J Mater Sci (2013) 48:1067–1084
DOI 10.1007/s10853-012-6839-7
Analysis of degradation process during the incorporation
of ZrO2:SiO2 ceramic nanostructures into polyurethane coatings
for the corrosion protection of carbon steel
D. Del Angel-López • M. A. Domı́nguez-Crespo •
A. M. Torres-Huerta • A. Flores-Vela •
J. Andraca-Adame • H. Dorantes-Rosales
Received: 18 June 2012 / Accepted: 24 August 2012 / Published online: 12 September 2012
Ó Springer Science+Business Media, LLC 2012
Abstract Three different molar ratios of ZrO2:SiO2
mixed oxides (25:75, 50:50, 75:25) were produced by the
sol–gel technique and sintered at different temperatures
(400, 600, 800, and 1000 °C) in order to analyze differ-
ences in mechanical and electrochemical properties of a
wide variety of organic–inorganic hybrid coatings on AISI
1018 commercial carbon steel. For this purpose, 2, 4, and 6
wt% of the obtained ZrO2:SiO2 nanoparticles were incor-
porated to the polymeric matrix under vigorous stirring and
spread on metallic substrates to reach between 40 and
55 lm of dry film. Light microscopy, scanning electron
microscopy, confocal laser scanning microscopy studies,
atomic force microscopy, and nanoindentation tests were
used to evaluate morphological, topographical, and
mechanical properties; whereas atmospheric corrosion and
electrochemical impedance spectroscopy (EIS) were
D. Del Angel-López  M. A. Domı́nguez-Crespo (&) 
A. M. Torres-Huerta
CICATA-Altamira, Instituto Politécnico Nacional, IPN,
Km 14.5 Carretera Tampico-Puerto Industrial Altamira,
C.P. 89600 Altamira, Tamaulipas, Mexico
e-mail: adcrespo2000@yahoo.com.mx
M. A. Domı́nguez-Crespo
CICATA-Querétaro, Instituto Politécnico Nacional,
Cerro Blanco No. 141, Col. Colinas del Cimatario,
C.P. 76090 Santiago de Querétaro, QRO, Mexico
A. Flores-Vela  J. Andraca-Adame
Unidad Profesional Adolfo López Mateos, Centro de
Nanociencias Micro y Nanotecnologı́as, Instituto Politécnico
Nacional, Luis Enrique Erro s/n, 07738 Mexico, DF, Mexico
H. Dorantes-Rosales
Departamento de Metalurgia, Escuela Superior de Ingenierı́a
Quı́mica e Industrias Extractivas, Instituto Politécnico Nacional
(IPN), C. P. 07300 Mexico, DF, Mexico
performed using a 3 wt% NaCl medium in continuous
immersion for 226 days. The crystallite size of the
as-prepared ZrO2:SiO2 nanoparticles changed according to
the sintering temperature from 4 to 9 nm. It was found that
an adequate dispersion and homogeneity was achieved
when 2 wt% of sintered ZrO2:SiO2 nanoparticles were
mechanically mixed with polymer (MDI) to produce
hybrid coatings on the metallic substrate. Free-bubble
surface and hardness enhancement can be achieved by
adding nanostructures assuming fact that the particles are
capable of occupying the gas bubble sites. Atmospheric
corrosion in the coatings without reinforced particles was
more severe than that observed in hybrid coatings, and for
these, corrosion was higher according to the increasing
zirconia molar ratio. The EIS studies indicated that the
synergetic effect between the organic–inorganic phases to
seal the surface enhances the barrier properties on this
metallic substrate.
Introduction
To protect steel from corrosion and increase metal-coating
adhesion, a primer followed by an organic coating are
frequently applied. Organic coatings such as polyurethanes
(PUs) are some of the most widely used materials against
corrosion in aggressive environments [1]. In industrial
applications, it is common to use polyfunctional isocya-
nates to prepare PU coatings, for instance, aromatic,
aliphatic, cycloaliphatic, or polycyclic. Specifically, the
aromatic isocyanates have higher reactivity than the ali-
phatic or cycloaliphatic di-isocyanates, therefore one can
modulate the PU properties in different manners depending
on the monomer used during the synthesis [2, 3]. From
these monomers, 4,40 -methylene bis (phenyl isocyanate) or
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1068 J Mater Sci (2013) 48:1067–1084

MDI is one of the most widely applied during PU pro- 800, and 1000 °C). Thereafter, 2, 4, and 6 wt% of the
duction to protect steel in corrosive environments; its nat- obtained ZrO2:SiO2 nanostructured powders were incorpo-
ure allows it to be chemically tailored according to the rated to the polymeric matrix and spread on metallic sub-
requirements of specific applications and processes (Fig. 1) strates. Additionally, morphology, dispersion, and quantity of
[4–6]. This coating acts as a barrier between the aggressive nanostructures were also discussed and correlated with barrier
media and the metallic substrate, but in practice, all poly- properties.
meric coatings are permeable to destructive species such as
water, chloride, and oxygen, reducing the coating adhesion
and favoring corrosion of the metal underneath the film [7–9].
Experimental method
In addition, when the coating barrier is mechanically dam-
aged and the corrosive species penetrate the metal surface, the
Synthesis of ZrO2–SiO2 nanoparticles by the sol–gel
corrosion process cannot be avoided [10–19]. A possible
method
alternative to improve the corrosion resistance of PU coatings
on carbon steel substrates is by combining them with other
The ZrO2:SiO2 nanoparticles were prepared from zirco-
protection mechanism. One of them is the incorporation of
nium n-propoxide, Zr-P (70 wt% in n-propanol), tetra-ethyl
ceramic nanostructures inside the polymer matrix, which are
orthosilicate, TEOS (98 % purity), acetylacetone (AcAc)
commonly known as hybrid materials [2, 20, 21]. The
(Reagent Plus C 99 %, Sigma-Aldrich), together with
incorporation of nanoparticles enables the composite materi-
deionized water, ethanol 99.9 % and isopropanol 99.9 %
als to display superior properties than those of the neat
(Fermont). Three different ZrO2–SiO2 systems were syn-
polymer matrix [22]. The most useful methodology used
thesized to obtain different molar ratios: 25:75, 50:50,
properly to either obtain ceramic particles or to incorporate
75:25 mol %, respectively. The sols were prepared in a
inorganic compounds into an organic matrix before coating is
two-step process. During the first step, TEOS was mixed
the sol–gel method [23–26]. Thus, these composites are
with ethanol and stirred for 1 h at room temperature up to
defined as materials that combine organic and inorganic
hydrolyzed; thereafter, a particulate sol was prepared by
domains on a nanometric scale bound by covalent bonds
adding a solution of 0.01 N NH4OH and water up to a 2:1
[27, 28]. The interest in developing hybrid coatings is due to
molar ratio H2O:TEOS. On the other hand, Zr-P was mixed
the unique properties displayed by both components. Whereas
in 9 mL of isopropanol and stirred for 20 min. In this step,
the inorganic part increases adhesion by forming chemical
during the gelation process, and once hydrolysis has star-
bonds between the interfaces that corresponds to the metal-
ted, two simultaneous reactions occurred involving the
surface coatings, improving the overall polymer performance
hydrolysis of the monomeric alkoxide and the polymeri-
in the coatings, the organic areas, with properties such as
zation of hydrolysis products. The resultant network
hydrophobicity, increase the cross-linking density. It is then
structures are strongly affected by the respective kinetic of
clear that the bond kind and dispersion of ceramic nano-
the reactions, which can be modified with the addition of
structures into the polymer matrix play an important role
chelates or complex agents or catalysts. Thus, with the
during the cross-linking [29], which affects the degree of
purpose of carrying out the hydrolysis of Zr-P slower [35],
reinforcement and weakens the mechanism of protective
the obtained solution was complexed by using AcAc with
coatings. In this way, it has been recognized that the degra-
an AcAc/Zr-P molar proportion of 1:1.5 and isopropanol
dation of a protective organic coating can be commonly
until sol dissolution; finally, the Zr-P solution was main-
promoted by filiform corrosion, cathodic delamination or
tained for 10 min under stirring at room temperature.
both. Hence, an understanding of the characteristics of the
In the second stage, the obtained solutions were mixed
hybrid coatings can be a crucial step towards the formulation
under magnetic stirring at 25 °C for 10 min. The pH was
of effective mitigation strategies and factors such as the ratio
fairly constant during the synthesis process (pH 6). The
of inorganic and organic components, cure temperature
synthesized gel was dried at 100 °C for 24 h; afterwards, the
(crystallinity), and pigments need to be optimized for attain-
xerogel samples were powdered in an agate mortar and
ing films with the maximum corrosion resistance [17, 30–34].
sintered under static air in a muffle furnace. The samples
In the present paper, mechanical properties and degradation
were annealed at different temperatures (400, 600, 800, and
of different PU ? ZrO2:SiO2 hybrid coatings applied on AISI
1000 °C) to follow changes in the structure and particle size.
1018 commercial carbon steel were investigated by nanoin-
dentation determinations, atmospheric corrosion, and elec-
trochemical impedance spectroscopy (EIS). To reach this Preparation of coatings
objective, three different molar ratios of ZrO2:SiO2 mixed
oxides (25:75, 50:50, 75:25) were produced by the sol–gel Ethyl acetate (EtOAc) (TOPCHEM S.A de C.V.), and
technique and sintered at different temperatures (400, 600, polyurethane coating of one component MDI polymer

