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The role of crosslinkers in epoxy–amine crosslinked silicon sol–gel barrier

protection coatings

Article  in  Thin Solid Films · November 2008

DOI: 10.1016/j.tsf.2008.06.073

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 Thin Solid Films 517 (2008) 538–543

Contents lists available at ScienceDirect

Thin Solid Films

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t s f

The role of crosslinkers in epoxy–amine crosslinked silicon sol–gel barrier

protection coatings
A.J. Vreugdenhil a,⁎, V.J. Gelling b, M.E. Woods a, J.R. Schmelz b, B.P. Enderson b
a
Trent Centre for Materials Research, Department of Chemistry, Trent University, 1600 West Bank Drive, Peterborough Ontario, Canada
b
Department of Coatings and Polymeric Materials, North Dakota State University, 1735 NDSU Research Park Drive, Fargo, ND, USA

A R T I C L E I N F O A B S T R A C T

Article history: The search for chromate replacements in corrosion prevention materials has identified the use of hybrid sol–
Received 10 May 2007 gel coatings as one, very promising approach. Appropriately functionalized hybrid sol–gel materials can be
Received in revised form 11 June 2008 crosslinked to enhance their chemical durability and mechanical strength. In this work, we evaluate three
Accepted 20 June 2008
crosslinkers used in a tetramethoxysilane–glycidoxypropyltrimethoxysilane binary sol–gel system in order to
Available online 27 June 2008
identify the role of the crosslinkers in corrosion protection. The crosslinkers examined were ethylenedia-
Keywords:
mine, N-aminethylepiperazine, and diethylenetriamine. The sol–gel coatings were examined by contact
Epoxy–amine crosslinking angle, atomic force microscopy, and electrochemical impedance spectroscopy (EIS). Circuit modeling of the
Corrosion EIS results yielded valuable insights into the significant differences between the durabilities of the variously
Aluminum 2024-T3 crosslinked coatings. Crosslinker hydrophobicity was identified as not playing a significant role whereas the
Sol–gel number of reactive sites per crosslinker and the resulting morphology of the material may be an important
Electrochemical impedance parameter.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction chemical or chemical means. The type of crosslinking depends on the

Increasingly, regulations with respect to the use of corrosion inhibitors
for the protection of metals such as the aluminum alloy 2024-T3 have led
scientists to explore and develop novel, corrosion-inhibition coatings and
to identify new organic corrosion inhibitors. Traditionally, corrosion-
inhibition methods employed hexavalent chromium conversion coatings
principally based on strontium chromate pigments in organic primers and
using chromate based anodization surface treatments. However, in the
late 1990s these chromate species were identified as carcinogens and the
use of such coatings has steeply declined [1].
One promising approach for a chromate free corrosion protection
system is based on siloxane hybrid organic–inorganic materials
formulated using sol–gel techniques. The resulting thin barrier coatings
are very successful in protecting aluminum alloys and other metal
substrates against corrosion [2,3]. The approach to the formulation of
these coatings varies widely. Some groups have focused on the
formulation of sol–gel coatings that are highly hydrophobic to prevent
or slow the ingress of water and the resulting facilitation of corrosion on
the surface of the substrate [4,5]. The utility of high density crosslinked
sol–gel materials as barrier protection coatings has also been demon-
strated [6–8]. Typically, these materials are prepared through the
combination of alkylalkoxysilanes and alkoxysilanes with crosslinking
occurring between the organic functional groups via thermal, photo-
⁎ Corresponding author.
E-mail address: avreugdenhil@trentu.ca (A.J. Vreugdenhil).
precursors used. Precursors in use include tetramethoxysilane (TMOS),
and tetraethoxysilane in combination with alkylalkoxysilanes such as
vinyltrimethoxysilane, 3-methacryloxyproplytrimethoxysilane or 3-gly-
cidoxypropyl-trimethoxysilane (GPTMS) [9]. The organic crosslinking is
used to enhance the chemical durability and mechanical strength of the
inorganic Si–O–Si network but may also provide additional capabilities
including surface energy modification and chemical interactions.
Epoxide containing coatings have been shown to act as good barriers
against corrosion using a number of formulations including thermally
crosslinked epoxides, silica colloid pigmentation [10] and polyamine
crosslinked epoxides. In each case, the approach has been to create a dense
coating that forms a barrier between the metal surface and the
environment [11]. Coatings prepared with GPTMS and TMOS have been
further shown to act as excellent protective barriers for aluminum in
corrosive environments, particularly when the epoxide consumption is
high and the silica backbone is formed under conditions which favor
dense, three-dimensional condensation rather than pore formation. In
particular, it has been shown that the epoxy–amine crosslinking is an
efficient bench top method for preparing these highly crosslinked
coatings, and that high R values (large excesses of water to silicon to aid
in extensive hydrolysis and internal condensation reactions) with longer
aging periods result in the preparation of a more fully dense silica
backbone in the solid [7,8].
To continue the development of these amine–epoxy crosslinked sol–
gel-derived materials, it is important to understand the impact that
different crosslinking agents have on the properties and corrosion

