardous air pollutants (HAPs).
Key words: organic coating; trialkoxysilane; hydrophobicity

Introduction
Silicon compounds, especially organosilicon
chemistries, have been the subject of extensive
development for more than fifty years, producing
commercial advances in polymeric and composite
materials which have fueled industrial innovation in
the automotive, aerospace, and electronics markets. A
basic review of relevant chemical property
characteristics easily reveals the motivation for such
experimentation. Silicon has a normal oxidation state
like that of carbon; however, silicon is more
electropositive, resulting in bond strengths, bond
angles, and bond lengths that are quite different from
most organic compounds, especially those including
electronegative elements, such as oxygen, fluorine, and
chlorine
[1-3]
. Such inorganic compounds often
display enhanced properties including thermal
endurance, chemical or moisture resistance, increased
mechanical strength, and electrical performance over
materials with a completely organic nature. One
general class of monomers and oligomers with a large
variety of organic functionalization, called alkoxy-
silanes, were identified early on by researchers as
excellent coupling agents, a material which assists in
adhesive bonding between dissimilar surfaces,
allowing for better bulk and interface properties
[4-6]
.
Trialkoxysilanes and similar silicon compounds are
currently the subject of intensive research due in
significant part to the need for green technology in
the metal-finishing and the adhesive industries.
Chromate and similar hexavalent chromium com-
pounds have been reported to be toxic and carcino-
genic, and thus their use and waste are regulated
heavily by most environmental legislation
[7,8]
. Volatile
organic carbon (VOC) in coatings and other sources
have been linked to smog formation
[9]
. The proposed
lower emission levels have forced many companies to
look for water-based solutions to their corrosion
prevention needs. Isocyanate type cross-linking agents
have been identified as being hazardous air pollutants
(HAPs)
[10]
and are making polyurethane and other
resin systems more difficult to employ.
Received: 2005-06-09

To whom correspondence should be addressed.
E-mail: vanooiwj@email.uc.edu;
Tel: 1-513-556-3194; Fax: 1-513-556-3773

Chromate performs two major applications in
corrosion control. The first is conversion sealing
Tsinghua Science and Technology, December 2005, 10(6): 639-665

640
pretreatments for metals alloys of iron, aluminum, zinc,
copper, and magnesium. The second application is as
leachable inhibitive pigments in many primer and
general coating formulations. Both of these uses of
chromate compounds produce strong corrosion
inhibiting effects and it is not readily apparent how to
use the barrier and hydrophobic effects of siloxane
films to duplicate the overall performance effects.
The exact chromate solution composition and
structure of the final conversion coating may vary
between substrates, application method or even
specific products, but traditionally, chromic acid
(H
2
CrO
4
) is used as a rinse which reacts with and
dissolves the surface and near surface metal layer.
Subsequent reduction reactions precipitate Cr(OH)
3
on
the surface as a coherent layer, with a certain amount
of unreacted Cr
6+
still remaining within the film
[11]
.
This layer provides both adhesion and stability to
subsequent coating systems applied on top of it. The
inhibition mechanism of the conversion layer was
studied by Kendig, who concluded that the Cr
6+
still
present

allows for repair of defects and breaks in the
film, otherwise denoted as the so called self-healing
effect
[12]
. It is unclear just how effective this
mechanism is beyond cut edge protection as the
majority of the chromate treated surface is often
encapsulated by an organic primer or topcoat.
The general silicon compound type that
Plueddemann first explored as coupling agents
[6]
has
already gained industrial accepted application as
adhesion promoting surface treatment for metals
[13]
.
Compounds of this sort, so called mono-silanes,
have the general structure X
3
Si(CH
2
)
n
Y, where X
represents a silicon ester which can transform using a
hydrolysis reaction to a silanol group; Y represents an
organofunctional group such as chlorine, primary or
secondary amines, or vinyl. Typically, the value of n is
around 3, but individual moieties can vary. Both the
type of Y group and the value of n have a strong
influence on whether a particular monomer is water-
soluble, but in general most of them are. The standard
application method is solution deposition followed by
an immediate condensation reaction upon drying with
any available hydroxyl groups present on the inorganic
substrate or metal surface to form stable siloxane
bonds.
Studies have shown that so called bis-silanes or
dipodal silanes display superior protection on metal
surfaces, especially when used in conjunction with
organofunctional mono-silane treatments for adhesion
to other organic layers
[14-17]
. These compounds have
structures X
3
Si(CH
2
)
n
Y(CH
2
)
n
SiX
3
or can exist with
no functional group with the following structure
X
3
Si(CH
2
)
m
SiX
3
. They enhance performance by
depositing a more pronounced hydrophobic
polysiloxane layer (SiOSi linkages) during
condensation, but still allow chemical coupling using
the functional group present either in the dipodal silane
itself or with a mono-silane solution additive. Thus,
combinations of silanes (mixtures) usually perform
better than films of silanes alone. Table 1 summarizes
the silanes that will be discussed in this paper and the
abbreviations used for them. Unfortunately, many of
the bis-silanes are not water-soluble, which limits their
immediate industrial use to those with water stabilizing
functional groups such as amines. Regardless, certain
optimal mixtures have been obtained, clearly showing
the potential of silane deposited films to be able to give
equivalent performance to chromate underneath paint
systems and even as a stand alone passivation
treatment
[18,19]
.
Table 1 The silanes discussed and the abbreviations used for them
Material Structure Abbreviation
Mono-silanes
Vinyltriacetoxy silane CH
2
CH Si(OCOCH
3
)
3 VTAS
Bis-silanes
Bis-1,2-(triethoxysilyl) ethane (C
2
H
5
O)
3
Si CH
2
CH
2
Si(OC
2
H
5
)
3 BTSE
Bis-[trimethoxysilylpropyl]amine (CH
3
O)
3
Si (CH
2
)
3
NH (CH
2
)
3
Si(OCH
3
)
3 Bis-amino
Bis-[triethoxysilylpropyl]tetrasulfide (C
2
H
5
O)
3
Si (CH
2
)
3
S
4
(CH
2
)
3
Si(OC
2
H
5
)
3 Bis-sulfur
Universal mixtures Ratio
Bis-sulfur/bis-amino 3/1
Bis-amino/VTAS e.g., 5/1

W. J . van Ooij et alCorrosion Protection Properties of Organofunctional 641
One major drawback to the widespread use of silane
films as a passivating treatment is that despite their hy-
drophobicity, eventually moisture reaches the metal-
silane interface. The hydrolysis reaction that allowed
the formation of Si O Me bonds is reversible, espe-
cially if the substrates metal hydroxide is somewhat
soluble
[1,6]
. This enables a mechanism by which the
coatings performance can be undermined. There is
evidence to suggest that the superior performance of
dipodal silanes can further be enhanced by having
higher concentration of Si O Me bonds that are
formed during condensation and film formation which
can mitigate this reversible effect to varying degrees
[20]
.
Future advancements necessitate formulating a more
robust coating; however, thicker films of silane are
usually too brittle, and the stability of the solutions
used to deposit such layers are relatively poor. Several
alternative methods have been attempted, starting with
the inclusion of additives in the silane film such as
nano-sized filler and inhibitors
[21,22]
. Research has also
progressed into investigating the modification of silane
technology with conventional paint coating
methodology. This has been accomplished through
resin and/or pigment additions to sol-gel processes or
direct network formation of siloxane using large silane
precursor additions to paint formulations
[23-25]
. It is
hoped that the inorganic and hydrophobic nature of the
incorporated siloxane will provide superior barrier
protection as well as suggest interesting alternatives to
the current crosslinking and cure methods.
1 Experimental
1.1 Silane surface treatment
An important aspect in the interaction of silanes with
metallic surfaces is the nature and preparation of the
inorganic surfaces. The cleaning of the metal
substrates prior to the film deposition is a critical step
in the bonding process. Sabata et al.
[26]
have studied
the effect of different cleaning procedures on steel
surfaces for the deposition of films. They have
concluded that the surface of the substrate has to be
cleaned appropriately for the silanes to become
effective. According to them, alkaline cleaning seems
to be the best pretreatment before the application of
silanes. Moreover, from the chemical bonding theory
of Plueddemann
[6]
it can be expected that oxide
surfaces with a high density of hydroxyl groups will be
preferred. Child and van Ooij
[27]
have reported that
acid or neutral cleaners are less desirable compared to
alkaline cleaners because of their lower hydroxyl
group content. Franquet et al.
[28]
also studied the effect
of surface pretreatment but on aluminium. They
demonstrated that the amounts of hydroxyl groups at
the aluminium surface provided by the different
pretreatments strongly influence the initiation and the
formation of non-functional silane films.
In summary, the interaction of the silane coupling
agents with the metals seems to be dependent on the
condition of the metallic surface. The substrates are
usually degreased ultrasonically in various solvents
such as hexane, ethanol, and acetone for 3-5 min, and
then cleaned in a diluted alkaline cleaner (AC1055
,
provided by Brent P L C, Lakebluff, I L, USA) at 60-
70C for 3-5 min, after which they are rinsed with
deionized (DI) water and air dried. The cleaned panel
surfaces should be completely water-breakfree (i.e.,
thoroughly wettable by water).
1.2 Silane hydrolysis
Before application on any substrate silanes needs to be
hydrolyzed so that they have sufficient silanol Si OH
groups to interact with the metal substrate. Usually,
silanes are applied from dilute water solutions onto the
metal surface. In the solution, the silanes are
hydrolyzed and silanol groups are formed according to
the following reaction:
(CH
3
CH
2
O)
3
Si CH
2
CH
2
Si(OCH
2
CH
3
)
3
+6 H
2
O

(OH)
3
Si CH
2
CH
2
Si(OH)
3
+ 6 CH
3
CH
2
OH (1)
After hydrolysis, the hydrolyzed silanol groups can
undergo condensation reactions, resulting in slow po-
lymerization and eventual precipitation The factors in-
fluencing the kinetics and equilibrium of hydrolysis
and condensation of silanes in solutions are the nature
of the organofunctional groups, the concentration of si-
lanes and water, the value of the solution pH, the tem-
perature, and the aging of the solution
[27,29,30]
. Be-
cause both hydrolysis and condensation reactions
are acid or base catalyzed, solution pH is the major
factor governing the stability of silanes in aqueous
solutions
[31,32]
.
Figure 1 illustrates the pH dependency of the
hydrolysis and condensation reactions of a typical
silane. From Fig. 1, it can be seen that under acidic or


642
basic conditions, the rates of both hydrolysis and
condensation reactions are high, while at or near
neutral pH they are slow. Although acids and bases are
catalysts for both hydrolysis and condensation of
alkoxysilanes, these two processes have different pH
dependences. When the reactions are OH

catalyzed, a
high rate of condensation is favored with rapid gelation.
On the contrary, when reactions are H
+
catalyzed, a
high rate of hydrolysis is favored with slow gelation.
Hydrolysis and condensation will proceed
simultaneously unless one of them is limited under
specific conditions. For example, preventing
precipitation or gelation by using suitable solvents
can slow down or even halt condensation
[33]
.
Tesoro and Wu
[29]
showed that for silanes such as -
APS, -MPS, and -GPS the rate of hydrolysis reaches
a minimum at pH 7 while the rate of condensation
shows a minimum at pH 4.3. Premachandra et al.
[34]

obtained similar results for -UPS in the water-
methanol system. Experimental studies
[35,36]
have
shown that the hydrolysis of alkoxy groups proceeds in
a step-wise manner. The first alkoxy group hydrolyzes
slowly, due to steric effects, followed by rapid
consecutive hydrolyses of the other alkoxy groups.