123
J Mater Sci (2013) 48:1067–1084
Fig. 1 Chemical structure of 4,40 -methylene bis (phenyl isocyanate) (MDI) and formation of crosslinked networks
grade (Desmodur E21Ò) BayerÒ were used to obtain hybrid
materials as follows: 10 g of one component polyurethane
base MDI were dissolved in 20 mL of EtOAc under stirring
and after 20 min 2 wt% of ZrO2:SiO2 mixed oxides were
added to the MDI solution to form different PU ? ZrO2:SiO2
hybrid mixtures. In order to reach the nanoscale, ZrO2:SiO2
particles, well dispersed in the PU solution, were vigorously
stirred for 2 h. Thereafter, hybrid coatings were spread on
commercial carbon steel (1018) plates (20 mm 9 20 mm 9
1 mm). Finally, the coated samples were annealed at 120 °C
for 15 min. The process was repeated to obtain different
hybrid coatings with 4 and 6 wt%.
It is important to note that before coating, the metallic
substrates were mechanically polished with different paper
grids (180, 320, 600, and 1500), and after, the plates were
washed with a soap–distilled water–acetone solution.
X-ray diffraction and analysis of particle sizes
The structure of the ZrO2:SiO2 powders and hybrid coat-
ings was followed with X-ray diffraction patterns using a
D8 Advance Bruker AXS and a Cu Ka radiation
(k = 1.5405 Å). The samples were scanned in the 2h range
of 20°–90°.
For the particle size, a scanning electron microscope
(SEM), FEI Company Model Quanta 3D FEG (SEM/FIB)
at High vacuum (6 9 10-4 Pa), backscattered electrons
(BSED), 30 kV, and 5 mm was used.
Confocal scanning laser microscopy (CLSM)
and atomic force microscopy (AFM)
The hybrid coatings were also characterized by CLSM by
using a Carl ZEISS Microscope, Model LSM 700, using
the fluorescence properties of the system: Carbon steel
(1018) plate 636 nm, MDI in 500 nm and ZrO2–SiO2
1069
nanoparticles in 519 nm. The topography and roughness
were analyzed and measured by an AFM, Veeco, Model
diMultiMode V, controller diNanoScope V, with cantilever
RTESP tips.
Nanoindentation test
The surface mechanical properties of hybrid coatings were
determined using a Nano-Hardness TesterÒ from CSM
Instruments SA (Peseux, Switzerland) with a Berkovich
diamond indenter. A loading rate of 10 mN min-1 was
maintained during the incremental increase of the load until
the indenter reached a maximum load of 50 mN. The load
was held for 20 s in order to account for creep effects
before the indenter was unloaded. Five indentations were
measured to obtain average values.
Hardness and elastic modulus can be determined by the
method developed by Oliver and Pharr [36], in which the
hardness, H, is equal to the indentation peak load (Pmax)
divided by the projected contact area (A), as shown in the
following equation:
Pmax
H¼ ð1Þ
A
where Pmax represents the maximum load applied between
the indenter and the sample surface. Considering an ideal
Berkovich indenter, the area can be calculated as follows:
A ¼ 24:5  h2c ð2Þ
In this case hc is the contact or plastic depth, which in
turn is determined by the following expression;
 
Pmax
hc ¼ hmax  e ð3Þ
S
where e is a constant generally considered as 0.75 and S is
the unloading stiffness measured at the maximum pene-
tration depth (hmax).
123
1070
Furthermore, it is commonly necessary to obtain a
relationship between the reduced modulus Er and the
elastic modulus Es, which is shown as follows:
    of the molar ratio; at low temperatures (400 and 600 °C),
1 1  v2s 1  v2i
¼ þ ð4Þ
Er Es Ei
In this equation, Ei and vi are the Young’s modulus and
Poisson’s ratio of the indenter, respectively; whereas vs is
the Poisson’s ratio of the test material. Considering that:
pffiffiffi
p Smax
Er ¼ pffiffiffi ð5Þ
2 A
Smax is the slope of the unloading curve at the point of
maximum load.
Electrochemical testing
Atmospheric corrosion
The exposure site of steel sheets was located on the roof of a
laboratory under severe environment conditions that are
characteristic of this region (south part of Tamaulipas, Mexico):
high relative humidity, considerable duty traffic, beach prox-
imity (less than 5 km) and industrial area location. Data of the
environmental conditions of this site are presented in Table 1.
The plates were analyzed on open-air at an angle of 45° from the
horizontal plane after 280 days. After this time, the corrosion
products and morphology were analyzed.
EIS measurements
The electrochemical measurements (EIS) were recorded in a
potentiostat/galvanostat (Reference 600, Gamry Instruments)
in a three-electrode cell; the substrate of the working electrode
was coated so as to expose an area of 1.13 cm2. A saturated
calomel electrode was used as the reference electrode, and the
counter electrode was graphite. The frequency range was
100 kHz down to 10 mHz. The EIS curve was measured
periodically during an exposure period of 226 days; the
samples were immersed in an electrolyte solution of NaCl
(3 wt%) to simulate the atmospheric conditions. The corrosion
products were also characterized by XRD for identification of
crystalline phases; SEM/EDS in combination with light
microscopy for morphological studies and elemental analyses
of the surface, using the equipment mentioned above.
Results and discussion
Structural analyses of ZrO2:SiO2 nanoparticles
Figure 2a–d shows the X-ray diffraction patterns of
ZrO2:SiO2 nanoparticles with different molar ratios and
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J Mater Sci (2013) 48:1067–1084
sintered for 1 h at four different temperatures 400, 600,
800, and 1000 °C, respectively. The XRD analyses of the
ZrO2:SiO2 nanostructures seem to indicate self-governing
the spectra displayed an amorphous phase [37–39].
This non-diffracting structure also remains with low
ZrO2:SiO2 ratios (25:75 mol %) and 800 °C. Supple-
mentary ZrO2:SiO2 molar ratios (50:50, 75:25) annealed
at 800 °C and all the samples sintered at 1000 °C dis-
played a crystalline structure that apparently matched
with the tetragonal phase, although, due to the vicinity of
cubic structure reflections, this phase could not be dis-
carded initially. However, a more detailed analysis of the
XRD spectra and in agreement with previous research
works, the peaks around 2h = 30.2°, 50.3°, and 60.2° are
assigned to the (011), (112), and (121) reflections of
tetragonal ZrO2, which is corroborated with the splitting
peaks that emerge at higher temperatures close to 35°
(002), (110) and at 63° (202) [34]. In addition, the
presence of (011) broad peaks produced by the most
frequent ion–ion distances, corroborates that the local
order in the amorphous phase was similar to the local
order in the tetragonal phase [34] and validates the
assumption that the most abundant crystalline phase
formed during the crystallization of the amorphous phase
was the tetragonal one. The observed broadening of
diffraction peaks was attributed to the small crystallite
size or poor crystallinity. The preliminary crystal size
d of the as-densified sample was estimated from Scherrer
equation [40]. The mean crystallite sizes were about 4
and 6 nm for molar ratios of 50:50 and 75: 25, respec-
tively, at 800 °C, whereas at 1000 °C, the average crystal
sizes were 6, 7, and 9 nm, respectively.
From these results, it can be inferred that at 800 °C,
the formation of a crystalline structure started above a
50:50 molar ratio of ZrO2:SiO2 and that under the stated
experimental conditions; the molar ratio and sintering
temperature have significant effect on the crystalline
structure of ZrO2:SiO2 mixed oxides [41, 42]. It is well
known that there are two competition processes during
heat treatment, which are crystallization and sintering.
Crystallization makes densification more difficult, and
can be activated throughout a reduction of activation
energies, but the low activation energy for a crystal can
result in abnormal growth; whereas during the sintering
process occurs a reduction of surface energy of the
particles (compactness) caused by a reduction of their
vapor–solid interfaces.
Thus, a gradual increase in the diffraction peak inten-
sities as well as in crystallinity with increasing temperature
is commonly referred to growth grains; i.e., the increase in
the sintering temperature provokes an improvement of the
interfacial reaction [41].
J Mater Sci (2013) 48:1067–1084 1071