0040-6090/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2008.06.073
 A.J. Vreugdenhil et al. / Thin Solid Films 517 (2008) 538–543 539

prevention performance of these materials. In this work, we compare three

amine crosslinkers for a TMOS-GPTMS hybrid coating prepared with a high
R-value. The three crosslinkers used are diethylenetriamine (DETA),
ethylenediamine (EDA) and N-aminoethylpiperazine (AEP). DETA has
been shown to act as an efficient crosslinker for this type of material [12].
EDA, a truncated version of DETA that contains only two amine centers, and
AEP, an amine containing organic corrosion inhibitor are included to
explore the effect of crosslinker structure on the corrosion prevention
performance of the resulting crosslinked sol–gel coatings. As shown in
Fig. 1, DETA possesses two primary and one secondary amine allowing it
to function as a 3-D network forming crosslinking agent. EDA is a less
elaborate, linear crosslinking species providing two primary amines and
AEP provides only one primary amine and one secondary amine but is
the most potentially hydrophobic crosslinking agent of the three species.
In previous work, we have characterized sol–gel coatings crosslinked
with these amines with respect to their crosslinking efficiencies and the
effect that these crosslinkers have on the triggered release of additives
from these materials [13,14]. However, the effect of the crosslinking agents'
structures and the resulting impact on the density and corrosion
prevention of the coatings has not previously been described. Their
corrosion prevention performance has been evaluated by continuous
immersion in dilute Harrison's solution, electrochemical impedance
spectroscopy (EIS) and atomic force microscopy surface roughness
measurements.
In this paper, we demonstrate that the choice of crosslinking agent
can play an important role in the corrosion prevention performance of
the material. We have identified this effect as primarily arising from
changes to the epoxy–amine crosslinking morphology due to the
number and type of amines available for reaction rather than being due
to changes in the surface energy of the material itself. The differences Fig. 2. From left to right AEP, EDA and DETA crosslinked sol–gel coatings on Al 2024-T3
between the three coatings and their modes of failure in a corrosive (a) with and (b) without 12 months of immersion in dilute Harrison's solution.