Fig. 1 Hydrolysis and condensation rate of a typical
silane
[6]
.
Osterholtz and Pohl
[31]
have reviewed the kinetics of
hydrolysis and condensation of organofunctional
alkoxysilanes. They have concluded that the slower
rate of hydrolysis is found at approximately pH 7
(neutral) and that a change of pH by one unit in either
the acidic or the basic direction results in an
acceleration of the hydrolysis rate. In order to
minimize condensation, concentrations of silanes
below 1% by weight should be used
[31]
. Additionally,
Arkles et al.
[32]
have shown that the hydrolysis rate
decreases when the carbon chain of the alkoxy groups
becomes longer. Moreover, they have also reported
that the hydrolysis rate is enhanced by an increase in
the amount of organic substitution.
In general, silanes with multifunctionality such as
the bis-(triethoxysilyl)ethane have a very limited
stability in water because of hydrolysis and
condensation. Therefore, a high amount of organic
solvents is needed in the preparation of solutions of
multifunctional silanes. The stability, hydrolysis, and
condensation kinetics of a typical bis-silane BTSE in
water-ethanol-silane solution have been investigated
by Pu et al.
[33]
using Fourier transform infrared (FT-IR)
spectroscopy. They showed that at pH of around 4.5,
the BTSE solution had the best stability, a high
hydrolysis rate, and a low condensation rate.
Silane solutions are usually prepared by adding the
silane to a mixture of DI water and solvent. A 5 vol.%
bis-silane solution, for example, was prepared by
adding 5 mL of the silane to a mixture of 5 mL DI
water and 90 mL ethanol. The ratio of bis-silane/DI
water/ethanol was 5/5/90 (v/v/v). In order to study the
hydrolysis depending upon the silane, acetic acid or
potassium hydroxide is used to reduce or raise the pH
of the silane solution, respectively. Hydrolysis time is
of high importance. A water based silane like bis-UPS
hydrolyzes very fast from 15 min to 1 h. However,
solvent-based silanes like bis-sulfur take 18 h to 48 h
for hydrolysis. Although complete hydrolysis is not
necessary, a sufficient number of active SiOH groups
should be generated in the solution. In this way, a solid
rather than an oily silane film is formed on metal
substrates.
1.3 Silane deposition
After hydrolysis, silane coupling agents are generally
deposited directly onto inorganic surfaces by means of
different techniques. These deposition methods include
deposition from solution, vapor, plasma, and the
electrodeposition method
[15,37,38]
. Recently, Gandhi and
van Ooij
[39]
have demonstrated the advantages of the
electrodeposition technique, which results in a uniform
film and a strong interfacial layer between the silane
and metal substrate. Among these various processes,
deposition from solution is the most widely used
method as it is the simplest and the cheapest one
[40]
.
Deposition from solution is very fast and the thickness
of the film remains virtually unchanged, even if the
immersion time is varied between 30 s to 30 min.

When the metal is dipped into a dilute silane
solution of 2%-5% by volume strength for a few
seconds, silanol groups get adsorbed instantaneously
on the metal surface through hydrogen bonds, as
shown schematically in Fig. 2 (Ref. [22]). Upon drying
or curing, the SiOH groups and MeOH groups further
condense to form metallo-siloxane (MeOSi), as shown
in Fig. 2 and water evaporates during this process:
Me O H + H O Si Me O Si + H
2
O (2)
Figure 2 further illustrates that simultaneously with
reaction (2) silanol groups (SiOH) react with each
other by crosslinking and contribute to the formation
of an SiOSi network according to the condensation
reaction:
Si O H + H O Si Si O Si + H
2
O (3)

Fig. 2 Adsorption of partly hydrolyzed silane on a
clean metal
[22]
.
Several studies have shown that the silane film
thickness on metals increases with the concentration of
the silane solution. The relationship between silane
film thickness and solution concentration is practically
linear
[19,27,41-43]
. It should also be mentioned that in
comparison with the conventional chromate layers
(about 3 m thick), the typically used silane films,
such as the films corresponding to 5% and 2%, are
much thinner. For instance, a bis-amino/VTAS mixture
silane film corresponding to 5% has the thickness of
less than 250 nm, while the one for a 2% silane
solution is only around 50 nm thick. Therefore, it is
safe to say that the silane films outperform the
conventional chromates on a per weight basis
[19]
.
It is well known that silane films on metals inhibit
corrosion primarily by functioning as hydrophobic
barrier coatings preventing the transport of water/ions
to the metal/coating interface
[44-46]
. Numerous recent
studies
[19,41-47]
have shown that the cross-linking of the
siloxane film can be accelerated by increasing the
curing temperature and time. Curing of the silane film
also results in reduction of the film thickness, because
upon curing a denser film is obtained
[19,41-47]
. Curing
and/or aging of silane films has been investigated in
the temperature range of 0-250 and curing time of 0 -
180 min
[19,41-47]
. van Ooij and others typically use a
curing temperature of 100 and a curing time of
20-30 min.
Recently, van Schaftighen et al.
[48]
used a drying
method such that steel panels treated with silanes were
dried by a rotating spinning method. By this drying
method a very homogeneous and reproducible silane
coating can be obtained on the metal surface. Their
results also indicated that the bis-amino and -APS
films are fully cured after 20 min of curing at 100,
whereas the BTSE film is fully cured after 40 min of
curing at 200.
Very recently, van Ooijs group has found that some
of the most promising silane solutions for corrosion
protection of metals are unstable, which means that as
soon as silanol groups have been formed, condensation
to siloxane units will occur. In such solutions, the total
amount of hydroxyl groups changes with time. Upon
hydrolysis, the number of OH-groups reaches a
maximum, and upon further condensation, the
hydroxyl content decreases. This solution behavior
affects the binding of the siloxane structure to the
metal. Upon maximum hydrolysis, a well structured
film is formed. With solution aging, the silane coating
performance degrades, because of an insufficient
number of Si OH groups in the solution. The silane
metal interaction decreases resulting in less anchoring
via Al O Si bonds, eventually leading to poorer
corrosion protection
[49]
.
2 Characterization and Testing
2.1 Characterization techniques
Two major characterization techniques, Fourier-
transform infrared reflection-absorption (FTIR-RA)
spectroscopy and electrochemical impedance spectros-
copy (EIS), have extensively been employed in our
work. The FTIR-RA technique is well known as a
powerful tool in the field of polymer surface charac-
terization. EIS has been known as one of the most


644
valuable techniques in the field of corrosion, yet its
function as a characterization tool has not been identi-
fied until very recently
[50,51]
. Other surface characteri-
zation techniques, such as X-ray photoelectron spec-
troscopy (XPS), scanning electron microscopy (SEM),
and time-of-flight secondary ion mass spectroscopy
(ToF-SIMS), have also been used in our work
[52]
. Very
recently, nuclear magnetic resonance (NMR) has
proven to be a valuable technique to characterize the
hydrolysis degree of silane solutions
[49]
.
Infrared spectroscopic ellipsometry (IRSE) is a
technique that combines in one measurement the
possibilities of traditional FT-IR methods (molecular
information) with those of visible spectroscopic
ellipsometry (SE) (morphologicalfilm thickness
and opticalrefractive index/extinction coefficient
information). Franquet et al.
[41-43,47,48]
have used EIS,
IRSE, and SE along with SEM, Auger electron
spectroscopy (AES), and transmission electron
microscopy (TEM) to study the effects of silane
solution concentration and curing time on the structure
and homogeneity of organosilane layers on aluminum
and steel. Of these characterization techniques, FTIR-
RA and EIS are presented and discussed here.
2.1.1 FTIR-RA spectroscopy
Among all surface characterization techniques, FTIR-
RA spectroscopy is probably the most powerful tool
for observing chemical structure and transformation
(or chemical reactions) in coatings/films, because IR
absorbance peaks are characteristic of chemical bonds.
Since highly reflective metals such as aluminum are
usually used as substrates in our work, external
reflection spectroscopy can be used to study the
surface species or film structures. The incident light
with parallel polarization has sufficient amplitude at
the metal surface to interact with the surface species.
Such technique is called reflection absorption (RA)
spectroscopy.
FTIR-RA has been successfully used to monitor the
structural changes in silane films during different
processes. An example is given in Fig. 3, which
displays FTIR-RA spectra of bis-sulfur silane film
deposited on AA 2024-T3, after curing at 100 for
various time
[44]
. The bands centered at 1100 cm
1
due
to SiOSi become more intensive as the curing
time increases. The region becomes broader as
compared to that without curing. In addition, the major
band for Si O Si has shifted to higher frequencies
from 1110 cm
1
at 0 min to 1133 cm
1
at 1440 min (24
h). All of these changes indicate that the bis-sulfur
silane film has experienced extensive crosslinking
upon siloxane network formation during curing of the
film. It is also notable that the band at 885 cm
1
due to
hydrogen-bonded Si OH decreases in intensity with
curing time, confirming that the siloxanes have formed
via the consumption of the silanols.
2.1.2 Electrochemical impedance spectroscopy (EIS)
In the field of aqueous corrosion science, EIS is
considered as one of the most valuable techniques to
investigate the degradation of polymer coated metal
systems in corrosive aqueous media. An abundant of
literature on this technique exists
[53-56]
, providing
information about theories and applications of EIS.
Here, a brief introduction of EIS fundamentals is