Table 1 Environmental conditions in the South of Tamaulipas, Mexico

Emission NOx SOx COV CO PM10 PM2.5 NH3
sourcea
mg per % mg per % mg per % mg per % mg per % mg per % mg per %
year year year year year year year

Altamira 9,467 44 91,794 70 2,763 7 7,055 16 947 24 637 24 1,989 79

Tampico 5,948 28 38,942 30 29,465 78 19,015 43 2,505 64 1,674 62 221 9
Madero 5,870 28 904 1 5,522 15 17,898 41 445 11 373 14 316 13
Total 21,285 131,640 37,750 43,968 3,898 2,685 2,525
b
Data Value

Annual average temperature (°C) 24.9

Annual average maximum temperature (°C) 30.5
Annual average minimum temperature (°C) 20.9
Annual average humidity (%) 79.8
Cumulative annual total precipitation (mm) 868.69
Annual average visibility (km) 16.1
Annual average wind speed (km h-1) 10.8
a
SEMARNAT 2006
b
Data reported by the meteorological station 765480: latitude 22.2°, longitude 97.85°, altitude 26°

ZrO2fase (c) JCPD 89-9069 ZrO2 (c)phase JCPD 89-9069

ZrO2-SiO2 400°C Δ ZrO fase (t) JCPD 50-1089 ZrO2-SiO2 600°C
2
Δ ZrO (t)phase JCPD 50-1089
2

(a) 25:75 (b) 25:75

Intensity (a.u.)
Intensity (a.u.)

50:50
(111)

50:50
(111)
(011)

(011)
(112)
(220)

(121)

(220)
(112)
(311)

(202)

Δ Δ
(311)

(202)
(121)

Δ Δ
ΔΔ ΔΔ
75:25 75:25

20 30 40 50 60 70 80 20 30 40 50 60 70 80
2θ (degrees) 2θ (degrees)

(c) ZrO2-SiO2 800°C ZrO2(c)phase JCPD 89-9069

Δ ZrO (t)phase JCPD 50-1089 (d) ZrO2-SiO2 1000°C ZrO2 (c)phase JCPD 89-9069
2
Δ ZrO (t)phase JCPD 50-1089
2

25:75
25:75
Intensity (a.u.)
(111)
Intensity (a.u.)

(200)

(311)
(220)

(011)
(222)

(112)

(114)
(331)
(400)

(002)
(110)

(013)
(121)
(202)

(123)
(220)

Δ
50:50 Δ Δ
Δ Δ Δ ΔΔ
Δ Δ 50:50
(011)

(112)

(121)

(420)
(110)

(013)

(202)

(031)

(111)

Δ
(220)

(311)
(222)
(220)
(200)

(331)
(400)

Δ Δ Δ Δ Δ
Δ Δ 75:25 75:25

20 30 40 50 60 70 80 90 20 30 40 50 60 70 80

2θ (degrees) 2θ (degrees)

Fig. 2 XRD patterns of ZrO2:SiO2 mixed oxide using different molar ratios and heat treatments

123
1072
Scanning electron microscopy analyses of ZrO2–SiO2
The SEM micrographs of the sintered and ultrasonic pre-
dispersed powders using different ZrO2:SiO2 ratios are
presented in Figs. 3 and 4a–l. The microstructure of the
powders displayed uniform spherical and very fine particles
with an equiaxed-rounded shape; these particles are
agglomerated into larger clusters of irregular form and it
was possible to obtain some hard-aggregates. Then, the
agglomerates are defined as a limited arrangement of pri-
mary particles formed by cementation of individual parti-
cles. These agglomerates are based on chemical bonds and
physical attraction forces at interfaces. The powder
agglomeration degree indicates that the synthesized parti-
cles consisted of mostly primary particles with less
clusters; this indicates that smaller grains can form
agglomerates easily due to a small-size effect. From the
micrographs, it was hard to compare both sizes, fine par-
ticles versus coarse particles; so it was considered neces-
sary to obtain two distributions for each system. Most of
the average particle size at low temperatures (400 °C)
ranged from 60–100 nm and 1.5–4 lm for fine and coarse
particles, respectively, which varies depending on the
molar ratio of mixed oxide, but increases in relation to the
calcination temperature up to 116, 231, and 330 nm for fine
particles and 2.8, 2.2, 3.1, and 5.4 lm for coarse particles
at 600, 800, and 1000 °C, respectively. The trend matched
with previous results observed by other authors [43]. It is
usually reported that the liberation of volatile components
of xerogels such as water, R–OH, and CO2 (from alkyl
groups) provokes porosity and high surface area in the
nanostructures, which is partially eliminated with the sin-
tering temperature, so we assumed that this phenomenon
also occurred during the crystallization process.
Characterization of MDI/ZrO2:SiO2 hybrids coatings
Confocal laser scanning microscopy studies (CLSM)
Different amounts of annealed nanoparticles (2, 4, and
6 wt%) were added to the PU matrix, but after several
trials, it was found that an adequate dispersion and homo-
geneity was achieved when 2 wt% of sintered ZrO2:SiO2
nanoparticles was mechanically mixed with polymer
(MDI), and used to produce hybrid coatings on AISI 1018
commercial carbon steel by spray technique. For this rea-
son, from now the discussion focus on hybrid coatings
when 2 wt% of ZrO2:SiO2 nanoparticles are incorporated
to the polymer, whereas some results incorporating 4 and 6
wt% of nanoparticles as well as films with pure polyure-
thane are shown for comparison. As a matter of fact, all the
samples prepared were colorless and transparent before and
after the thermal treatments. The coated substrates were
123
J Mater Sci (2013) 48:1067–1084
Fig. 3 Particle size distribution and morphology of ZrO2–SiO2 par- c
ticles with different molar ratios and sintered at 400 and 600 °C. In
this figure are considered two kinds of distributions: a, c, e, g, i, k
corresponds to fine particles, whereas b, d, f, h, j, l relates to coarse
particles
characterized by using CLSM as a nondestructive tech-
nique before electrochemical evaluation. The CLSM has
demonstrated to be a powerful technique to study the film–
core interface; CLSM combined with computational image
analysis allowed the quantitative determination of the
thickness, pores, and composition of the wall materials of
the nanostructures [44]. In addition, the technique has been
employed successfully to examine the surface morphology
of different substrates and evaluate inclusions, pits, grain
boundaries, etc., before and after the corrosion process
[45–52]. The CLSM images shown in Fig. 5a–e, illustrate
the morphology and distribution into the polymeric matrix
of the ZrO2:SiO2 nanoparticles using an amount of 2 wt%
at 400 °C. A comparison of the images recorded on the
coated specimens with 4 wt% of the particles is also shown
in this figure. From the measurements, it can be observed
that the particles are well dispersed into the polymeric
matrix, but tend to form agglomerates as the ZrO2/SiO2
ratio increases. CLSM reveals a film free of pores or cracks
with an irregular morphology and extensive size of the
nanostructures, which varies with the quantity of mixed
oxide added to the matrix. The sintered particles seal the
gas bubbles commonly formed during the normal PU
polymerization process (Fig. 6); water reacts with some of
the isocyanate groups producing carbon dioxide, some of
these gas bubbles become trapped, eventually pop and lead
the permeation of corrosive species such as oxygen, water
and ions, provoking the reduction of the coating adhesion
(blistering) [53]. Thus, the free-bubble surface is achieved
by the addition of nanostructures, assuming that the parti-
cles are capable of occupying the gas bubble sites. The
three-dimensional structure revealed the spatial position of
the ceramic particles in all the directions, which is helpful
to evaluate the differences among corrosion properties. In
addition, the film thickness was found to be between 40 and
55 lm, which was in agreement with profilometry mea-
surements. The depth of the embedded nanoparticles also
seems to be uniform, which began to appear at 15 lm
approximately. The particles incorporated to the polymer
networks act as a network former, and therefore, the
motion of the organic polymer can be restricted as a
function of the Si–O–Si and Zr–O–Zr linkages, needing
much more energy to decompose or erode the organic
chains.
It is well recognized that different morphologies cause
modification in the corrosion mechanism, but in this case,
the distribution of the particles can also play an important
role in the mechanical properties.
J Mater Sci (2013) 48:1067–1084 1073