environment have been explored using circuit modeling of the EIS data.
1.1. Experimental details
The 1:3 TMOS:GPTMS (Sigma-Aldrich) sol was prepared by the
dropwise addition of a mixture of 2.96 ml (0.02 mol s) of TMOS and
14.20 ml (0.06 mol s) of GPTMS to 21.60 ml of acidified deionized H2O
(0.05 M acetic acid). Once the addition of the silanes was complete, the
solution was sealed and allowed to age for 72 h with continuous stirring.
Following aging, the solution was removed from the stir plate and 20 ml
of a surfactant solution was added. The surfactant solution was a 0.1% w/
w solution in deionized H2O of the fluorochemical surfactant Flourad
FC403 manufactured by 3M. The crosslinking agent (DETA, EDA, or AEP)
was added with equal volume of water to the sol in a 1:1 molar ratio of
GPTMS to amino hydrogen i.e. 5 for DETA, 4 for EDA and 3 for AEP. This
corresponds to an addition of 1.38 mL of DETA, 1.08 mL of EDA and
2.81 mL of AEP for the silane formulations described above.
Following addition of the crosslinker, the solution was applied by
dipcoating substrates prepared as described in the following section.
Each slide was dipped three times into the resulting solution before
being allowed to air dry at room temperature for 24 h. Previous
research has shown that this process yields dry film thicknesses of
between 0.5 and 0.7 μm [12].
1.2. Substrate preparation
The coatings were applied to substrates of aluminum alloy 2024-T3
(McMaster-Carr) which had been cleaned as follows: 3 min sonication
in methanol, followed by 3 min of immersion in concentrated solution
of equal volumes of acetic acid and nitric acid. The substrates were
rinsed between steps with distilled water to avoid contamination of
the different baths. A GPTMS surface treatment was applied to the
substrates via 20 min of immersion in a 30 minute old dilute solution
of GPTMS (4.42 ml) in acidified H2O (0.05 M acetic acid, 36.0 ml).
1.3. Exposure to dilute Harrison's solution
Coated substrates were immersed in 50 ml of dilute Harrison's
solution (3.5 g (NH4)2SO4 and 0.5 g NaCl in 1 l of ultrapure water with
an initial resistivity of 18.2 MΩ) for a total of 11 months. Initially, four
samples of each coating were immersed in the solution two of which
were scribed to bare metal using a diamond tipped pen. All samples
were kept in a sealed plastic cabinet during immersion. During the
first 3 months of exposure, samples were removed from solution
every two weeks and the substrates were inspected and returned to
the solution. Solution volume was maintained continuously and the
solution was changed three times over the duration of the experiment.
Ambient dissolved oxygen levels were not monitored during the
experiment however the typical dissolved oxygen content in NaCl
solutions of this type are 6.5 ppm [15].

1.4. Atomic force microscopy (AFM)

AFM was used to characterize the surface roughness of the

polyamine crosslinked coatings before and after immersion in dilute
Harrison's solution. AFM images were acquired on a Digital Instru-
ments Nanoscope III operating in tapping mode using a silicon nitride
Fig. 1. Amine crosslinking agents (a) DETA, (b) EDA, (c) AEP. probe with a spring constant of 0.58 Nm.
540 A.J. Vreugdenhil et al. / Thin Solid Films 517 (2008) 538–543

Table 1 The results are presented as both Bode and Nyquist plots. The Bode plot
Root mean square roughness of the surface (Rq) of the polyamine crosslinked sol–gel is a graph of the Zmodulus (ohms) plotted versus the applied frequency
coatings before and after exposure to a corrosive environment
(Hz). This provides an easy view of the low frequency portion of the
EDA DETA AEP impedance, which is an indicator of coating condition as a function of
Prior to exposure 6.3 nm 78.6 nm 18.6 nm continuous immersion. The Nyquist plot is constructed by plotting the
After exposure 235.7 nm 421.6 nm 665.2 nm imaginary component of Z (Zimag) versus the real component (Zreal).
From the Nyquist plot, the degree of capacitive or diffusion controlled
behaviour of the impedance can be identified allowing the coating
1.5. Contact angle analysis performance to be modeled using various circuit fitting components. A
common circuit used in this type of analysis is a Randles cell, which
A 2 µL drop of Millipore water was placed on to the surface of each contains a resistor followed by a capacitor and resistor in parallel. Data sets
sample using an Eppindorff pipette. Digital images were acquired and from the EIS results were circuit fitted using Scribner's Zview Version 2.1.
the equilibrium contact angle was measured directly from the image.
Ten points were measured over a 10 cm2 area for each sample. 2. Results and discussion

1.6. Electrochemical impedance spectroscopy 2.1. Exposure to dilute Harrison's solution

EIS was performed during constant immersion in dilute Harrison's
solution with a three-electrode cell. The reference electrode consisted
of a saturated calomel electrode and the counter electrode consisted of
a platinum mesh electrode. The tests were carried out using a Gamry
Instruments potentiostat (either PC4 or FAS2) over the frequency
range of 100,000 Hz to 0.01 Hz. The alternating current perturbation
applied was 10 mV versus open circuit potential. The sample area was
7 cm2.
Coatings were visually evaluated following immersion in a
corrosive environment, dilute Harrison's solution. Typical samples
are shown in Fig. 2 both with and without dilute Harrison's solution
exposure. Prior to immersion, all of the sol–gel coatings were clear and
macroscopically smooth. Following twelve months of immersion in
dilute Harrison's solution, visual inspection of the samples indicate
that of the three coatings, the EDA crosslinked material provided the
greatest corrosion protection while the AEP crosslinked had the
poorest. The DETA crosslinked material has previously been shown to