Fig. 3 FTIR-RA spectra of bis-sulfur silane films on AA 2024-T3 after curing at 100 in air for various times
[44]
.

presented. In EIS measurements, a frequency
dependent impedance, Z(f ) (in ), is obtained by
applying a sinusoidal alternating potential signal to
tested systems (e.g., epoxy-coated steel) in a range of
frequencies. The expression for Z(f ) is
Z(f ) = V(t)/I(t) (4)
where f is the frequency, t is the time, V(t) is the
sinusoidal alternating potential signal, V(t)=V
0
sin (2ft);
I(t) is the time-dependent current response,
I
0
sin(2ft+); and is the phase angle between V(t)
and I(t). EIS measurements are carried out in a
conducting solution (i.e., electrolyte). A sodium
chloride (NaCl) solution is commonly used for EIS
monitoring of an organic coated metal substrate. A
schematic of the EIS plots (in the form of Bode plots)
for a polymer-coated metal system is shown in Fig. 4a.
Two distinct steps (time constant, or RC) are observed
in the impedance plot and two maxima in the phase
angle plot. The one at high frequencies is believed to
contain information about the coating; the other one at
low frequencies is related to corrosion occurring at the
metal surface under the coating. The associated EIS
parameters shown in the Fig. 4 are usually used to
describe the coating properties and corrosion kinetics
at the metal surface. These EIS parameters can either
be roughly read from the graph, as illustrated in Fig. 4a,
or can be precisely found by regressing (or fitting) the
associated mathematical equation to the experimental
EIS data
[55]
. The fitting process can be done by
inputting a proper equivalent electric circuit model
(ECM) into commercial-available software. The ECM
shown in Fig. 4b is used to fit the data in Fig. 4a. Two
EIS parameters related to the coating properties are the
coating capacitance (C
c
), and its pore resistance (R
po
),
the changes in which are used as a measure of the
coating performance during exposure to the electrolyte.
Coating capacitance (C
c
) in the unit of farad (F) for
a non-defect coating is given by
C
c
=
0
/ (A/d) (5)
where
0
is the permittivity of free space (8.854 19
10
12
F/m); is the dielectric constant of the coating; A
is the total area exposed to the electrolyte (m
2
); and d
is coating thickness (m). A typical value for a dried
polymer is 3-4, 8.5 for an oxide layer, and 80 for water.
It is noted that of water is much greater than that of a
dried polymer. Thus, of the polymer changes
significantly when water penetrates into the polymer.

Fig. 4 Schematic EIS plots of a polymer coated metal
system (a), and equivalent electric circuit model (ECM)
for EIS data fitting (b) (Ref. [44]).
For a given coating, the changes in C
c
are often taken
as a measure of water uptake in the coating
[54,57]
. If the
specific conductivity of a polymeric coating is
negligible with respect to that of the electrolyte, R
po
of
the coating containing cylindrical defects/pores with
the same length is expressed as
R
po
=(d/A
p
) (6)
where is the specific electrolyte resistivity in the
defects/pores (m), which is constant for a given
electrolyte system; d is the length of the cylindrical
defects (m) or coating thickness; and A
p
is the
defect/pore area in the coating (m
2
). For a given
coating, R
po
is inversely proportional to A
p
. Once the
electrolyte (water and ions) penetrates into the coating
through defects and pores, conducting shortcuts
develop between the electrolyte and the metal substrate.
This would cause a decrease in the value of R
po
. Thus,
R
po
is another EIS parameter that is used to evaluate
the coating performance in an aqueous environment.
It should be noted that the time constant mentioned
above is the product of resistance (R) and capacitance
(C), in the unit of seconds. The time constant for a
polymeric coating is thus given as R
po
C
c
. When a
silane film is crosslinked, a majority of the pores in the
film would be sealed and water as condensation
product would evaporate. This pore sealing would
decrease the total pore area (A
p
), resulting in an
increase in R
po
. In the meantime, water removal


646
would cause a reduction in C
c
.
The other EIS parameters shown in Fig. 4a are: R
so

is the uncompensated solution resistance (), the value
of which is small (only several tens of and has no
effects on the coated system; R
t
is the charge
transfer resistance polarization resistance (); and C
dl

is the capacitance of the double layer formed at the
coating-metal interface (F). The latter two parameters
are often observed when corrosion starts on the metal
substrate under the coating. It should also be noted that
the phase angle plot, in some cases, is more valuable
than the impedance plot. It has been reported
[57]
that
some subtle changes in coating structures are clearly
reflected in the phase angle plot but not in the
impedance plot.
EIS has been first employed in our silane work for
characterization purpose
[44,58]
. The study clearly
showed that EIS actually has the ability to monitor
chemical structural changes in silane films in different
processes. An example is shown in Fig. 5. The Bode
plots for the bis-sulfur silane-treated and cured (0.16 h
at 80 ) AA 2024 -T3 as a function of immersion time
in the 0.5 mol/L K
2
SO
4
solution
[58]
. It can be seen that
the total impedance of the system increase with
immersion time throughout most the measured
frequency range, with the appearance of a distinctive
additional time constant after 4 h of immersion. The
additional time constant is shown more clearly in the
phase angle plot than in the impedance plot.
At the initial immersion stages (0.16-2 h), only two
time constants are observed, one (RC
1
) located at high
frequencies (~10
4
Hz), and the other (RC
2
) at low
frequencies (~ 0.1 Hz). Since the bis-sulfur silane film
was coated uniformly on the AA 2024-T3 surface,
these two time constants can be assigned to the silane
film (RC
1
) and the aluminum oxide (RC
2
), respectively.
As the immersion process continues (after 4 h of
immersion), the impedance of the silane film (RC
1
)
increases remarkably and, correspondingly, the time
constant RC
1
is shifted to lower frequencies. It is
interesting to notice that an additional time constant
(RC
3
) occurs in the phase angle plot in the medium
frequency range between RC
1
and RC
2
. It is also
noticed that the low-frequency impedance keeps
increasing even after 24 h of immersion (Curve 5 in
Fig. 5), but instead of two distinctive time constants,
only one broadened time constant appears in the
medium frequency range. This is probably due to the
overlap of the two time constants (RC
3
and RC
1
).

Fig. 5 Bode plots for bis-sulfur silane-treated AA
2024-T3 panels during immersion in 0.5 mol/L K
2
SO
4

solution for 0 to 24 h (Ref. [58]).
With the help of FTIR-RA analysis, the above
changes in EIS plots can be explained as follows.
The significant increase of the total impedance of the
system was attributed to: 1) the formation of siloxane
structure Si O Si in the existing silane films
by condensation of silanol groups SiOH generated
from the hydrolysis of residual ester groups
SiOC
2
H
5
; 2) the formation and growth of the
interfacial layer between the silane film and the
aluminum oxide.
2.2 Corrosion testsElectrochemical tests
DC polarization test and EIS are two popular
experimental methods in modern corrosion study.
Unlike conventional weight loss measurements which
require many more days to determine corrosion rate,
these two methods need considerably less time.
2.2.1 DC polarization tests
Popular polarization methods, such as Tafel
extrapolation and polarization resistance, to measure
corrosion rates have the following advantages as
compared to conventional weight loss measurements:
1) Usually only a few minutes are required to
determine corrosion rate; 2) The methods are highly
sensitive, and accelerating factors, such as elevated
temperature, to increase rates in the laboratory are
usually unnecessary. More fundamentals about DC
polarization methods appear in Ref. [59].
Figure 6 is an example of DC polarization curves of
AA 2024-T3 treated with and without the bis-sulfur

silane, obtained from a 0.6-mol/L NaCl solution (pH
6.5, open to air). The bis-sulfur silane treated AA
2024-T3 panels were immersed in the electrolyte for
5 h before data collection for the reason mentioned
earlier. It is seen that both anodic and cathodic current
densities of AA 2024-T3 have been reduced by more
than 2 decades after the silane treatment (Curve 2) at
the applied voltages with respect to that of the bare AA
2024-T3 (Curve 1). The E
corr
(corrosion potential) of
AA 2024-T3 and the shape of the curves, however, do
not show a substantial variation after the silane
deposition. This indicates that the bis-sulfur silane
mostly behaves as a physical barrier.