25 ZrO 2-SiO 2 (2 5:75) 4 00°C

(a) 40 (b) ZrO2 -SiO2 (25:75) 400°C

Frecuency (%)
Frecuency (%)

20

Frecuency (%)
30

Frecuency (%)
15

20
10
40 80 120 160
Particle size (nm) 5000 10000 15000
5 10 Particle size (nm)

0 0
40 60 80 100 120 140 160 180 400 0 8 000 1200 0 16 000 2000 0

Particle size (nm) Particle size (nm)

30 80
ZrO 2 -Si O 2 (50:50) 400°C Zr O2 -SiO2 (50:50 ) 400°C

25
(c) 70 (d)

Frecuency (%)
Frecuency (%)

60
Frecuency (%)

20 50

Frecuency (%)
15 40
40 80 120 160
Particle size (nm) 30
6000 12000 18000 24000
10 Particle size (nm)
20
5 10
0
0 5000 10000 15000 20000 25000
40 60 80 100 120 140 160 1 80

Particle size (nm) Particle size (nm)

25 1.0
(e) ZrO2-Si O2 (75: 25) 400 °C
0.9 (f) ZrO2 -SiO2 (75:25) 400°C

20 0.8
Frecuency (%)

Frecuency (%)

Frecuency (%)
12
0.7 10

Frecuency (%)
15 0.6 8
6
0.5 4
10 0.4 2
20 40 60 80 100 120
0
Particle size (nm) 0.3 0 3000 6000 9000 12000
Particle size (nm)
5 0.2
0.1
0 0.0
20 40 60 80 100 12 0 2000 4000 6000 8000 10000 1200 0

Particle size (nm) Particle size (nm)

25
ZrO 2 -SiO2 ( 25:75) 600°C
25
(g)
ZrO2 -Si O2 (25: 75) 600°C
(h)
Frecuency (%)

20

Frecuency (%)
20

Frecuency (%)
Frecuency (%)

15
15
1000 2000 3000 4000
Particle size (nm)
10 60 90 120 150 180
10
Particle size (nm)

5 5

0 0
60 80 100 12 0 1 40 1 60 180 500 1000 1500 2000 2500 3000 3500 4000

Particle size (nm) Particle size (nm)

25
ZrO2-Si O2 (50:50) 60 0°C ZrO2 -SiO2 (50:50 ) 600°C
(i) 35
(j)
20 30
Frecuency (%)
Frecuency (%)

Frecuency (%)

25
Frecuency (%)

15
20

10 60 90 120 150 180 15

Particle size (nm)

10 1500 3000 4500

Particle size (nm)
5
5

0 0
60 80 100 120 140 160 180 200 1000 200 0 3 000 4000 50 00

Particle size (nm) Particle size (nm)

80
24 (k) ZrO2-SiO2 (75:25) 600°C
70
(l) ZrO2-SiO2 (75:25) 600°C

20
Frecuency (%)

60
Frecuency (%)
Frecuency (%)

16 50
Frecuency (%)

60 90 120 150 180

40
12 Particle size (nm)
30
8
20 5000 10000 15000 20000
Particle size (nm)
4 10

0 0
60 80 100 120 140 160 180 5000 10000 15000 20000

Particlle size (nm) Particle size (nm)

123
1074 J Mater Sci (2013) 48:1067–1084

20
(a) ZrO2-S
SiO2 (25
5:75) 800°C
50 (b) ZrO 2 -SiO
- 2 (2
25:75) 8
800°C

Frecuency (%)
Frecuency (%)

Frecuency (%)
40
15

Frecuency (%)
30
10 80 100 120 140 160 6 180
Particle size (nm) 20
40
000 0 00 12 0 00 1600
80 00
5 10
Particle size (nm)

0 0
80 100
0 12
20 14
40 1
160 180 3000 6000 9000 1 2000 15000
Particle size (nm) Particle size (nm)

0
30
(c) ZrO2-S
SiO2 (50:50) 800°C
50 (d) ZrO2-S
SiO2 (50::50) 800°C
5
25
Frecuency (%)

Frecuency (%)

Frecuency (%)
0
20 40

Frecuency (%)
5
15 30
60 90 120 150 18 80
Particle size (nm)
0
10 20
1000 2000 3000 4 4000
Particle size (nm)
5
10
0
40 60 80 100 12
20 140
0 160
0 180 0
500 1000 1500 2000 2500 3000 3500 4000
Particle size (nm)
Particle size (nm)

0
40
ZrO2-S
SiO2 (75:25) 800°°C 24
5
35 (e) ZrO
O2-SiO2 (75:25) 800°C

(f)

Frecuency (%)
20
Frecuency (%)

0
30

Frecuency (%)
Frecuency (%)

5
25 16
0
20
12 1000 2000 3
3000 4000 5000
5
15 Particle size (nm)

100 200 300 400 500 600 700 8

0
10 Particle size (nm)

5 4
0
2
200 300 400 500
0 600
0 70
00 0
10
000 2000 30
000 4000
Particle size (nm)
Particle size (nm)

5
25 70
(g) ZrO2-SiO
O2 (25:7
75) 1000°°C
60
(h) Zr O2-SiO2 (25:75)
( 1
1000°C

0
20
Frecuency (%)

Frecuency (%)
Frecuency (%)

50
5
15

Frecuency (%)
40

0
10 40
0 80 1 120 160 200 30
Particle size (nm)

20 5000 10000 15000 20000

5 Particle size (nm)

10
0 0
40 60 20 140 160
80 100 12 0 180 40
000 8000 12000 1
16000 20000
Particle size (nm) Particle size (nm)

35
5
ZrO 2-SiiO 2 (50:5
50) 1000 °C
40 (i) (j) ZrO2 - SiO2 (50
0:50) 10 00°C
Frecuency (%)

30
0
Frecuency (%)

25
5
30
Frecuency (%)

Frecuency (%)

20
0
20 15
5
0 200 400 600 800 1000
Particle size (nm) 10
0 10000 20000 30000
Particle size (nm)
10
5
0 0
20
00 400 60
00 800 100 0 10000 20000 30000 40000
Particle size (nm) Particle size (nm)

4
40 ZrO2 - SiO2 (7
75:25) 1 000°C
8
80
ZrO 2 -SiO2 (7
75:25) 1000°C
1
3
35 (k) 7
70 (l)
Frecuency (%)
Frecuency (%)

3
30 6
60
Freccuency (%)

2
25 5
50
Frecuency (%)

2
20 4
40

3
30
15 300 450 600 750
Particle size (nm)
2
20 10000 20000 30000
10 Particle size (nm)