Fig. 3. (a) Bode and (b) Nyquist graphs for sample AEP during immersion in dilute Fig. 4. (a) Bode and (b) Nyquist graphs for sample EDA during immersion in dilute
Harrison's solution. The Nyquist plot inset shows an expansion of the low Z value region Harrison's solution. The Nyquist plot inset shows an expansion of the low Z value region
exhibiting multiple time constants. exhibiting a single time constant.
 A.J. Vreugdenhil et al. / Thin Solid Films 517 (2008) 538–543 541

act as a good corrosion prevention coating also performed well in
continuous immersion [12]; however, the shorter chain EDA cross-
linked coating surpassed it according to visual inspection. This may be
due to the decreased total carbon content in the EDA crosslinked
material. The similarity between the performance of DETA and EDA
crosslinked materials may be understood when considering the
number of primary and secondary amine hydrogens present in each
case. Both crosslinkers have two primary amine hydrogens which are
less sterically hindered and more reactive than the available
secondary amine hydrogens present. Following the initial reaction
with an epoxide at each primary hydrogen site, the remaining amine
hydrogens are all secondary, 2 in the case of EDA and 3 in the case of
DETA. The reduced reactivity of these secondary amine hydrogen sites
limits the impact of the increased number of sites present in the case
of DETA. Both crosslinked materials have been shown to have similar
epoxide consumption numbers and degree of amine substitution as
determined by infrared and Raman spectroscopy [13].
For all of the coatings that were scribed before exposure to dilute
Harrison's solution, corrosion was observed at the scribe, particularly
for the AEP crosslinked sol–gel coating, which had significant pitting.
None of these barrier coating systems is expected to provide corrosion
protection in the event of coating removal. However, both the EDA and
DETA demonstrated excellent resistance to delamination or under-
cutting in the areas immediately adjacent to the scribe. The AEP
crosslinked coating did not perform as well in this respect, which is
consistent with the overall performance of the AEP crosslinked
materials. This is mostly likely due to the presence of only one
primary amine and therefore a limited number of multiple cross-
linking sites relative to the network forming DETA and linear EDA.
functional group immediately adjacent to the amine, it is not
unreasonable to suggest that this and other aspects of the crosslinked
sol–gel material overwhelm the hydrophobic effect of short aliphatic
carbon chains present in all three crosslinking agents.
The contact angles for other hydrophobic sol–gel coatings that have
been proposed for use as corrosion prevention barrier coatings have
been shown to range from 88° for pure tetramethoxysilane [4] coatings
to 172° for a vinyltriethoxysilane sol–gel coating [16,17]. It is evident that
the epoxy–amine crosslinked coatings investigated here are not as
hydrophobic as other sol–gel based corrosion prevention barrier
coatings. This suggests that the protection provided by these epoxy–
amine crosslinked materials is more likely due to their chemical
durability, extensive crosslinking and excellent adhesion to the substrate
rather than via surface energy modification.
2.4. Electrochemical impedance spectroscopy
In the EIS results presented below it is possible to observe many
details that provide insight into the overall condition of the sol–gel
coating and the way in which that condition evolves over time. Bode
and Nyquist plots are provided for each result in order to permit the
ready identification of coating performance (Bode plot) as well as
description of the coating impedance behaviour (Nyquist plot).
The results presented in the Bode plots of Figs. 3, 4 and 5 show that
the three sol–gel coatings initially displayed very similar EIS perfor-
mance as demonstrated by the Zmodulus values at 0.01 Hz of
approximately 5 × 106 Ω. However, over time, each coating exhibited

