Mater. Res. Soc. Symp. Proc. Vol.

1819 2016 Materials Research Society

DOI: 10.1557/opl.2016.77

Preparation and characterization of UV-cured epoxy/clay nanocomposite coatings

on carbon steel

Jenaro L. Varela Caselis1, Marco Morales Snchez2, Jos A. Galicia Aguilar2 and Efran
Rubio Rosas1
1
Centro Universitario de Vinculacin y Transferencia de Tecnologa/Benemrita
Universidad Autnoma de Puebla, Prolongacin de la 24 sur y Av. San Claudio, Col.
San Manuel, C.U., C.P. 72570, Puebla, Puebla, Mxico.
2
Facultad de Ingeniera Qumica/Benemrita Universidad Autnoma de Puebla, 18 sur y
Av. San Claudio, Col. San Manuel, C.U., C.P.72570, Puebla, Puebla, Mxico.
ABSTRACT
Polymer-clay nanocomposites are compounds in which nanoclay particles are
distributed in a polymer matrix. Epoxy-clay nanocomposites have become a very
interesting topic among researchers in the past two decades because nanoclays have a
positive effect on the mechanical, thermal and especially barrier anticorrosive
performance of the polymers. In this study, epoxy-montmorillonite organoclay
(OMMT) nanocomposite coatings were prepared and deposited on carbon steel
substrates. The coatings were prepared through in situ polymerization and by UV-curing
technique. The OMMT was added to epoxy resin at loadings between 0 wt.% and 5
wt.%, the particles of OMMT were dispersed using forced agitation-sonication and
deposited on carbon steel coupons. The nanocomposite coatings obtained have been
characterized by scanning electron microscopy (SEM), spectroscopy Fourier transform
infrared (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and
evaluated their corrosion protection effect on cold rolled carbon steel coupons by
performing visual analysis. The X-ray analysis showed that exfoliation occurred for the
OMMT in the polymer matrix, the SEM analysis showed that OMMT was homogenous
dispersed in the polymer matrix and the coatings were uniform. The FTIR analysis
showed the characteristic bands of epoxy resin and OMMT in the composite. The
results showed that 1 wt.% OMMT coating exhibit better anticorrosive properties than
pure epoxy.

INTRODUCTION
Organic or polymeric coatings on metallic substrates provide an effective barrier
between the metal and its environment and/or inhibit corrosion through the presence of
chemicals. During the early stage of corrosion protection engineering, various neat
organic or polymeric coatings were developed. These coatings generally function as a
physical barrier against aggressive species such as O2 and H+ that cause decomposition.
Examples of representative polymers are include epoxy resins [1,2], polyurethanes, and
polyesters [3,4].

Conversely, not all neat polymeric coatings are permanently impenetrable because small
defects in the coatings can lead to gateways that allow corrosive species to attack the
metallic substrate; thus, localized corrosion can occur. As a second line of defense
against corrosion, various nanoscale inorganic additives have been incorporated into
various polymer matrices to generate a series of organicinorganic hybrid anticorrosive
coatings. Recently, layered silicate (clay) has attracted intensive research interest for the
preparation of polymer-clay nanocomposites because its lamellar elements display high
inplane strength, stiffness, and high aspect ratios. Polymer-clay nanocomposites are
compounds in which nanoclay particles are distributed in a polymer matrix. Different
nanoclays can be employed as filler, in particular montmorillonite, bentonite, sepiolite,
and halloysita [5,8]. The nanocomposites containing montmorillonite show remarkable
barrier properties to gases and moisture as well as very good resistance to staining [911]. Thus, it is particularly interesting the preparation of montmorillonite reinforced
polymeric thin films for coating application. In that case, the ultraviolet (UV)-curing
technique can be successfully employed to produce hybrid materials, mainly in form of
films, building up polymeric thermoset matrices. UV light induces polymerization and
allows a fast transformation of the liquid monomer into the solid film with tailored
physico-chemical and mechanical properties. This process [12] is very fast and
environmentally friendly: complete conversion is usually obtained in seconds, the
substrate does not need to be heated as in the traditional thermal curing (therefore it
guarantees the saving of energy), the polymerization takes place in the bulk and no
solvent is employed (thus the release of volatile organic compounds, VOC, is
minimized). The purpose of this study was monitoring the effect of the presence of the
silica nanopowder on the kinetic of cationic photopolymerization of an epoxy based
system, and to study the properties of the obtained photocured nanocomposites films.

EXPERIMENTAL DETAILS
The Araldite 506 epoxy resin was purchased to Sigma-Aldrich, and use as
epoxy-system based. A mixture of triarylsulfonium hexafluorophosphate salts as 50%
solution in propylene carbonate was purchased to Sigma-Aldrich. The filler was an
organophilic montmorillonite (OMMT), nanoclay surface modified contains 20-30 wt.%
methyl dihydroxyethyl hydrogenated tallow ammonium. The OMMT was dispersed in
the liquid resin Araldite 506, at concentrations of 0.0, 1, 3 and 5 wt.%. The procedure
was as follow: mechanical mixing for 2 hours at 60 C and then sonication for 2 hours
at room temperature. The photocurable formulations were then added of the cationic
photoinitiator at 2 wt.%. The mixtures were coated onto a carbon steel substrate using a
wirewound applicator; they were exposed to UV light using a lamp at 20mW/cm2 for 5
min, and 113-116 m thick films were obtained. All the polymerization reactions were
performed at room temperature. The system based on OMMT and epoxy monomer was
investigated, through different characterization techniques. The nanocomposite coatings
obtained have been characterized by scanning electron microscopy (SEM) using a JEOL
SEM (model JSM-6610LV) equipped with an Oxford Instruments energy dispersive Xray spectroscopy, for the Fourier transform infrared spectroscopy (FTIR), a Bruker
spectrometer model Vertex 70 was used, operated in the interval of 5004000 cm-1, for
X-ray diffraction (XRD) analysis was used a Bruker diffractometer model D8 Discover,

thermogravimetric analysis (TGA) was made with a Netzsch thermal analyzer model
STA 449 F3 Jpiter, their corrosion protection effect was evaluated on cold rolled
carbon steel coupons by performing visual analysis according ASTM D610 and ASTM
D 714.