1
10
5
0
0 5000 10000 15000 20000 25000 30000
2
200 3 00 400 5 0 0 6 0 0 7 0 0 800 900
0
Particle size (nm)
Particle size (nm)

123
 J Mater Sci (2013) 48:1067–1084
b Fig. 4 Particle size distribution and morphology of ZrO2–SiO2
particles with different molar ratios and sintered at 800 and
1000 °C. In this figure are considered two kinds of distributions:
a, c, e, g, i, k corresponds to fine particles, whereas b, d, f, h, j, l
relates to coarse particles
AFM studies
The distribution and particle size of ZrO2:SiO2 within the
polymer matrix led to distinct differences in surface
topography and roughness of the prepared coating films and
it was investigated by AFM. As a reference, Fig. 7a–c
shows the AFM of the as-grown film on AISI 1018 com-
mercial carbon steel with and without ceramic particles,
using 2 and 4 wt% at 400 °C. In agreement with SEM
(a)
(c)
(e)
Fig. 5 CLSM images of hybrid coatings using a, c, e 2 wt% and b, d, f 4 wt% of ZrO2–SiO2 nanostructures into the polymeric matrix and its
corresponding 3D representation
1075
measurements, the AFM image shows clearly the inhibition
of gas bubble formation during the polymerization process
and also corroborates the assumption that average surface
roughness (Ra) and mean square of the Z data (Rq)
decreased up to one order in magnitude with the amount of
mixed oxides in comparison with polymer coating free of
nanostructures. The surface roughness is one of the quan-
titative magnitudes describing the surface relief. In this
case, the Z value is defined as the difference between the
highest and lowest points within the given area. The
hydrophilic character of the ZrO2:SiO2 system seems to be
the cause of the reduction of surface roughness, i.e., when
the particles are added to the MDI polymer; they have the
ability to absorb the moisture present in the system [31, 54].
(b)
(d)
(f)
123
1076
Fig. 6 Optical images of micro pores obtained during the PU polymerization without reinforced nanostructures at different magnifications
Nanoindentation hardness test
Table 2 shows the hardness results from indentation load-
ing–unloading curves of the as-deposited hybrid coatings,
using 2, and ZrO2:SiO2 mixed oxides with the three molar
ratios proposed in this investigation and 400 °C of sinter-
ing temperature. In these results, the indentation creep
(CIT) was defined as the relative change of the indentation
depth whilst the applied load remains constant:
h2  h1
CIT ¼  100
h1
where h1 and h2 are the indentation depth at t1, when
the force began to remain constant and the indentation
depth at the last time t2, respectively. Then, the hardness
value (H) signifies the resistance of a material to local
surface deformation and its counterpart (elastic modulus,
Es) denotes the overall stiffness of the polymer matrix.
A Poisson’s ratio vs = 0.49 was assumed for the
as-deposited coatings to extract the hardness and reduced
modulus values, using the previous equations. For
comparison, Fig. 8 also shows typical indentation load–
displacement curves for the as-deposited hybrid coatings
using 2, 4, and 6 wt% ZrO2:SiO2 mixed oxides with a
25:75 molar ratio and 400 °C of sintering temperature as
well as the curves for pristine PU coatings under the same
experimental conditions.
123
J Mater Sci (2013) 48:1067–1084
From these experimental data, it can be observed that
the incorporation of ceramic oxides into the PU matrix
resulted in its film surface being slightly more resistant to
penetration by the indenter in comparison with that of the
pure PU. For the pure PU, the maximum indentation depth
at the load of 5 mN was 1890 ± 13 nm; this value
diminished to 1860 ± 9 nm for PU ? 2 wt% ZrO2:SiO2
mixed oxides, 1835 ± 14 nm for PU ? 4 wt% ZrO2:SiO2
mixed oxides and finally, 1701 ± 8 nm for PU. The
addition of ZrO2:SiO2 particles to PU give a compact film,
acting as a mechanical reinforcement. Although, the
ð6Þ indentation measurements of the as-obtained coatings were
carried out at the same deformation rate and specific load
(50 mN), the indentation curve moved slightly with the
applied force according to the quantity of ceramic nano-
structures in an approximately linear manner. Clearly, as
was expected, the incorporation of higher content of
ceramic particles (especially zirconia) into PU coatings
presents an accumulative effect on the mechanical prop-
erties: both the hardness and elastic modulus steadily
increased with the increasing amount of SiO2:ZrO2 nano-
structure particles, whereas the longitudinal movement and
deformation (creep) almost remains constant; i.e., the
H and Es are self-governing on the amount of added
nanostructures, but the ZrO2:SiO2 molar ratio. The ratio of
hardness/elastic modulus is of significant interest in tri-
bology. Higher stress is expected in high H/Es, hard
materials, and high stress concentrations develop towards
J Mater Sci (2013) 48:1067–1084 1077

Fig. 7 AFM images of coatings 1.00 µ m 983.21 n m

on commercial carbon steel (a)
a PU, b PU ? 2 wt% ZrO2/SiO2
mixed oxides, and c PU ? 4
wt% ZrO2/SiO2 mixed oxides
using a 75:25 molar ratio and
400 °C of sintered temperature

200nm

0.00 µm 0.00 nm
998. 73 nm 974. 66 nm

(b)

200nm

0. 00 nm 0.00 nm
1. 01 µ m 790.82 nm

(c)

200nm

0. 00 µm
0.00 nm

Table 2 Values of hardness, H, elastic modulus, Es, and indentation creep, from the unloading response of conventional load–displacement
curves on hybrid coatings deposited on AISI 1018 commercial carbon steel
Coated H (MPa) Es (GPa) CIT (%) H/Es (10-3)

PU 84.21 ± 1.30 1.10 ± 0.01 6.92 ± 0.07 76.55 ± 1.18

PU ? 2 wt% ZrO2–SiO2 (25:75) 87.29 ± 1.01 1.12 ± 0.01 7.01 ± 0.09 77.93 ± 0.90
PU ? 4 wt% ZrO2–SiO2 (25:75) 87.47 ± 1.82 1.16 ± 0.02 7.20 ± 0.07 75.40 ± 2.62
PU ? 2 wt% ZrO2–SiO2 (50:50) 92.16 ± 1.87 1.20 ± 0.02 6.97 ± 0.09 76.80 ± 1.55
PU ? 4 wt% ZrO2–SiO2 (50:50) 96.46 ± 1.03 1.23 ± 0.01 7.11 ± 0.05 78.42 ± 1.78
PU ? 2 wt% ZrO2–SiO2 (75:25) 112.28 ± 0.76 1.27 ± 0.01 7.79 ± 0.02 88.40 ± 0.55
PU ? 4 wt% ZrO2–SiO2 (75:25) 138.29 ± 2.98 1.30 ± 0.02 8.18 ± 0.07 106.37 ± 2.29