Fig. 6 Representative DC polarization curves of AA
2024-T3 treated with and without bis-sulfur silane,
measured in a neutral 0.6-mol/L NaCl solution.
2.2.2 EIS measurements
Just as mentioned above, EIS measurements have been
proven to be one of the most valuable techniques to
investigate the degradation of polymer coated metal
systems in corrosive aqueous media. Instead of using
noncorrosive electrolyte such as K
2
SO
4
, corrosive
electrolytes like NaCl or HCl are often used in EIS
measurements to simulate real corrosive environments.
The changes of EIS parameters, i.e., C
c
,

R
po
, C
ct
, and R
p
are good indicators for degradation degree of
polymeric coatings on metals and corrosion extent at
the metal surfaces underneath the coatings.
2.3 Industrial performance tests
2.3.1 ASTM B117 (Salt spray (fog) test, SST)
This test was employed to evaluate bare corrosion
protection of silane-treated metals without topcoats.
According to the specification, 5% salt solution (NaCl)
is atomized in a salt spray chamber at 35 with the
solution pH around 7. The tested panels shall be placed
at an angle of 45 in the chamber, exposing to the salt
fog for a certain period
[60]
.
2.3.2 ASTM 1654-92 (Corrosion test for painted
or coated metals and alloys)
This test provides a method to evaluate the corrosion
performance and paint adhesion of painted alloys with
silane pretreatment. The testing conditions are similar
to that for ASTM B117, except that the painted metal
surfaces need to be scribed prior to salt spray testing.
Delamination area is measured along the scribe line
after exposure, the value of which is often used as a
measure for the corrosion performance and paint
adhesion of the painted systems
[60]
.
2.3.3 ASTM B368 (Copper-accelerated acetic
acid-salt spray testing, CASST)
This test is derived from ASTM B117. First, 0.25 g/L
copper chloride (CuCl
2
2H
2
O) is added into 5% NaCl
solution. The pH of the salt copper solution is adjusted
to the range of 3.0-3.3 by the addition of glacical acetic
acid. The temperature in the salt spray chamber is 49
(Ref. [60]).
2.3.4 A few examples of paint adhesion tests
On polymer coated pretreated metal panels, paint
adhesion is usually tested with a cross-cut adhesion
test, where a cross-hatch is drawn on the painted panel
and the adhesion of the coating is tested with adhesive
tape. The degree of adhesion is measured according to
standard ASTM D3359-93. Dry adhesion of painted
pretreated panels is usually very good. Therefore, this
test is usually combined with a water immersion or
humidity test. After exposing the panels to water
immersion or humidity, the wet adhesion of the panels
is tested as described in Refs. [61, 62].
van Ooij and Zhu
[19]
also used the Machu test to
evaluate paint adhesion and corrosion performance of
painted metals. The painted metal panels are cross-
scribed and then immersed into a solution of 5% NaCl
+ 10% H
2
O
2
at 37 for 1 day. The next day, another
10% H
2
O
2
is added into the original solution. After 2
days of immersion, the panels are taken out and tape is
used to pull off the delaminated paints along the scribe
lines. The delamination distance is taken as a measure
of paint adhesion and corrosion performance of the
tested system
[63]
.


648
3 Silane Films on Metals
3.1 Different types of corrosion uniform, localized,
and others
Uniform corrosion is defined as the uniform, regular
removal of the metal from the surface when the
corrosive environment has the same access to all the
parts of the surface of the metal
[64]
. Atmospheric
corrosion is probably the most prevalent example of
uniform corrosion and it is also visually apparent.
Barrier coatings of many sorts, both organic and
inorganic, can be used to inhibit uniform corrosion of
metals. Silane surface treatments have been
investigated at University of Cincinnati for over 13
years. Table 2 shows where unmodified silane films
have been shown to be effective. Table 2 indicates that
many forms, including localized forms, of corrosion
can be controlled for many metals of engineering
interest, ranging from stainless steel to magnesium
alloys. In addition to corrosion protection, improved
adhesion to paints, adhesives or rubber has also been
obtained.
Table 2 Metals and forms of corrosion where films of trialkoxy silanes have been shown to be effective.
Metal Forms of corrosion controlled Bonding
Cold-rolled steel Uniform, scribe creep, blistering Powder paints, E-coats, appliance paints, rubber
Hot-rolled steel Scribe creep Waterborne paints
Stainless steel SCC, pitting, IGC, crevice corrosion Powder paints, rubber, adhesives
Electrogalvanized steel Scribe creep E-coats, powder paints, rubber
Hot-dip galvanized steel White rusting, scribe creep Powder paints, E-coats, appliance paints
Zinc sheets (Ti-zinc) White rusting
Galvalume
sheet Edge creep, scribe creep, white rust Powder paints, coil paint systems
Galvannnealed sheet Scribe creep Automotive E-coats
Aluminum alloys
1XXX, 2XXX, 3XXX, 5XXX,
6XXX, 7XXX series
Uniform, pitting, SCC, filiform, CFC Powder paints, solvent-based paints, rubber
Copper, brass Uniform, SCC, dealloying
Nickel Galvanic
Magnesium alloys Pitting, uniform, galvanic

3.2 Two universal silane mixtures for corrosion
protection of various metals
For bare corrosion protection purposes van Ooij et
al.
[19,44-46]
usually use a silane solution concentration of
5% and for silane treatments under paint a concentra-
tion of 2%. For bare corrosion protection the hydro-
phobic silanes BTSE and bis-sulfur have already dem-
onstrated their corrosion protectiveness for many met-
als
[14,15,52,58,65]
. Unfortunately, their hydrophobic nature
requires a large amount of organic solvents such as
ethanol or methanol in the preparation of the silane
solutions.
A solvent-based silane system which has proven to
give excellent corrosion resistance in unpainted state is
the mixture of the bis-sulfur and bis-amino silanes with
the ratio 3:1. This system is able to protect many
metals, for instance, aluminum, HDG steel, and Mg
alloys. Figures 7 and 8 present the scanned images of
silane-treated AA 2024-T3 and HDG panels after EIS
measurements. It is clearly seen that no corrosion is
shown on both mixture-treated AA 2024-T3 and HDG
panels (Figs. 7c and 8c), indicating that the
combination provides good corrosion protection for
both metals. This mixture has a relatively short shelf
life and high VOC content. Despite these facts, it
may find a market nische in applications where
VOC is not a major problem.
One of the main objectives in recent years has been
to develop water-soluble silane solution mixtures with
corrosion protection properties as powerful as the
systems based on ethanol-water solutions. In this
respect, a universal water-soluble silane system based
on bis-amino and vinyltriacetoxy silanes was invented
by van Ooij and Zhu
[19]
. They studied the corrosion
resistance and paint adhesion of this mixture on several
metals. The silane mixtures and the deposited films
were also characterized.


Fig. 7 AA 2024-T3 panels after 32 days of immersion in 0.6 mol/L NaCl solution: (a) untreated; (b) bis-sulfur silane-
treated; (c) mixture-treated; and (d) bis-amino silane-treated
[46]
.

Fig. 8 HDG panels after 8 days of immersion in 0.6 mol/L NaCl solution: (a) untreated; (b) bis-sulfur silane-treated; (c)
mixture-treated; and (d) bis-amino silane-treated
[46]
.
with polyurethane and polyester powder-paints on The bis-amino/VTAS mixture is, by itself, quite stable
and hydrolyzes readily in the aqueous mixture. The
mixture works well, because with the addition of a
small amount of bis-aminosilane, the VTAS solution
becomes less acidic and the condensation of SiOH can
be effectively suppressed. A likely mechanism is that
the secondary amine groups in the bis-aminosilane
form a more stable hydrogen bond with silanol groups
than the one between silanols themselves. As a result,
condensation of silanols is prevented in the solution.
Figure 9 displays the salt spray testing results of AA
6061-T6 treated with the bis-amino/VTAS mixture, as
compared with untreated and chromated panels. It is
seen that the bis-amino/VTAS mixture treated AA
6061-T6 surface does not show any sign of corrosion
after 336 h of SST, while the chromated surface
exhibits a certain degree of discoloration. The bare AA
6061-T6 surface on the other hand, has corroded
heavily, showing uniform corrosion on the surface.
Performance tests also showed that the water-based
bis-aminosilane/VTAS mixture provides comparable
corrosion protection in the painted state, for example,

Fig. 9 AA 6061-T6 panels after 336 h of SST: (a)
untreated (20 h of exposure), (b) chromated (Alodine-
series), and (c) silane-treated (bis-aminosilane/VTAS =
[19]

1.5/1, 5%, pH 3.7) .
aluminum alloys, as compared with chromates
[19]
.
If the universal mixtures are, however, compared
with each other, it is obvious that the bis-amino/VTAS
mixture does not provide as good bare corrosion
protection on various metals as the hydrophobic bis-
sulfur/bis-amino mixture. This is because the bis-
amino/VTAS film is hydrophilic and contains positively
charged secondary amino groups which attract water


650
and electrolytes to the siloxane/metal interface
[19,46]
.
olution . On Al alloys
th
of these alloys make them thus
sli
ing particles (Al
2
CuMg) and Al-Cu-Fe-
M
f corrosion products,
l
an silane treatment
o
attribu
nt w

3.3 Aluminum and aluminum alloys
3.3.1 Character of the Al alloys
Numerous studies have shown that several aluminum
alloys can be protected by silane coatings
[19, 44-46, 66, 67]
.
Figure 7 demonstrated clearly that all three silane
systems: (b) the bis-sulfur silane-treated; (c) the
mixture-treated; and (d) the bis-amino silane-treated
are able to protect AA 2024-T3 panels after 32 days of
immersion in 0.6 mol/L NaCl s
[46]
e bis-amino/VTAS system also provides excellent
bare corrosion protection
[19]
.
The wide range of aluminum alloys available has
emerged from a need of high strength, light weight
materials in the aerospace and automobile industries.
However, the heat treatments of these aluminun alloys
result in dispersion of precipitates and second phases
which render the high strength and mechanical
properties. Since these precipitates are invariably
cathodic or anodic relative to the surrounding matrix,
this can lead to local corrosion pairs at phase interfaces.
The structures
ghtly vulnerable for local corrosion at phase
boundaries.
van Ooijs group has studied silane treatments
extensively on AA2024-T3, which is becoming the
best known and most widely used aerospace aluminum
alloy due to its excellent mechanical properties.
AA2024-T3 does, however, not have as good corrosion
resistance as most other aluminium alloys and it
suffers different forms of corrosion due to its intrinsic
electrochemical properties. Copper (Cu) is one major
alloying element in AA2024-T3 (3.8 wt.%-4.9 wt.%),
which makes it susceptible to corrosion
[68]
. In general,
AA2024-T3 suffers corrosion such as pitting,
intergranular, and stress corrosion. The microstructure
of AA2024-T3 is characterized by a uniform
distribution of second-phase particles such as the Al-
Cu-Mg-contain
n-containing particles [Al
6
(Cu
2
FeMn)] in the Al
matrix
[69-72]
.
Zhu and van Ooij studied the corrosion mechanism
of bare AA 2024-T3. They found that the corrosion of
this alloy starts from the dealloying of anodic Al-Cu-
Mg-containing particles (Al
2
CuMg), followed by
severe cathodic dissolution of the surrounding Al
matrix due to the local alkalization formed around the
particles. Such corrosion in AA 2024-T3 can be,
however, inhibited efficiently by silanes
[73]
. The films
of the bis-sulfur silane and the mixture of bis-
sulfur/bis-amino form a so-called interfacial layer onto
aluminium alloys. It has been found that this interfacial
layer heavily restricts pit growth underneath the silane
films via retarding the transport o
as wel as effectively blocks a number of cathodic sites
available for cathodic reactions.
3.3.2 Interaction of the silanes with the Al surface
Several studies have shown that the treatment of
aluminum with silanes is easier th
f other metals, for instance, HDG steel. This can be
ted to many factors such as:
The pH treatme indow for aluminum is
wider than for zinc
[47,19,74]
.
The covalent Al O Si bond is readily formed
between a hydr lyz d silane and alum o e inum, and
h c the bond formed is less ionic than t e or-
responding Zn O Si bond
[39,75]
.
Al is trivalent, and it can crosslink a Si O Si
bond by inserting into it. ZnO is divalent and is
unable to do the same, i.e., aluminun silicates