2.2. AFM surface analysis

AFM was used to quantify the surface degradation of the cross-

linked sol–gel materials before and after immersion in the dilute
Harrison's solution. Prior to the exposure, each of the coatings were
relatively smooth with microscopic pores visible on the surfaces.
Qualitatively, each of the coatings has a leveling effect on the surface
roughness as the pristine coatings in each case are smoother than the
original cleaned, aluminum alloy surface. The most valuable AFM
evaluation is in the comparison of the changes in the surface roughness
upon exposure. These results are shown in Table 1. For all materials,
significant surface roughening occurred as a result of the 12 month
exposure to dilute Harrison's. The post-exposure AFM images were
quite grainy and demonstrated a wide range of superficial features
relative to the uniform, smooth images prior to exposure. However, the
variation in the degree of roughening was consistent with the results
observed by visual inspection and was clearly related to the cross-
linking agent used. Both EDA and DETA crosslinked materials
demonstrated less roughening than the AEP material. Before and
after exposure, the EDA crosslinked coating was significantly less
rough than either the AEP or DETA crosslinked coatings.

2.3. Contact angle analysis

The results of the contact angle measurements are useful for

comparing the hydrophobicity of the surfaces of the polyamine
crosslinked materials. The aqueous contact angles for the crosslinked
materials are 82.4° (±0.7), 83.2° (±0.7) and 81.4° (±0.6) for EDA, DETA
and AEP respectively. All of the polyamine crosslinked sol–gel
materials had significantly high contact angles indicating that the
surface of the materials should be relatively hydrophobic and are not
significantly different from each other. This result suggests that while
the hydrophobic nature of the individual crosslinking agents may
vary, the hydrophobicity of the resulting coating is not significantly
altered by the use of different crosslinking agents. Bearing in mind, Fig. 5. (a) Bode and (b) Nyquist graphs for sample DETA during immersion in dilute
that in each case the product of the crosslinking reaction is a hydroxyl Harrison's solution.
542 A.J. Vreugdenhil et al. / Thin Solid Films 517 (2008) 538–543

appearance of multiple semi-circular features in the inset of Fig. 3. This is

Fig. 6. Model circuits used for fitting of the data sets. (a) was used for the initial EDA4
measurement, (b) was used for each of the samples at various times during immersion,
(c) was used for the final measurement of AEP, and (d) was used for the day 1
measurement of the surface sample.
different trends to failure, as determined by the low frequency decrease
in impedance with respect to immersion time. The coating with the
most significant decrease in barrier properties was crosslinked with AEP
as indicated by a drop in Zmodulus at 0.01 Hz to 1 × 105 Ω between
testing either within or just after 1 day of immersion. Both the EDA and
DETA crosslinked coatings demonstrated better performance, main-
taining a low frequency Zmodulus and dropping off in Zmodulus
between day 1 and day 5 of immersion. The coating that exhibited the
slowest decrease in barrier properties was crosslinked with DETA. These
EIS performances are consistent with the visual and surface roughness
results of the long-term immersion experiments. In each case, the
crosslinkers EDA and DETA, which contain more primary amines and
particularly the network forming DETA, with up to 5 crosslinking sites
available, demonstrate the best corrosion inhibition.
It is interesting to note that the behavior of the samples towards the
end of the immersion time varied greatly. This is most clearly observed in
the Nyquist plots shown in Figs. 3–5. The AEP crosslinked coating (Fig. 3)
displayed multiple time constants as demonstrated most clearly by the
consistent with diffusional processes occurring in the sample as early as
day 12 of immersion. The EIS results of the EDA crosslinked coating (Fig. 4)
also displays diffusional processes but not until day 18 of immersion. The
EIS results of the DETA crosslinked system (Fig. 5) displays no diffusional
processes over the course of the immersion testing. The circuit modeling
behavior for the DETA system instead displayed behavior consistent with a
modified Randles Cell such as the circuit shown in Fig. 6b. This Randles Cell
behavior is typical of a coated metal substrate prior to the ingress of
electrolytes or the onset of substrate corrosion.
Data sets from the EIS were circuit fitted and typical results are
shown in Table 2 with circuit diagrams shown in Fig. 6. Fig. 6a is
indicative of a purely capacitive coating and a solution resistance (R1).
However, in this case the capacitor has been replaced with a constant
phase element (CPE) to account for the non-ideal capacitance often
observed in a coated system. Fig. 6b is a Randles Cell, which includes a
solution resistance, a coating capacitance, and a coating pore
resistance (R2). Fig. 6c is a modified Randles Cell where diffusional
processes have been accounted for by the addition of a Warburg
element (W1) to the circuit [18]. Finally, Fig. 6d is a circuit model
containing induction loops (L1) in parallel with an additional resistor
(R3) as suggested by Hülser and Beck [19] to account for the low
frequency behavior observed in the AEP crosslinked system as
described above.
One of the most valuable aspects of developing effective circuit
models for the various coating is the ability to determine the pore
resistance (Fig. 7). Pore resistance occurs as the electrolyte penetrates
the sol–gel coating and creates a path to the substrate. For EDA and
DETA, the pore resistance is maintained over 1 × 107 Ω throughout the
first day of immersion. In particular for DETA, the pore resistance is
effectively constant over that time. For EDA, the pore resistance shows
a gradual but steady decline. In the case of AEP the decrease is more
rapid with a sudden drop after 8 h. This would indicate that the
linearly and network crosslinked sol–gels are better able to delay the
entry of electrolyte into the coating.
Even after the corrosion commences as indicated by the drop in
pore resistance and the ingress of electrolytes, there appears to be
inherent differences in the low frequency impedance observed for
each of the coatings. This could possibly be due to greater film
formation, and therefore greater adhesion, among the samples as the
DETA samples maintained a low frequency impedance roughly one
order of magnitude greater than the next best samples which used an
EDA crosslinking agent. Future studies into the affects of the adhesion
of the resulting sol–gel films will be conducted.