123
1078
5 of different contaminants such as NOx, SOx, volatile organic
PU
PU + 2wt-% ZrO2-SiO2(25:75)
PU + 4wt-% ZrO2-SiO2(25:75)
4 (V, Cr, Pb, Cd); and it is also characterized by a moderate
PU + 6wt-% ZrO2-SiO2(25:75)
Load, P (mN)
3 coatings without reinforced ceramic particles were also
2
1
0
0 200 400 600 800 1000 1200 1400 1600 1800 2000
Displacement, h (nm)
Fig. 8 Typical indentation load–displacement curves for the as-
deposited hybrid coatings on commercial carbon steel using 2, 4, and
6 wt% ZrO2/SiO2 mixed oxides with a 75:25 molar ratio and 400 °C
of sintered temperature. As a reference it is also shown the curves for
pristine PU coatings
the indenter tip, whereas in the case of low H/Es, soft
materials, the stress is lower and distributed more evenly
across the cross-section of the material. This statement
seems to be due to the fact that the ceramic particles have a
larger elastic modulus than polymer matrix and packing
events of the nanoparticles in the reinforced coatings or
could also be compactly packed during the nanoindentation
process or both; the hybrid coatings are composed of large
chains with altering soft and hard segments, which are
physically reinforced with mixed oxide particles; thus, the
interaction degree between the segments and molar ratio of
dispersed nanostructures plays a vital role in determining
the hardness and elastic modulus in overall coating. These
details may explain the observed increment in the elastic
modulus and hardness, which were improved up to 47 and
39 %, respectively. Finally, the results also show that an
incorporation of 2 wt% of mixed oxides was enough to
enhance mechanical properties.
Corrosion studies
Morphologies of corrosion products in initial stage
under atmospheric environment
Figure 9a–f shows the optical micrographs of the hybrid
coated steel samples using 2 and 4 wt% of sintered particles at
400 °C and three different molar ratios. The measurements
were evaluated for 180 days of exposure at the CICATA-
Altamira laboratory, which is close to a road with considerable
traffic, in an industrial area, and less than 5 km to the beach.
The marine atmosphere here is characterized by high relative
123
J Mater Sci (2013) 48:1067–1084
humidity (*80 % on average along the year) in the presence
compounds (VOCs),and/or small metallic suspended particles
number of rainy days (64 days per year). For comparison, the
evaluated, and it is shown in Fig. 9g. It is important to notice
that in order to accelerate the corrosion process in the mate-
rials, the edges of the coated specimens were intentionally
unsealed. The different carbon steel samples almost showed
the same patterns to start the corrosion process; filiform cor-
rosion, which is characterized by thin meandering threads of
corrosion beneath the coating, began to appear from the edge
of the plates up to some random points. Classical differences
in color of the filament head attributable to variations in local
pH are also evidenced to the growth mechanism. It is well
documented that the most reasonable interpretation of the
growth mechanism is that water and oxygen diffuse through
the coating into the space at the head of a growing filament.
Oxygen concentration in the head is lower than in the dry tail
because of the reduced solubility of oxygen in water [55, 56].
The atmospheric corrosion in the coatings without reinforced
particles was more severe than that observed in hybrid coat-
ings, and from these, corrosion increased with higher zirconia
molar ratios. Williams and McMurray [57] have reported that
in chloride environments, two different mechanisms can take
place; anodic iron dissolution localized in a defect site which
is coupled to cathodic delamination of the surrounding coat-
ing. Cations migrate beneath the delamination coating to form
an alkaline under-film electrolyte layer and become progres-
sively replaced in external (defect site) electrolyte by Fe2? and
Fe3? cations; in these cases, corrosion finishes when the ions
are exhausted. A second pathway is followed, when different
polarities coexist under the film; the anode fragments to form
filiform corrosion, where the filament heads only contain Fe
and Cl- anions. Thus, by taking into account previous
observations, a scheme of the corrosion process for these
hybrid coatings with unsealed edges is proposed (Fig. 10)
[55, 58]. In this image, it is illustrated that the initiation of the
corrosion process began when marine water droplets con-
dense on the edges of the carbon steel and under-film. As the
edge of a marine water droplet is thinner than in the inside,
diffusion of oxygen from the atmosphere underneath the steel
coating is provoked, and the mismatch between water and
oxygen concentration causes corrosion to occur, i.e., electrons
flow from the low oxygen region (anode) to the high oxygen
region with the following reactions:
Fe0 ! Fe2þ þ 2e ð7Þ
1
O2ðgÞ þ H2 O þ 2e ! 2OH
ðaqÞ ð8Þ
2
J Mater Sci (2013) 48:1067–1084 1079

Fig. 9 Optical morphologies in 2 wt-% ZrO2/SSiO2 4 wt-% ZrO2 /SiO2

the initial step of the corrosion
process in the as-deposited (a) (b)
hybrid coatings using particles
sintered at 400 °C
25:75

(c) (d)

50:50

(e) (f)

75:25

(g)
Pure
PU

Fe2þ þ 2OH ! FeðOHÞ2 ð9Þ 1

2Fe (OH )2 + O2 2FeOOH + H 2O (12a)
2
Fe2þ þ 2Cl ! FeCl2 ð10Þ
1 γ − FeOOH, α − FeOOH, γ F e2O3 (12b)
2FeðOHÞ2 þ O2 ! H2 O ! 2FeðOHÞ3 ð11Þ
2
or
2FeOOH ! Fe2 O3 þ H2 O ð13Þ

123
1080 J Mater Sci (2013) 48:1067–1084

Fig. 10 Filiform corrosion

mechanism and corrosion
products in initial stage of
atmospheric corrosion of
PU ? ZrO2–SiO2 hybrid
coatings on AISI 1018
commercial carbon steel

Fig. 11 SEM micrographs showing a combination of typical mor- respectively, which were evaluated on PU ? ZrO2–SiO2 (25:75, 2
phologies of a goethite globular, b a combination of lepidocrocite and wt%) hybrid coatings when the reinforced particles were sintered at
akaganeite structures, fine plates and rosette morphologies, 400 °C

These reactions suggest that FeCl2 does not play an

PU + 2wt% ZrO 2:SiO2 (25:75) 400°C
important role in the mechanism of filament advance and
Fe (c) phase ICDD 87-0721
M Magnetite ICDD 87-0245 that the reinforced nanostructures did not modify the cor-
L Lepidocrocite ICDD 44-1415 rosion mechanism (filiform). On the other hand, it is well
G Goethite ICDD 81-0464
recognized that the formation mechanism and morphology
Intensity (a.u.)

A Akaganeite ICDD 34-1266

(110)

depend on the synthesis method; so a wide range of mor-

(211)

phologies and crystal sizes can be obtained; and mis-

ML
(200)

G
M L
matches are documented between the different researchers
G L L at the moment of assigning a determined morphology to a
M AM
MG
particular corrosion product [59–61]. Thus, the rust mor-
A phology observed after 280 days on PU ? ZrO2–SiO2
(25:75, 2 wt%) hybrid coatings, when the reinforced
particles were sintered at 400 °C (Fig. 11), seems to be
20 30 40 50 60 70 80 90 correlated with different phases such as goethite, lepido-
2 θ (degrees) crocite, and akaganeite structures. Typical dark flat regions
with circular discs commonly correlated with magnetite
Fig. 12 XRD patterns of corrosion products obtained in PU ? ZrO2– were not observed in the surface samples; however, the
SiO2 (25:75, 2 wt%) hybrid coatings when the reinforced particles
were sintered at 400 °C after 280 days of evaluation under atmo- XRD diffraction pattern of the selected specimens (Fig. 12)
spheric environment corroborates the presence of these phases on the obtained

123
J Mater Sci (2013) 48:1067–1084 1081

14
10
Carbon steel + PU Carbon steel + Hybrid coatings 2 days
2 days (c) 2 wt-% ZrO2-SiO2 (25:75) 400°C 30 days
10
7 30 days 12
60 days
10 60 days
106 days 105 days
10 226 days
10
6 226 days 10

lZl ( Ω cm )

lZl (Ω cm )
2

2
8
4
10
10
5 Bare carbon steel
10 3
10

cm )
6

2
2
10 10

lZl (
1
10
4
10 0
10 -2 -1 0 4
1 2 3 4
10 10 10 10 10 10 10 10
5
10
Frequency (Hz)

3
(a) 2
10 10
-2 -1 0 1 2 3 4 5 -2 -1 0 1 2 3 4 5
10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
Frequency (Hz) Frequency (Hz)

8
10
(b) 10
12 Carbon steel + Hybrid coatings (d)
2 wt-% ZrO2-SiO2 (25:75) 400°C
11
Rp ( Ω cm )

7 10
2

10

Rp ( Ω cm )
2
10
10
6
10 9
10
8
10
5 10
Carbon steel + PU
7
10
0 50 100 150 200 250 0 50 100 150 200 250
Exposure time, days Exposure time, days