o matches the spacing of
(e.g., zeolites) exist in all kinds of ratios and
forms but there is no zinc silicate.
Aluminum oxide, Al
2
O
3
, has an affinity for
silicate. The spacing of hydroxyl groups on
aluminum als
comparable groups on silane coupling agent
oligomers
[6]
.
A few studies
[39,75]
provide recent, new evidence for
the existence of Al O Si bonds at the alumi-
num/silane film interface. In both papers, electrodepos-
ited and immersion deposited nonfunctional silane
films were studied. A BTSE film was depo ited by
immersion, immediately rinsed with ethanol and the
existence of the instantaneously formed Al
s
O Si
monolayer was analyzed by XPS and TOF-SIMS. The
latter work provided direct evidence for the presence
of O
2
Al (O Si O) and OAl (O SiO)
2
groups at
the silane-aluminum oxide interface of the electrodepos-
ite e e d film. Such bonds hav be n suggested, but they
have largely remained elusive over the years
[39,75]
.
The existence of the Al O Si bonds at the silane
film/aluminum interface does not, however, automati-
cally guarantee the corrosion protection of the metal.

Although corrosion inhibition of the metal is intimately
related to the formation of Al O Si bond, the bond
itself is not hydrolytically stable
[6]
. When exposed to a
large amount of water, the Al O Si bond is hydro-
lyzed back to reform hydrolphilic AlOH groups and
SiOH groups. This obviously destroys the hydropho-
bicity of the metal surface. Therefore, suppression of
water uptake in a silane film is of virtual importance in
terms of maintaining a good adhesion between the si-
lane film and the substrate. This can be achieved by
fully crosslinking the silane film, i.e., by making the
film denser and by enhancing trin ic silane film hy-
drophobicity. In this way, water uptake in the films is
suppressed
in s
, hydrolysis of Al O Si bond is pre-
ve
er
d with
nted, and corrosion protection of the metal is guaran-
teed
[46]
.
Zhu and van Ooij
[44-46,58]
have shown that the film
deposited from the bis-sulfur silane solution on alumi-
num actually is made up of three different regions as
illustrated in Fig. 10, which shows the lay structure
from the outside to the inside: a crosslinked outermost
bis-sulfur silane film enriche Si O S bo s;
an extensively crosslinked or dense bis-sulfur interfa-
cial layer dominant with Si
i nd
O Si and Al O Si
bonds; and the inner Al oxide layer on the alloy sub-
strate. Referring to this structure, the high-frequency
time constant centered at 10
4
Hz in an EIS phase angle
plot (as in Fig. 5) is due to the outermost silane film;
the mid-frequency one at 10 Hz is the response of the
interfacial layer; and the small tail appearing below 0.1
Hz is related to the Al oxide layer. The dense silane
film structure described is formed when the silane film
is cured at elevated temperatures (100) due to
extensive crosslinking of SiOH groups. The thickness
of the interfacial layer has estimated to be in the or-
der of about 5 nm (Ref. [39]). The bis-sulfur/bis-
amino mixture (3:1) shows an EIS behavior similar
to that of the bis-sulfur silane
[45]
. Franquet et al.
confirmed this result by studying these films by
surface analy
have also studied silane layers on aluminum and
tical, optical, and electrochemical
methods
[41-43]
.

Fig. 10 Schematic of structure of bis-sulfur silane-
treated AA 2024-T3 system
[46]
.
3.4 Galvanized steels and zinc
d state in the building and appliance
in
he film which highly promotes
w
t are
po
The bis-sulfur/bis-amino mixture enhances the
Galvanized steel is a generic term used to describe
steel, which has been coated with zinc or a zinc alloy.
Galvanized steels are widely used both in unpainted
and in painte
dustry
[76]
.
Figure 8 clearly demonstrated that the bis-sulfur/bis-
amino mixture gives HDG steel very good bare corro-
sion protection while the silanes alone are unable to
protect HDG steel. Figure 11 explains schematically
the reasons for the failure of the bis-amino and bis-
sulfur silanes on HDG steel. The reason for the failure
of the bis-amino silane film on HDG steel is due to the
hydrophilic nature of t
ater/ion penetration.
The hydrophobic bis-sulfur silane performs very
well on AA 2024-T3, but failed on HDG. This is
because AA 2024-T3 has a higher surface energy than
HDG steel; and therefore, the bis-sulfur silane is able
to wet the Al surface but not the HDG surface. This
obviously leads to an insufficient wetting of the Zn
oxide. As a result, a non-homogeneous bis-sulfur
silane layer is formed on HDG (Fig. 11). Local
corrosion initiates at those defective sites tha
orly covered by the bis-sulfur silane film
[46]
.

Fig. 11 Schematic structure of bis-amino, bis-sulfur, and mixture treated HDG steel
[20]
.


652
corrosion resistance of HDG steel. This improvement
is due to the fact that a small portion of bis-amino
silane makes the mixture solution hydrophilic enough
to wet the Zn oxide on HDG, which facilitates the
formation of a homogeneous film on HDG. On the
other hand, a large portion of bis-sulfur silane
enhances the hydrophobicity of the mixture film,
which is the basis for good protective performance of
the mixture. However, unlike the mixture-treated AA
2024-T3 system which exhibits two time constants in
the EIS phase angle plot, only one time constant is
shown for the mixture-treated HDG. This indicates that
rather than forming two distinct layers (i.e., outermost
silane layer and interfacial layer) as in the case of AA
2024-T3, the mixture only forms one single structure
on HDG steel (Fig. 11)
[46]
.
This result is probably due to the different behaviour
of the oxides on the metals, discussed in Section 3.3.2.
The trivalent aluminum in the Al
2
O
3
oxide surface is
able to form covalent Al O Si bonds and thereby
crosslink and interpenetrate into the siloxane network
upon curing the mixture film. The divalent ZnO is
unable to do this. Therefore, an interfacial layer rich in
Me O Si and Si O Si bonds is not formed on
HDG steel, even if the film is cured at elevated
temperatures. It may, however, be possible to form this
type of interfacial layer on HDG steel by modification
of the HDG surface before depositing the silane
mixture film onto the HDG steel.
The solvent-based bis-sulfur/bis-amino mixture also
provides good corrosion protection of galvanized steel
under paints. This silane mixture passivates the metal
paint interface to such extent that paint thicknesses can
be reduced substantially (e.g., from 25 m to 5 m)
without loss in performance
[67]
. Also, the water-based
bis-amino/VTAS mixture works well on HDG steel in
the painted state but poorer in the unpainted state. The
Machu test results of polyester powder painted HDG
steel shown in Fig. 12 exhibit an example. The
behavior of the bis-amino/VTAS silane mixture and
the chromated are comparable, i.e., no paint
delamination was observed after testing (Figs. 12b and
12c), while that of the untreated panel (Fig. 12a) shows
severe paint delamination an considerable amount of
corrosion along the scribe line
[19]
.

Fig. 12 Machu testing results of HDG panels: (a) untreated, (b) silane-treated (bis-amino silane/VTAS = 5/1, 2%, pH
6), and (c) conventional chromate-treated (Granodine 108B
)
[19]
.
4 Modified Silane Films on Metals
4.1 Objectives of modified silane films on metals
Silanes have been demonstrated to provide excellent
corrosion resistance and paint adhesion in the previous
sections. These excellent anticorrosion properties can
be further tailored and improved by strengthening the
coatings through various methods. The corrosion
behaviour and mechanical properties of the films on
metals can, however, be further improved if they are
modified and strengthened using various methods. The
objective of the modifications is to improve the
following drawbacks that silane films on metals have
in comparison to chromates:
1) Silane films are very thin (about 200-300 nm).
This limits their capability to provide long-term bare
corrosion protection.
2) Chromates have defect-healing capabilities,
which neither silanes nor any other proposed chromate
replacements have. The self-healing capability means
that chromates are able to seal small defects in the
conversion coating by dissolving hexavalent chromate
ions, which then protect the defect by passivating it by

forming trivalent chromium oxide at the damaged site.
3) Silane films are colorless, whereas chromate
films can be detected by their yellow color. This is
useful in coil coating applications, because it enables
the observer to see the film after running the sheet
through the bath.
Our research currently aims at solving the above
mentioned problems and in addition we will add some
useful properties to the silane films by modifying them.
The objective is to completely replace the chromates
with the improved silane films. The improvements
focus on:
1) Increasing the silane film thickness and thereby
improving the corrosion resistance and mechanical
properties of the films. This is achieved by adding
nanoparticles such as alumina and silica into the
systems.
2) Modifying, the silane films with leachable
inorganic or organic inhibitors in order to give the
films the self-healing effect described above.
3) Giving color to the films by adding dyes to the
silane films.
Additionally, the silane group investigates new
techniques such as the electrodeposition method for
depositing silanes films on metals in order to make
films that are very dense and uniform.
4.2 Loading silane films with nano-particles
A primary study on this subject was done on AA5005
treated with the water-based bis-amino/VTAS mixture
loaded with a small amount of alumina nano-particles.
The 336 h-SST results showed that the corrosion
protection offered by the nano-structured silane film
was comparable to that of the chromate control.
Recently, a systematic study has also been done on
colloidal silica nano-particle loaded bis-sulfur silane
films on AA2024-T3 substrates
[22,77]
.
Figure 13 shows the DC polarization test curves of
the AA2024-T3 panels coated with the bis-sulfur silane
with and without silica nanoparticles. The cathodic
shift observed for the bis-sulfur film loaded with 5
ppm of silica (Curve 3 in Fig. 13) indicates that the
incorporation of a small amount of silica alters the
cathodic kinetics on the alloy surface. It is also
observed that the polarization curves of the silica
loaded bis-sulfur silane treated AA2024-T3 samples
have two cathodic regions while the curves of the bis-
sulfur treated and untreated AA2024-T3 only have one.
This suggests that a small amount of silica in the silane
film also changes the mechanism of the cathodic
reactions on the alloy. Instead of one major cathodic
reaction, two cathodic reactions reflected by the two
cathodic regions dominate over the applied cathodic
voltages. The proposed mechanism for this
phenomenon is explained in Section 5 (Mechanisms).
In Fig. 14 the values of corrosion potential (E
corr
)
and corrosion rate (I
corr
) of nano-structured bis-sulfur
silane treated AA 2024-T3 panels are plotted as a
function of silica content in the silane solution. A
reduction in E
corr
is observed for the film obtained
from the silane solution containing 5 ppm silica,
indicating that the film behaves as a cathodic barrier
like cerium compounds
[78,79]
. A small amount of silica
in the silane film suppresses the cathodic reactions. As

Fig. 13 DC polarization curves of AA2024-T3 treated with and without silica loaded bis-sulfur silane films
[22]
.