Table 2
Selected circuit fitting results for circuit elements as shown in Fig. 6

R1 CPE1 R2 R3 L1
Surface
Hour 0 54.83 4.92E− 06 9.71E+ 05
Day 1 45.49 1.94E−05 2.80E+ 04 4.30E+04 1.01E+ 04
Day 42 43.12 3.46E− 05 2.76E+ 04
AEP
Hour 0 1387 3.19E−06 5.08E+ 07
Day 1 67.81 5.25E− 06 1.19E+ 05
Day 42 54.58 1.68E−05 7.30E+ 03
EDA
Hour 0 887.2 2.92E− 06
Day 1 293.2 3.93E− 06 5.74E+ 06
Day 42 45.05 8.03E− 06 8.47E+ 03
DETA
Hour 0 1224 2.96E− 06 7.70E+07
Fig. 7. Pore resistance (R2) changes during immersion time as determined by circuit
Day 1 588.1 3.35E−06 7.53E+ 06
fitting over 42 days of immersion. Inset shows the same changes over the first 12 h
Day 42 116.3 5.14E−06 3.44E+ 05
expanded for clarity.
 A.J. Vreugdenhil et al. / Thin Solid Films 517 (2008) 538–543
3. Conclusions
The physical and electrochemical characteristics of three cross-
linked sol–gel materials have been evaluated with respect to their
ability to protect an aluminum alloy substrate from corrosion. The
materials' durability in dilute Harrison's solution, surface roughness
and EIS behaviour were found to be dependent on the amine
crosslinking agent used. Better overall performance was demon-
strated by the network forming triamine DETA followed by the linear
diamine EDA. The potentially more hydrophobic crosslinker AEP was
not effective in increasing the aqueous contact angle nor in delaying
electrolyte ingress. These results demonstrate that, for these formula-
tions, the creation of a densely crosslinked coating is primarily
responsible for improved substrate corrosion protection and can be
related principally to the number of primary and secondary amine
reaction sites present on the amine crosslinking agent. These results
are supported by circuit modeling of the samples’ EIS performance as a
function of immersion time. DETA crosslinked coatings demonstrated
consistent Randles’ cell performance while AEP crosslinked materials
exhibited multiple time constants and a rapid decrease in pore
resistance while immersed in dilute Harrison's solution.
Acknowledgements
M. Woods acknowledges the support of an Ontario Graduate
Scholarship and Trent University for funding. This research was
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543
conducted with generous support from the U.S. Army Research
Laboratory, Contract No. W911NF-04-2-0029 and the Canadian
National Science and Engineering Research Committee.
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