Fig. 13 Impedance modulus spectra and polarization resistance and c, d hybrid coating using 2 wt% of sintered ZrO2–SiO2 (25:75)
values of as-prepared coatings on commercial carbon steel after nanostructures at 400 °C, respectively
exposure to 3 wt% NaCl solution for 226 days a, b pure polyurethane

corrosion products in the Altamira atmosphere, Tamps, 75:25 molar ratio were tested. The specimens were exposed
Mexico. to continuous immersion to naturally aerated aqueous 3
wt% NaCl solutions. Figure 13a–d depicts the selected
EIS of hybrid coatings impedance module spectra and Rp values obtained during a
226-day-immersion period for the coatings with and
The stability of the metal–polymer interface is governed by without reinforced ZrO2:SiO2 particles, respectively. For
three crucial properties: The electron-transfer properties at comparison, it is also shown in an inset Fig. 13a the
the interface, the redox properties of the oxide between the impedance modulus for bare steel after 1 h of immersion.
metal and the polymer and the chemical stability of the The coating with pure polyurethane displayed a trend to
interface with respect to those species that are formed form one time constant or electrochemical interface
during the electron transfer reaction [62]. Then, in order to (composed by a capacitor in series–parallel with electrolyte
assess the barrier properties of hybrid coatings with 2 wt% resistance and coating resistance) during the first 30 days
of sintered ZrO2–SiO2 nanostructures on commercial car- of evaluation, whereas after this period a second time
bon steel, long-term EIS measurements were carried out. In constant (a second slope, indicating two electrochemical
this way, it is known that high ohmic resistance of organic interfaces) began to appear at intermediate and low fre-
coatings impedes the use of dc-type electrochemical mea- quency regions (Fig. 13a). As a consequence, it was
surements, since during a potentiostatic polarization of a observed that the polarization resistance values, Rp, as
polymer-coated metal surface; the potential drops across determined from the low-frequency limit of the corre-
the polymeric layer in orders of magnitude larger than the sponding spectra have a tendency to decrease–increase
potential drop across the metal–polymer interface. EIS has with immersion time (Fig. 13b). This indicates that the
found widespread application for electrochemical studies coating samples suffer a degradation process after few days
of degradation of polymer-coated metals [61, 62] and is of exposure in the aggressive medium provoking that the
normally measured using a small excitation signal. Only electrolyte penetrates the coating, creating a path to reach
PU coated steel samples with and without 2 wt% of the substrate surface; i.e., after a certain amount of time,
ZrO2:SiO2 nanostructures sintered at 400 °C and using a water penetrates into the coating and forms a new liquid