654

Fig. 14 E
corr
and I
corr
of bis-sulfur silane treated AA2024-T3 systems as a function of silica content in the bis-sulfur
silane solution
[22]
.
the amount of silica in the films is increased up to 15
ppm such cathodic inhibitive behavior disappears. The
I
corr
value is lowest for the AA2024-T3 sample treated
in the solution containing 15 ppm silica (Fig. 14). As
the silica content is further increased the I
corr
value
gradually rises, showing that the corrosion inhibition
of the silane film on AA2024-T3 degrades when
loaded with too much of silica (50 ppm).
A similar trend was observed in the EIS results. The
low-frequency impedance values (Z
lf
) of the systems
increase with the increase of the silica content until 15
ppm compared with the unloaded panel. The Z
lf
value,
however, drops sharply for the film obtained from the
silane solution containing 50 ppm silica. This, again,
confirms that a large amount of silica particles is not
required from the corrosion protection point of view.
The two time-constant behavior observed for the
sample corresponding to 50 ppm silica indicated that a
double layer had formed at the silane/metal interface.
The formation of the double layer in the sample
containing 50 ppm silica indicates that an excess of
silica particles in the film has a negative effect on the
interfacial adhesion, leading to a premature film
delamination from the substrate
[22]
.
The hardness of the films was measured using MTS
Nanoindenter XP. The hardness results indicated that
the interfacial layer of the bis-sulfur silane film is
preferentially hardened by the incorporation of a small
amount of silica. With a further increase in silica (e.g.,
15 ppm), not only the interfacial layer but also the
silane surface is hardened by showing an improvement
in its hardness value. However, an extra amount of
silica (50 ppm) seems only to strengthen the silane
surface but not the interfacial layer, as no further
increase was seen for the hardness of the interfacial
layer after 15 ppm
[22]
.
Based on the results presented, it can be concluded
that a small amount of silica nano-particles (15 ppm)
does improve both the corrosion performance and
the mechanical properties of the bis-sulfur silane
film on AA2024-T3. Corrosion resistance, however,
diminishes when further increasing the amount of
silica in the film (15 ppm). Moreover, an extra large
amount of silica particles in the film even degrades the
corrosion performance of the silane film (> 50 ppm).
Therefore, the optimum silica amount in the bis-
sulfur coating solution appears to be between 5 ppm to
15 ppm
[22,77]
.
4.3 Loading silane films with inhibitors
4.3.1 Adding inorganic and organic inhibitors to
the bis-amino/VTAS film on AA2024-T3
One of the ways to increase the corrosion resistance of
the silane films on metals is to add corrosion inhibitors
into the films. Such inhibitors can leach out slowly
from the film when corrosion initiates in a defect or a
scratch on the metal. After establishing the corrosion
resistance of various inorganic and organic inhibitors
that work for the AA2024-T3 alloy, three inhibitors
were selected for further studies. The results for a rare-
earth metal salt, cerium nitrate
[80]
, organic inhibitors
such as benzotriazole
[81]
, and tolyltriazole
[82]
are
discussed here. The selected inhibitors suppress the
corrosion on AA2024-T3 by covering the surface
and/or by forming complexes with the alloy
[83, 84]
. The
compounds are also non-toxic and environmentally
acceptable as compared with chromate.
Varying concentrations of the above mentioned
inhibitors were added to the bis-amino/VTAS silane
solution and the silane films were deposited onto Al

2024-T3. The corrosion resistance and the self-healing
capabilities of the inhibitor-loaded silane films on
AA2024-T3 were examined. The effectiveness of non-
chromate inhibitors in the silane film depends on a
number of factors such as the solubility of the
inhibitors, leachability of the inhibitors, the
permeability of the silane coating, and the
compatibility of the inhibitors with the silane. The
inhibitors were chosen considering the above
mentioned factors.
4.3.2 DC polarization test results of the inhibitor
loaded silane film samples
Figure 15 shows the DC polarization curves for the
AA2024-T3 panels coated with bis-amino/VTAS
silane with and without varying concentrations of
cerium nitrate and the blank as control. For the panels
containing 1000 and 2000 ppm cerium nitrate, a shift
in E
corr
in the cathodic direction is observed. A
reduction in the cathodic current density values is also
detected. This is an electrochemical effect as the rare
earth metal salts act by blocking cathodic areas of the

Fig. 15 DC polarization curves for the bare AA2024-
T3 panel (1) and panels coated with bis-amino/VTAS
silane film (2) and bis-amino/VTAS silane films doped
with 100 ppm (3), 1000 ppm (4), and 2000 ppm (5) of
cerium nitrate inhibitor on AA2024-T3 (Ref. [80]).
material and consequently reduce the overall corrosion
rate. A decrease in both I
corr
and E
corr
also indicates that
the inorganic inhibitor does not interact with the silane
network.
Loading the bis-amino/VTAS film with different
amounts of tolyltriazole results in a reduction of the
cathodic current density (I
corr
), implying a reduction of
the cathodic reaction rate and a better corrosion
resistance as compared to the silane film without
tolyltriazole. The performance of the film increases
upon increasing the amount of tolyltriazole. Similar
results were obtained for the bis-amino/VTAS film
loaded with benzotriazole. The reduction in I
corr

indicates a geometric blocking effect of active metal
reaction sites. The triazole inhibitor in the silane film
can react with the copper phases and form Cu-triazole
complexes making the copper unreactive to the
corrosive medium. The inhibitor thus gets immobilized
at the reactive metal surface and gives a reduction in
the cathodic current density.
4.3.3 Self-healing effect and paint adhesion of the
inhibitor loaded silane films
The panels coated with the cerium nitrate (810
4

g/m
2
) loaded bis-amino/VTAS silane films were
scribed. The width of the scribe was about 100-120 m.
The scribed panels were immersed in 0.5 mol/L NaCl
electrolyte for 7 days. Figure 16 shows the SEM
images of the scribes in the bis-amino/VTAS film (a)
with and (b) without cerium nitrate. The scribe in Fig.
16b shows corrosion products along the scribe whereas
the scribe in Fig. 16a shows less or no corrosion
products indicating that the cerium inserted imparts
self-healing capabilities to the film. The scribes of the
cerium nitrate containing panel were analyzed by
SEM/EDX. Figure 17 shows a part of the EDX

Fig. 16 SEM image of AA2024-T3 coated with bis-amino/VTAS silane mixture (a) containing cerium nitrate and (b)
without cerium nitrate, after 7 days immersion in 0.5 mol/L NaCl (Ref. [80]).


656
spectrum obtained. The analysis result confirmed the
presence of cerium in the scribe. A Ce peak is
observed of the same order of intensity as the copper
peak, the major alloying element of AA2024-T3. This
indicates that cerium ions have leached out of the
silane film and precipitated into the scribed area, where
they reduce the rate of the cathodic reaction.

Fig. 17 SEM/EDX analysis of an area on the scribed
AA2024-T3 coated with silane containing cerium ni-
trate, immersed in 0.5 mol/L NaCl for 7 days
[80]
.
The idea is that the water-soluble inhibitor should be
released only on demand, i.e., the inhibitor should not
be washed away when exposed to water. Ideally when
the electrolyte penetrates the silane film (containing
cerium inhibitor), local anodic and cathodic reactions
start to occur at the metal surface. The areas where the
cathodic reactions occur (at high pH) should trigger the
release of cerium (cathodic inhibitors). Therefore, the
AA2024-T3 panels coated with the bis-amino/VTAS
film containing 100 ppm cerium nitrate were immersed
in deionized water at different pH values (2, 7, and 11)
for different periods of times; 1 h, 48 h, and 96 h.
The same test was conducted by exposing Ce
containing panels to 3.5% NaCl for 48 h. After
exposure, the immersion solution of each test panel
was analyzed for cerium by ICP/MS.
It was found that inorganic Ce(III) is leached out of
the hydrophilic bis-amino/VTAS film at pH 2, pH 7,
and pH 11, but the amount at pH 11 was 100 times
higher than at pH 2 and pH 7. There was no difference
in the amounts obtained at pH 2 and pH 7. This
indicates that at high pH a cathodic reaction occurs and
the cerium nitrate is released into the solution. The
generation of hydroxyl ions due to the cathodic
reaction swells up the silane film leading to the release
of inhibitor. This shows that the cerium is not washed
away when exposed to water and is released only on
demand to achieve self-healing. The amount
released during salt water exposure was comparable
to that released at high pH. The organic inhibitors
(tolyltriazole and benzotriazole) were also examined in
a similar way but they were not able to impart a self-
healing effect to the bis-amino/VTAS film.
AA2024-T3 panels coated with the bis-amino/VTAS
mixture containing small amounts of cerium nitrate
and natrium chromate were exposed for 336 h to a
neutral salt spray test. The amounts of Na
2
CrO
4
in the
films were a factor 10
4
lower than that in a regular
chromate conversion layers. The overall protection of
the metal was substantially improved by the small
chromate addition. Further, the scribes in the panels
remained clean and Cr could be detected in the scribes
by SEM/EDX. Thus, not only inhibitor cations (Ce
3+
),
but anions as well can be leached out from the silane
films.
The AA2024-T3 panels treated with the bis-
amino/VTAS silane mixture with and without 1000
ppm of cerium nitrate were coated with a polyester
powder paint and tested for paint adhesion. The cross-
cut test was made before and after exposure to water.
The results indicated that there was no loss of adhesion
after doping the silane with cerium nitrate. Thus, the
inhibitor in the silane film does not affect its adhesion
to the paint.
In summary, cerium nitrate reduces both I
corr
and
E
corr
and imparts the self healing effect to the silane
film studied. Ce nitrate also works well with small
amount of chromates. The organic inhibitors added to
the bis-amino/VTAS silane films improved the overall
corrosion resistance of the AA2024-T3 alloy but did
not impart a self-healing effect to the films.
4.4 Adding color to silane films
Two dyes were examined: Basonyl Yellow NB 122
dye and Basonyl Red 482 (xanthene) red powder dye.
They were added to a 5% hydrolyzed bis-sulfur silane
solution and films were deposited onto AA2024-T3.
Mainly, the effect of the dyes on the corrosion and
adhesion performance of the bis-sulfur silane films was
studied
[77]
.
Both the yellow and the red xanthene dyes were
soluble in the bis-sulfur silane solution and the films
deposited onto AA2024-T3 were visible to the naked
eye. The bare corrosion resistance results investigated