DISCUSSION
The synthesized coatings were studied in terms of homogeneity and surface
morphology by SEM. SEM images showing the surfaces of epoxy and nanocomposite
coatings are presented in Figure 1. The epoxy coating had a relatively smooth surface
morphology, with no cracks or discontinuities being detected (Fig. 1a). SEM images
show that the brittle fracture surface of the cured epoxy resin becomes rougher when the
clay is incorporated into the polymer matrix (Figure 1b). The bright spots observed on
the surface correspond to the finely dispersed clay aggregates with in the epoxy resins.
The coatings thickness was in the order of 113-116 microns (figures 1c and d).

Figure 1. SEM micrographs, showing the surface of (a)

epoxy coating, (b) epoxy-OMMT coating and (c,d) cross
section of the coatings deposited on carbon steel.
TEM is one of the most widely applied tools to investigate nanocomposite
superstructure. With magnifications of up to 300,000 times, this powerful technique
allows the edges of individual silicate platelets to be imaged. TEM analysis is the main
method that provides sharp images on a nanometer dimension. The TEM picture of
figure 2, confirmed a certain degree of intercalation (occurred during the dispersion).

20

nm

Figure 2. TEM photograph of epoxy-organoclay

nanocomposites with 5% OMMT
The dispersion state of OMMT in epoxy resin was studied by XRD. Figure 3
illustrates the XRD patterns of pure organoclay, the epoxy-OMMT coatings with 15
wt.% organoclay content and the cured epoxy resin. The XRD pattern of organoclay
shows one very intense diffraction peak of the (001) plane at 4.9 and one weak peak of
the (002) plane at 9.5 corresponding to the clay interlayer d-spacing. The existence of a
very broad and stretched peak at about 20 in the diffractograms, is related to
amorphous structure of cured epoxy resin. Also, it can be noticed the relative intensity
of the small overlapped peak situated around 19.5, which corresponds to
crystallographic (110) and (020) planes of the clay layer and which is independent of
the basal spacing. The absence of two diffraction maxima of the (001) and (002) planes
for the epoxy-OMMT samples indicate that organoclay was dispersed.

Figure 3. DRX diffractograms of the epoxy/organoclay

composites

The synthesized samples were analyzed by FTIR with the aim of monitoring the
UV curing reaction of epoxy resin. Epoxy group conversion was followed by
monitoring the decrease of the absorbance of the oxirane group band in the region 760
780cm-1. In figure 4, spectra before and after UV-illumination of the coating present the
main band characteristics. The absorption band located at 780 cm-1 corresponds to the
oxirane group. The figure clearly shows that the band corresponding to oxirane group is
present in the samples corresponding to 1, 3 and 5 wt.% OMMT, this band is observed
with greater intensity in the sample containing 5 wt.% OMMT. These results assume
that the UV curing was not carried completely and UV curing was being affected by a
high concentration of OMMT.
The thermal properties of the nanocomposite coatings were characterized by
TGA in nitrogen atmosphere. Figure 5 shows the TGA thermogram of the
nanocomposites, it can be seen that the sample had better thermal stability corresponds
to sample epoxy resin whereas the sample that had lower thermal stability corresponds
to the sample containing 5 wt.% OMMT. The cause of these results may be due to
incomplete curing of the samples containing OMMT, in Figure 4 the sample containing
5 wt.% OMMT shows a band of increased intensity of the oxirane group indicating that
this sample had the poorest curing compared to the other samples.

Figure 4. FTIR spectra of coatings

Figure 5. TGA thermograms

Figure 6 show the coatings before and after immersion testing in a solution of
sodium chloride 5 wt.%. After exposure of the samples for about 768 h, as shown in
Figure 6b, a brown adherent corrosion product (which is a mixture of iron hydroxides)
was observed all over the samples surface. Delamination and water penetration were
observed around the scratches which decreased in the order of 5 wt% OMMT sample
>3 wt% OMMT sample > epoxy sample >1 wt% OMMT sample. Immersion tests
clearly indicate that the coating that showed less corrosion coating was the 1%
montmorillonite, this is clearly seen in Figure 6b. This result enables us to conclude that
particularly montmorillonite may be used to improve corrosion protection properties of
the epoxy coating.

Figure 6. Epoxy-montmorillonite coatings: a)before and b)after of 768 hours

immersion in solution 5% NaCl.

CONCLUSIONS
The X-ray analysis showed that intercalation was occurred for the OMMT in the
polymer matrix, and it was confirmed by TEM. SEM analysis showed that OMMT was
homogenous dispersed in the polymer matrix. The addition of 5% of OMMT to an
organic polymer such as epoxy resin affects the UV curing. Epoxy-OMMT coatings
uniform and free of defects were obtained on a corrodible surface as carbon steel.
Visual evaluation test in a solution of 5% NaCl showed that the 1 wt% OMMT coating
have better resistance to corrosion for carbon steel that epoxy coating.

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