123
1082
under the coating (interface), where corrosion phenomena
began to occur forming corrosion products. The barrier
formed by corrosion products causes an increase in the Rp
values which was perfectly observed after 30 days,
although, it is necessary to consider that this film was non-
stable, with high porosity and low adherent which caused
that Rp to vary and finally, it began to decrease after
reaching a maximum value.
On the other hand, the as-prepared hybrid coatings
displayed a purely capacitive behavior (Fig. 13c), which is
characteristic of an effective barrier film. In this system, the
low-frequency limit of the impedance modulus displayed
very high values ([1011 X cm2). Only one constant was
observed from the inspection of the impedance spectra of
these samples during the first 100 days, highlighting the
barrier characteristics of the hybrid coatings. As a matter of
fact, with increasing exposure time, the coating layer was
gradually attacked and thinned down by the electrolyte,
and some ceramic nanostructures began to appear, which
were characterized by a small second time constant, fol-
lowed by a decrease in the coating resistance and shifted
the phase angle towards to high frequency; however, the
electrolyte never penetrated the coating layer to attack the
substrate, which it was evidenced by the absence of both a
second time constant and typical red rust on the substrate
(a)
(b)
Fig. 14 SEM/EDS observations after 226 days of continuous immersion in 3 wt% NaCl solution a, b without reinforced nanostructures and b,
c adding 2 wt% of sintered ZrO2–SiO2 (25:75) nanostructures at 400 °C
123
J Mater Sci (2013) 48:1067–1084
surface. It is also important to notice the important decay of
the coating resistance during the evaluation time. However,
even this falling the Rp values after; 226 days were greater
than 107 X cm2 indicating that the hybrid film barrier
properties are still an effective isolation of the metallic
substrate from the aggressive environment (Fig. 13d); i.e.,
the barrier-type behavior extended above 226 days for
hybrid coatings applied on carbon steel, even though a
rather thin film of about 50 lm was applied.
It is well documented that the ability of the mixed
oxide to bind the inorganic and organic constituents, in a
manner that enables passivation, is necessary for maxi-
mum protection of the substrate. In this way, Ooij et al.
[63] reported an enhanced film performance by deposit-
ing a more pronounced hydrophobic polysiloxane layer
(Si–O–Si linkages) on metallic substrate. Then, from
previous results it can be assumed that a good interaction
between the inorganic and organic phases produced
better protective films.
The protection mechanism against corrosion of hybrid
coatings can be explained on the basis of the formation of a
compact, uniform and impermeable barrier layer at the
interface of corrosive media and the metal substrate which
prohibits the permeation of electrolyte ions through coat-
ings. In agreement with previous reports [64], the
(c)
(d)
J Mater Sci (2013) 48:1067–1084
protection provided by these hybrid coatings is purely
through the barrier property as indicated by a similar
decrease in both cathodic and anodic values [65, 66]. The
inorganic domains along with polyurethane are combined
to form a compact dense and well adherent coating, sealing
the metal surface which impeded the migration of the
corrosive ions, thereby providing protection to the metal
substrate.
Finally, in order to verify the degradation process and
surface damage on each coating SEM measurements were
carried out on the samples. Figure 14a–d displays SEM/
EDS micrographs of as-synthesized specimens after eval-
uation for 226 days. Important differences can be observed
in the organic coatings with and without reinforced nano-
structures. In Fig. 14a, some greater cavities (bigger than
the other ones observed with hybrid coatings, Fig. 14c)
were observed on the surface of degraded polymer when
the samples were coated with pure polyurethane. In this
surface C, O, Na, Cl, and Fe were identified which are
characteristic elements of corrosion products (Fig. 14b). In
the case of hybrid coatings, the detected elements in these
cavities correspond to the organic polymer ? mixed oxide
(Fig. 14c), in that surface only C, O, Zr, Si elements and a
small quantity of Fe emerging from the substrate were
detected by EDS (Fig. 14d). Therewith, the above facts
together with the important enhancement of the corrosion
properties pointed out the synergetic effect between inor-
ganic/organic phases to seal the surface, the improvement
of the barrier properties on the AISI 1018 commercial
carbon steel and the analysis of the role of the interpreta-
tion process of ceramic nanostructures into the polymeric
matrix during its immersion in an aggressive medium. This
synergetic effect limits the faradaic reaction at the interface
and also leads to large diffusion resistance [67].
Conclusions
Based on the above results, the following conclusions can
be withdrawn: The crystalline structure of ZrO2:SiO2
mixed oxides depends on the molar ratio and annealing
temperature when the compounds are synthesized by the
sol–gel technique. The microstructure of these powders
displayed a combination of uniform spherical fine particles
with an equiaxed-rounded shape that varies from 60 to
330 nm and coarse particles from 1.5 to 5.4 lm. CSLM
measurements demonstrate that it is possible to achieve a
free-bubble surface by the addition of ZrO2:SiO2 nano-
structures to a polymer matrix, provoking a reduction in the
surface roughness. As expected, the incorporation of
ceramic oxides into the PU matrix resulted in its film
surface being slightly more resistant to penetration by the
indenter in comparison to that of the pure PU; however, the
1083
mechanical properties are ruled by the mixed oxide ratios,
and from these, the integration of higher zirconia content
into PU presents an accumulative effect on the mechanical
properties. The samples evaluated by atmospheric corro-
sion demonstrated that the addition of these nanostructures
to the polymeric matrix did not modify the corrosion
pathway: filiform corrosion. The corrosion products cor-
respond to goethite, lepidocrocite, magnetite, and akag-
aneite structures. EIS measurements using small powder
contents displayed (2 wt%), at low-frequency limit, very
high values ([1011 X cm2) with one constant during the
evaluation time (226 days), and after this period, the hybrid
film barrier properties still are an effective isolation of the
metallic substrate from the aggressive environment.
Finally, the corrosion properties pointed out the synergetic
effect between the inorganic/organic phases to seal the
surface, enhancing the barrier properties on the AISI 1018
commercial carbon steel.
Acknowledgements The authors wish to acknowledge the financial
support provided by CONACYT through the 133618 and 132660
projects, SIP-IPN 2012-0454, 2012-0562 and SNI-CONACYT.
D. Del Angel-López is grateful for her postgraduate fellowship from
SIP-IPN and CONACYT. The authors would also like to thank M. en
C. Marı́a de Jesús Perea Flores, Dr. Hugo Martı́nez Gutiérrez,
Dr. Israel Azrate Vázquez and Dr. J. Vicente Méndez for their
technical support.
References
1. Baldan A (2004) J Mater Sci 39:1. doi:10.1023/B:JMSC.0000
007726.58758.e4
2. Chattopadhyay DK, Raju KVSN (2007) Prog Polym Sci 32:352
3. Król P (2007) Prog Mater Sci 52:915
4. Prisacariu C, Olley RH, Caraculacu AA, Bassett DC, Martin C
(2003) Polymer 44:5407
5. Chattopadhyay DK, Prasad PSR, Sreedhar B, Raju KVSN (2005)
Prog Org Coat 54:296
6. Chattopadhyay DK, Prasad PSR, Sreedhar B, Raju KVSN (2006)
Polymer 47:3814
7. González-Guzmán J, Santana JJ, González S, Souto RM (2010)
Prog Org Coat 68:240
8. Souto RM, Fox V, Laz MM, González S (2000) J Adhes Sci
Technol 14:1321
9. Walter GW (1991) Corros Sci 32:1041
10. Veleva L, Chin J, Del Amo B (1999) Prog Org Coat 36:211
11. Grundmeier G, Rossenbeck B, Roschmann KJ, Ebbinghaus P,
Stratmann M (2006) Corros Sci 48:3716
12. Yang LH, Liu FC, Han E (2005) Prog Org Coat 53:91
13. Popa MV, Drob P, Vasilescu E, Mirza-Rosca JC, Santana-Lopez A,
Vasilescu C, Drob SI (2006) Mater Chem Phys 100:296
14. Kalendova A, Veselý D, Kalenda P (2006) Pigment Resin
Technol 35:83
15. Kalendova A, Vesely D, Kalenda P (2007) Pigment Resin
Technol 36:3
16. Veselý D, Kalendová A, Němec P (2010) Surf Coat Technol
204:2032
17. Szocinski M, Darowicki K, Schaefer K (2010) Polym Degrad
Stab 95:960
123
1084
18. Njuguna J, Pielichowski K (2003) Adv Eng Mater 5:769
19. Baer DR, Burrows PE, El-Azab AA (2003) Prog Org Coat 47:342
20. Ash BJ, Rogers DF, Wiegand CJ, Schadler LS, Siegel RW,
Benicewicz BC, Apple T (2002) Polym Compos 23:1014
21. Ou Y, Yang F, Yu ZZ (1998) J Polym Sci, Part B: Polym Phys
36:789
22. Zhao G, Wang T, Wang Q (2011) J Mater Sci 46:6673. doi:
10.1007/s10853-011-5620-7
23. Castro Y, Aparicio M, Moreno R, Durán A (2005) J Sol-Gel Sci
Technol 3541:50
24. Carmona N, Villegas MA, Fernández Navarro JM (2006) Thin
Solid Films 515:1320
25. Schmidt H (2006) J Sol-Gel Sci Technol 40:115
26. Lópes AC, Gallardo J, Durán A (2001) Bol Soc Esp Ceram
40:429
27. Gurunathan T, Rao CRK, Narayan R, Raju KVSN (2012) J Mater
Sci. doi:10.1007/s10853-012-6658-x
28. Gomez-Romero P (2004) Functional hybrid materials. Wiley-
VCH, Weinheim
29. Zheng SX, Li JH (2010) J Sol-Gel Sci Technol 54:174
30. Ischenko SS, Rosovitskii VF, Pridatko AB, Babkina NV, Lebe-
dev EV (1998) J Appl Chem 11:1929
31. Brinker CJ, Scherer GW (1990) Sol–gel science: the physics and
chemistry of sol–gel processing. Academic Press, San Diego
32. Yoldas BE (1986) J Mater Sci 21:1087. doi:10.1007/BF01117399
33. Bokhimi X, Morales A, Novaro O, López T, Sánchez E, Gómez R
(1995) J Mater Res 10:2788
34. Bokhimi X, Morales A, Novaro O, Portilla M, López T, Tzom-
pantzi F, Gómez R (1998) J Solid State Chem 135:28
35. Papet P, Le Bars N, Baumard JF, Lecomte A, Dauger A (1989)
J Mater Sci 24:3850. doi:10.1007/BF01168946
36. Oliver WC, Pharr GM (1992) J Mater Res 7:1564
37. Nogami M (1986) J Mater Sci 21:3513. doi:10.1007/BF02402996
38. Aguilar DH, Torres-Gonzalez LC, Torres-Martinez LM (2000)
J Solid State Chem 158:349
39. del Monte F, Larsen W, Mackenzi JD (2000) J Am Ceram Soc
83:628
40. Burton AW, Ong K, Rea T, Chan IY (2009) Microporous
Mesoporous Mater 117:75
41. Scherer GW (1997) J Sol-Gel Sci Technol 8:353
42. Huang W, Yang J, Meng X, Cheng Y, Wang C, Zou B, Khan Z,
Wang Z, Cao X (2011) Chem Eng J 168:1360
123
J Mater Sci (2013) 48:1067–1084
43. Khimich NN, Semashko OV, Khimich EN, Voronkov MG (2006)
Russ J Appl Chem 79:351
44. Lamprecht A, Schäfer U, Lehr CM (2000) Int J Pharm 196:223
45. Pidaparti RM, Rao AS (2008) Corros Sci 50:1932
46. Bilmes PD, Llorente CL, Saire Huamán L, Gassa LM, Gervasi CA
(2006) Corros Sci 48:3261
47. Gesnouin C, Hazarabedian A, Bruzzoni P, Ovejero-Garcı́a J,
Bilmes P, Llorente C (2004) Corros Sci 46:1633
48. Yasakau KA, Zheludkevich ML, Lamaka SV, Ferreira MGS
(2007) Electrochim Acta 52:7651
49. Holme B, Lunder O (2007) Corros Sci 49:391
50. Sukamto JPH, Smyrl WH, Casillas N, Al-Odan M, James P, Jin W,
Douglas L (1995) Mater Sci Eng A 198:177
51. Leiva-Garcı́a R, Muñoz-Portero MJ, Garcı́a-Anton J (2009)
Corros Sci 51:2080
52. Leiva-Garcı́a R, Garcı́a-Antón J, Muñoz-Portero MJ (2010)
Corros Sci 52:2133
53. Wang L (2006) Chem Eng News 84:48
54. Nakamura M, Kobayashi M, Kuzuya N, Komatsu T, Mochizuka T
(2006) Thin Solid Films 502:121
55. Hare CH (2001) Paint film degradation: mechanism and control.
SSPC The society for protective coatings, Pittsburgh, PA
56. Wicks ZW Jr, Jones FN, Pappas SP, Wicks DA (2007) Organic
coatings science and technology, 3rd edn. Wiley, New York
57. Williams G, McMurray HN (2003) Electrochem Commun 5:871
58. Roberge RP (2000) Handbook of corrosion engineering. McGraw
Hill, New York
59. Raman A, Nasrazadani S, Sharma L (1989) Metallography 22:79
60. Razvan A, Raman A (1986) Prakt Metallogr 23:223
61. de la Fuente D, Dı́az I, Simancas J, Chico B, Morcillo M (1998)
Corros Sci 40:61
62. Grundmeir G, Schmidt W, Stratmann M (2000) Electrochim Acta
45:2515
63. Zhu D, Ooij WJV (2004) Prog Org Coat 49:42
64. Ahmad S, Zafar F, Sharmin E, Garg N, Kashif M (2012) Prog
Org Coat 73:112
65. Phanasgaonkar A, Raja VS (2009) Surf Coat Technol 203:2260
66. Vuc AS, Fir M, Jese R, Vilcnik A, Orel B (2008) Prog Org Coat
63:123
67. Ferraz O, Cavalcanti E, Di Sarli AR (1995) Corros Sci 37:1267