by the DC polarization technique showed that the
addition of the dyes did not affect the corrosion
resistance of the silane films on AA2024-T3. The dyed
and undyed silane treated panels were also immersed
in 3.5% NaCl solution for one week. The corrosion
performance of all samples was equal and the dyes of
the film did not leach out into the salt solution.
Paint adhesion of the dyed silane treated panels was
also tested. The panels were coated with a solvent-
based polyester paint, and the cross-cut adhesion test
with and without exposure to humidity was used for
testing. Good results were obtained for the red
xanthene dye but the yellow dye made the paint peel
off. The reason for the failure of the yellow dye was
examined. Both dyes are water and alcohol soluble and
do not leach out when exposed to salt solution. This
suggested that the solvent solubility of the dye after
incorporating it into the silane network could be of
importance. Therefore, the dyed silane coated
AA2024-T3 panels were exposed to ethanol. In a few
days, the yellow dye gradually started to leach out of
the film into the ethanol changing the solvent yellow,
while the red xanthene dye did not leach out of the film.
Apparently the xanthene dye becomes part of the
silane matrix after curing the film and does not affect
the structure of the silane film or its corrosion and
adhesion properties. Xanthene has two hydroxyl
groups at both ends. When the bis-sulfur silane
solution containing the xanthene dye is cured on the
metal, the dye reacts with the silanol groups that are
present in the hydrolyzed bis-sulfur silane solution
giving rise to an insoluble complex upon drying the
film.
Based on the results obtained certain requirements
were set for dyes which are to be added into silane
films
[77]
. They should: 1) be water and alcohol soluble;
2) not react with the silane solution or destabilize it;
3) become incorporated into the silane network, i.e.,
become insoluble after curing the film; 4) not leach out
when exposed to water or solvent.
4.5 Electrodeposition of silanes
4.5.1 The aim with the electrodeposition method
Electrodeposition is a process of depositing a coating
on a metal substrate by the application of electric
current. Hydrolyzed silanes are water-soluble ionized
molecules, and so they can be deposited on metals by
this method. Compared with the conventional
immersion process, the electrodeposition technique
seems to provide a more uniform, highly thickness
controlled, and more crosslinked silane coating
[85-88]
.
Various combinations of silane mixtures have been
tested in our silane lab at different voltages, pH
values, bath concentrations, and exposure times on
aluminum and iron. The surface structure of these
samples has been characterized by surface analytical
methods, ellipsometry and corrosion resistance by the
DC polarization technique and EIS (Refs. [39, 75]).
4.5.2 Preparation of the electrodeposited silane films
The non-functional bis-silane BTSE was electro-
deposited onto mirror polished ferroplate and Al-5052
sheet and unpolished Al-6111. The electrodeposition
set up comprised of an electrolytic cell with the silane
solution as the electrolyte and the metal substrate as
the cathode (negative) and graphite as the anode
(positive). A 5-V constant voltage was applied to the
cell for 60 min on the Al-6111 substrate, for 30 min on
the Al-5052 substrate, and different deposition times
were used on mirror polished ferroplate to see the
variation of film thickness with time. After
electrodeposition, the substrates were dried at 100
for 60 min. The Al-5052 substrate was immediately
rinsed in ethanol for 5 min in an ultrasonic cleaner and
then dried at 120 for 30 min. The immersed BTSE
films were treated and dried as described in the
experimental section
[39,75]
.
4.5.3 Results of the electrodeposited silane films
The DC polarization results showed a slight reduction
in the current densities for the electrodeposited sample
as compared with the immersed sample, indicating that
the electrodeposited film slows down corrosion more
effectively than the immersed film. The EIS results
also showed higher impedance values for electro-
deposited films than for the immersed films.
Figure 18 presents the phase angle curves for the
immersed and electrodeposited BTSE films on Al-
6111. A phase constant at high frequencies and a
second time constant at low frequencies can be
detected for the electrodeposited sample during the
initial hours of testing whereas the immersed film only
shows one time constant (Fig. 18). The second time
constant is due to the presence of an interfacial layer
between the silane film and the metal substrate as
verified also by ellipsometry. The EIS results indicated


658
that the immersion deposited BTSE film did not form
an interfacial layer onto Al-6111.

Fig. 18 Phase angle curves for the immersed and
electrodeposited BTSE film on Al-6111 after 8 h of
immersion in 3.5% NaCl solution. T
C
is the time
constant, and W is the Warburg impedance
[39]
.
Figure 19 shows the pore resistances of the silane
films as a function of time. The pore resistance of the
siloxane film on the electrodeposited sample was
equivalent to the immersed film but the pore resistance
of the interfacial layer in the electrodeposited film was
extremely high and it decreased with time as can be
seen from Fig. 19. This occurs as the electrolyte
penetrates into the film
[14,53,55,58,89-91]
.

Fig. 19 The pore resistance of immersed and
electrodeposited BTSE films on Al-6111 as a function
of electrolyte immersion time
[39]
.
The thickness of the BTSE film on ferroplate was
measured at three different points. The average
thickness was 227.5 nm with a non uniformity of 55%.
The mean standard error (MSE) for this measurement
was 9.8. When deposited by immersion the silane film
thickness is virtually independent of immersion time
but when the film is electrodeposited the film thickness
was found to increase with deposition time. Table 3
summarizes the results of thickness, uniformity, and
MSE measured by ellipsometry on the electrodeposited
panels.
Table 3 The results of thickness, uniformity, and MSE
measured by ellipsometry on the electrodeposited panels
Time
(min)
Thickness
(nm)
Uniformity
(%)
MSE

1 214.1 20 8.4
10 242.0 7 20.8
30 275.4 7 9.2
60 272.7 7 10.5
A graph of the results showed that the film thickness
increases almost linearly with electrodeposition time
until a deposition time of about 30 min is reached, after
which a plateau in film thickness is reached. For the
films which were deposited onto Al-5052 and
immediately rinsed in ethanol afterwards, the film
thickness obtained by immersion was 0 but for the
electrodeposited films thicknesses of 4.6 nm and 4.9
nm were measured with mean standard errors of 3.8
and 10.5, respectively. These results, like the EIS
results, indicate that a highly cross-linked interfacial
layer of about 5 nm in thickness is formed onto the
aluminum when the BTSE film is deposited by
electrodeposition. The interfacial layer is tightly bound
to the substrate and cannot be washed away with
ethanol, not even right after deposition. After
electrodeposition, two layers, the interfacial layer, and
the siloxane layer are present on the metal surface. The
total film thickness is about 255 nm including the 5 nm
thick interfacial layer.
SEM images of the BTSE films deposited by
immersion showed patches on the surface, indicating
that the film formed was rather nonuniform. The
patches were rich in silicon whereas hardly any silicon
could be detected on the rest of the surface by
SEM/EDX. The SEM images of the panel
electrodeposited for 10 min showed a more uniform
film. The film was, however, torn at certain spots. No
silicon was detectable on the torn portions whereas on
the rest of the surface Si peaks of significant intensity
were observed. As the electrodeposition time was
increased to 30 min and 60 min, the film got healed up
with no torn spots and became highly uniform
covering the entire surface. EDX analysis on the whole
surface showed silicon peaks of moderate intensity
indicating that 60 min of electrodeposition results in a
rather uniform film like the ellipsometry results had
already indicated.
It can thus be concluded that electrodeposition

results in an organized void-free and uniform film with
low porosity on the metal surface. The layer formed at
the interface between the silane and the oxide has a
very high ohmic resistance and low permeability for
the electrolyte.
5 Mechanism of Corrosion
Protection of Metals by Silanes
The mechanism by which thin films of organo-
functional silanes protect metals from various forms of
corrosion appears to be quite simple. There is no
evidence that silanes are electrochemically active in
solution or in the solid state. They cannot be reduced
or oxidized, unless they carry functional groups that
have electrochemical activity. Most functional groups
are not electrochemically active, so it can be assumed
that silane films are primarily barrier coatings. They
reduce the rate at which water and electrolyte can
reach the interface where they would induce corrosion
reactions. Thus, the most important property of silanes
films is their hydrophobicity. Figure 20 shows a
schematic of a film of a bis-silane without functional
groups deposited on aluminum. If sufficiently
crosslinked, such a film is fairly hydrophobic. The
water contact angle of a film of this type is of the order
of 90 and remains at that level during immersion in
water or salt solution for a few weeks. Eventually,
however, the contact angle will become lower. This
indicates that the Si O Si siloxane groups are not
indefinitely stable, but slowly hydrolyze back to
silanol groups, which are considerably more
hydrophilic. Consequently, silane films cannot protect
metals indefinitely. Even the most hydrophobic films
will, when immersed continuously, hydrolyze so that
water can eventually penetrate and reach the interface.
However, the siloxane hydrolysis is a reversible
process, so siloxane groups are reformed if the partly
hydrolyzed film can dry out again.
Si O Si + H
2
O
Si OH + HO Si
In agreement with this simple mechanism, it is
commonly found that silane molecules which are more
hydrophilic do not provide good corrosion resistance.
An example is -APS, which provides good adhesion
between coatings and metals, but is not very effective
in preventing the metal substrate from general
corrosion
[92]
. This phenomenon illustrates that good
adhesion of a coating to a metal does not automatically
imply good corrosion resistance.
In Ref. [92], the corrosion resistance of an
aluminum alloy coated with several different powder
coatings was determined using a variety of test
methods. The silanes used were -APS, BTSE, a

Fig. 20 Schematic of the structure of a bis-silane film on aluminum.


660
mixture of the two, and a two-step process consisting
of a BTSE rinse followed by a second rinse by -APS.
The two-step system had the best performance in all
tests, including adhesion tests. This can be explained
on the basis of our simple model as follows. The BTSE
treatment provides a hydrophobic interface to the metal
which slows down the water diffusion to the metal-
silane interface. The second film by -APS, formed on
top of the BTSE film, adheres well to the BTSE film
via interaction between silanol groups in both films,
and at the same time adheres well to many paint
systems via its primary amino groups. By itself a film
of -APS is too hydrophilic and, as a result, too
permeable to water for corrosion protection. Mixtures
of BTSE and -APS also worked reasonably well, but
were not as hydrophobic as the film formed from
BTSE by itself.
The question why bis-silanes seem to perform better
as a class than the standard mono-silanes has often
been asked. When we consider Fig. 20 and our
mechanism of hydrophobicity of silane films being the
most important criterion, the answer is as follows. If
we would compare the silanes BTSE and methyl
trimethoxysilane (MTS), then a 5 wt.% solution of
each silane will have the same concentration of silicon
atoms, carbon atoms and silanol groups in the solution.
Yet, a film of BTSE will work considerably better than
a film formed by MTS, assuming equal hydrolysis,
deposition, and curing conditions
[20]
. Inspection of Fig.
20 tells us that only a film of BTSE can be dense and
three-dimensionally crosslinked, but a film of MTS
cannot, as there are free methyl groups in the film
which, due to their mobility, necessarily result in a
higher permeability of the film to water and other
diffusing species. The film of BTSE is more rigid and
has lower diffusion rates for water and ions
[20]
.
However, even for bis-silane films, the condition that
the molecules should not contain hydrophilic
functional groups remains. As an example, films of
bis-[trimethoxy silylpropyl]amine (bis-amino), do not
work well by themselves. The secondary amino groups
will attract water, become protonated, and will then
also attract chloride ions into the film when exposed to
a salt solution
[20]
.
Films of bis-[triethoxysilylpropyl]tetrasulfide (bis-
sulfur) form films that provide much better corrosion
protection to metals, such as aluminum, zinc, and steel.
Such films are considerably more hydrophobic due to
the sulfur chain in the molecule
[20]
. However, a
solution of this silane does not wet metals very well.
Therefore, films made from bis-sulfur silane solutions
are often porous. If mixtures of the bis-amino and the
bis-sulfur silane are used, one can tune the wettability
and the hydrophilicity accurately and the result is a
film that wets perfectly but is still sufficiently
hydrophobic to provide excellent corrosion protection.
Thus, such a mixture can display a performance far
superior to those of the two individual silanes
[20]
. In
addition to this wettability effect, the secondary amino
groups have a catalytic effect on the silanol
condensation, so films made from mixtures of the bis-
amino and the bis-sulfur silane are more completely
hydrolyzed and crosslinked than those made from the
bis-sulfur silane alone.
Another question that has often been asked is
whether the bonds formed between metals and silanes
are hydrolytically stable. The answer to that question is
that the type of bond that actually exists at the interface
is still not well known. In the case of silane films on
aluminum, it appears to be a more complex silicate
than simply an Al O Si bond
[20]
. However,
whatever the nature of the bond, this bond is not
resistant to water. That is the reason why the silane
film has to be hydrophobic. If water manages to reach
the interface, it will hydrolyze the bonds with
formation of Me OH and Si OH groups which are
very hydrophilic and more water will be attracted to
the interface as a result. Corrosion can then start. It is
reasonable to assume that if even Si O Si
groups can hydrolyze at the silane surface (see above),
bonds of the type SiO Me (shown in this
form for simplicity only) will hydrolyze even faster, as
such bonds have a higher ionic character resulting in
easier attack by polar water molecules than in the case
of siloxane bonds.
As in the case of Si O Si , the metal-silane
bond hydrolysis by water is reversible, as the
experiment shown in Fig. 21 convincingly
demonstrates. Shown are two panels of cold-rolled

steel coated with the same epoxy paint. Under the paint
two different silanes were used. The one on the left
was more hydrophilic (porous) than the one on the
right. It is seen that the dry adhesion (top of each panel)
passed the ASTM D-3339 test for each silane. The wet
adhesion (24 h in deionized water) was poor for the
hydrophilic silane and excellent for the other silane.
However, after allowing a sufficient amount of time
for drying (1 week at room temperature), the system on
the left had regained the original adhesion, illustrating
that the interfacial bond hydrolysis in this system was
reversible. It should be noted that the delaminated area
in this system due to hydrolysis of the interfacial bonds
revealed a steel surface that was clean and entirely
devoid of rust. This delamination was not related to
corrosion, but to bond hydrolysis only.
In summary, silane film performance on metals in
terms of corrosion protection and adhesion to paints,
depends on the hydrophilicity of the film, its crosslink
density, wettability of the metal by the silane solution,
and film thickness, which will all have an effect on the
rate at which water can reach the silane-metal interface.

Fig. 21 Dry and wet adhesion of an epoxy paint to cold-rolled steel treated with a hydrophilic silane (left) and
a more hydrophobic silane mixture (right).
6 Conclusions
It has been demonstrated in this paper that thin films of
organofunctional silanes can successfully replace
chromate or other metal pretreatments. The silane
technology is very versatile and works with many
metals and paint systems. Good adhesion can be
obtained to almost any paint by a judicious choice of
the silane system. Often mixtures work better than
individual silanes as such mixtures can be fine-tuned
for optimum wettability and hydrophobicity properties.
Dipodal silanes, also called bis-silanes, typically are
more effective in preventing corrosion of metals than
the more widely known mono-silanes. This difference
is directly related to the mechanism by which silanes
protect metals. Although the actual bonds between
silane film and the metal oxide remain elusive, there is
little doubt that with some metals, notably aluminum,
covalent bonds are formed. In other cases, e.g., iron,
the bond may not be more than a hydrogen bonding.
Nevertheless, whatever the nature of the bond, it has
been shown that such bonds are not resistant to water.
They will hydrolyze back to metal hydroxide and
silanol groups. Such groups are very hydrophilic, so
that more water will be attracted and corrosion will
start. Thus, for good corrosion performance, the silane
film needs to be as hydrophobic as possible, so that
water ingress is minimized. This poses a dilemma as
hydrophobic silane films that perform well in corrosion
tests, are typically soluble in organic solvents only.
Silanes that are water-soluble form films that are more
hydrophilic. Thus, the environmental low-VOC
requirement is incompatible with the hydrophobicity


662
requirement for good corrosion protection by silanes.
Thus, it has been explored whether hydrophobic
silane films can somehow be obtained from
hydrophilic silanes. It has been shown here that films
can be made more hydrophobic and thus more
effective by increasing the cure time and temperature
or by adding nanoparticles to the films. Alternatively,
additional silane crosslinkers such as TEOS can be
added in small amounts to increase the film
hydrophobicity by increasing the crosslink density of
the films. Other additives to silane have been explored.
It has been shown that small amount of water-soluble
inhibitors can increase the effectiveness of silane films
by a leaching effect. Such slow leaching is possible as
the silane films have a much lower permeability to
water than paint films, where such water-soluble
inhibitors cannot be used. The use of inhibitors in
silane films extends a defect-healing capability to the
films, similar to that of chromate films.
The strength of the silane technology, as compared
with other metal pretreatments, lies in its universal
applicability. It can be used in almost any metal-paint
combination. Further, the process is easy to apply and
requires only a few steps. Silane solutions are not
aggressive, as their pH is close to neutral. It has also
been demonstrated that silane films can protect against
various different forms of corrosion, including many
forms of localized corrosion.
The silane technology also has some limitations and
weaknesses. First of all, their effectiveness as stand-
alone treatment, i.e., without paint overcoat, is limited,
although remarkably good in certain instances. Silane
films are not inhibitors. Their performance depends on
their barrier action. For thin films of the typical silane
thickness of 0.5 m, such barrier action is limited.
Further, the degree of cleanliness of the metal substrate
plays a greater role in the silane technology than for
the chromating process. A chromate solution is acidic
and etching and is, therefore, not very sensitive to low
amounts of residual oils or other contaminants on the
metal surface. Silane solutions are not etching and
require a greater degree of surface cleaning. Another
limitation is that silane solutions often are not stable
and tend to condense, leading to poor films. Thus, the
silane solutions can only be used for a short time
before they have to be discarded. Attempts have been
made to develop silane mixtures which are stable over
a longer time period. An example, described in this
paper, is the mixture of the bis-amino silane and
vinyltriacetoxy silane. Individually, these silanes are of
limited stability, but their mixture is stable for over a
year. A third limitation is that the silane technology is
more sensitive to bath contaminations than the
chromate technology.
As an overall conclusion, the use of silanes offers a
viable and environmentally compliant alternative to the
chromate technology. More work will be needed,
however, before the full breadth of this technology will
be realized. Many more silane molecules can be
envisaged to be effective. Their number is almost
unlimited. More additives can be developed for
improving the effectiveness of silanes further, such as
organic resins. With such additives, they may
eventually also become effective stand-alone
anticorrosion processes.
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