Progress in Organic Coatings 60 (2007) 117–120

Preparation of epoxy–clay nanocomposite and investigation

on its anti-corrosive behavior in epoxy coating
M.R. Bagherzadeh ∗ , F. Mahdavi
Coating Research Center, Research Institute of Petroleum Industry, N.I.O.C, Tehran, Iran
Received 22 November 2006; received in revised form 4 June 2007; accepted 9 July 2007

Abstract
An epoxy–clay nanocomposite was synthesized using a quaternary ammonium-modified montmorillonite clay and diglycidyl ether of bisphenol
A (DGEBA) type epoxy resin, in order to produce anti-corrosive epoxy coating. Anti-corrosive properties of the nanocomposite were investigated
using salt spray and electrochemical impedance spectroscopy (EIS) methods. The results showed an improvement in the barrier and anti-corrosive
characteristics of epoxy-based nanocomposite coating and a decrease in water uptake in comparison with pure epoxy coating. Wide-angle X-ray
diffraction (WAXD) patterns and transmission electron microscopy (TEM) analysis showed that the interlayer spacing of clays increased after
addition of epoxy resin along with applying shear force and ultrasound sonicator. The best performance of this coating was achieved at 3 and
5 wt.% clay concentration.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Nanocomposite; Epoxy coating; Nanoclay; Water uptake; Barrier; EIS

1. Introduction silane-coupling agents, preparation of epoxy–siloxane hybrid

binders or other methods such as decrease in coating/membrane
Polymer–clay nanocomposites (PCNs) are compounds in permeability of aggressive species [4].
which nanoclay particles are distributed in a polymer matrix. Yasmin et al. [5], Becker et al. [6] and Kim et al. [7]
In recent years, such substances have attracted interest in engi- have studied the mechanical, barrier and molecular permeability
neering and scientific aspects of coating due to their excellent properties of epoxy–clay nanocomposites. Good anti-corrosive
properties, such as high-dimensional stability, heat deflection properties of epoxy–clay nanocomposites and their reduced
temperature, reduced gas permeability, optical clarity, flame gases and moisture permeabilities are the aspects which make
retardancy and enhanced mechanical properties [1,2]. them attractive in order to produce protective coatings.
The barrier, adhesion and inhibiting features have an impor- All types of layered silicates such as smectite, montmo-
tant role in lifetime of coatings. The strength of coating/metal rillonite and saponite are the effective and reinforcing agents
system is in proportion with contact time of system with the in making polymer clay composites. Pristine-layered silicates,
corrosive medium, changes in adhesion, barrier and inhibiting which contain layered Na+ or K+ ions, are only miscible with
properties. Aging and diffusion of corrosive agents such as H2 O, hydrophilic polymers. Through ion-exchange reactions with
O2 and H+ into coating/substrate interface can lead to blister- cationic surfactants layered silicates render miscible with other
ing, reduce stability of the adhesion bond, increase the speed of polymers. Cations reduce the surface energy of the organic host
cathodic reaction and degradation of coating and substrate [3]. and improve wetting characteristics of polymer, resulting in a
Recently many efforts have been done to improve anti- larger interlayer spacing.
corrosive properties of epoxy coatings such as: modifying Several types of morphologies may occur when the poly-
formulation of organic epoxy resins through introduction of mer is mixed with layered silicates: (a) conventional composites
(b) intercalated nanocomposites and (c) exfoliated nanocompos-
ites. Their differences can be related to the polymer permeation
∗ Corresponding author. Tel.: +98 21 55901078; fax: +98 21 55901078. between clay layers and dispersion uniformity of silicate sheets
E-mail address: Bagherzadehmr@ripi.ir (M.R. Bagherzadeh). in polymer matrix. The high aspect ratio of silicate layers plays

0300-9440/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.porgcoat.2007.07.011
118 M.R. Bagherzadeh, F. Mahdavi / Progress in Organic Coatings 60 (2007) 117–120

an important role in production of anti-corrosive coating systems

[1,7,8]. In this study an epoxy–clay nanocomposite coating was
synthesized and its anti-corrosive properties were investigated
using salt spray and EIS test methods.

2. Experimental

2.1. Materials

The nanoclay used in this study was a modified montmo-

rillonite with commercial grade of cloisite 30B® , obtained
from Southern Clay Products. The diglycidyl ether of bisphe-
nol A (DGEBA) epoxy resin (Araldite Razeen LR-2257)
and polyamide hardener (Aradure43SBD) was purchased from
Huntsman Corporation.
Fig. 1. WAXD patterns of cloisite 30B, epoxy–organoclay, epoxy–clay
2.2. Preparation of epoxy–clay nanocomposite coating nanocomposite and pure epoxy.

The desired amount of resin and nanoclay were mixed organoclay, the clay attracts polar epoxy molecules due to its
together. The mixing process was performed in an oil bath high surface energy. Also the presence of alkyl ammonium
(50–70 ◦ C). Then the mixture was subjected to sonication for cations with the strong polarity of the N–H groups in the primary
8–12 h. For fabrication of nanocoating after addition of some and secondary amines catalyze the epoxy homopolymerization
additives to epoxy–clay mixture, the stoichiometric amount of [9–11].
the hardener was added to mixture. By this method, three sam- When the hardener was mixed with epoxy–organoclay mix-
ples containing different amounts of clay (1, 3, and 5 wt.%) were ture the peak shifted to the lower angle with d-spacing of 40.7 Å,
prepared. again indicating an increase in spacing of clay platelets. The
appropriate balance between inter- and extra-gallery reactions,
2.3. Surface preparation and applying the coating together with the resin and amine diffusion, are the key fac-
tors to control the organoclay exfoliation [12]. TEM image
The metallic panels were sandblasted using ASTM D7055 of epoxy–clay nanocomposite, indicate 3–4 nm gallery spacing
and then the nanocoatings were applied by spray on metallic (Fig. 2), and demonstrates that an intercalated nanocomposite
panels. The panels were dried at 23 ◦ C for 1 week. The dry film has been formed.
thickness was 60 ± 5 ␮m.
3.2. Adhesion analysis
2.4. Characterization
Adhesion of coating films on metallic substrates was also
Wide-angle X-ray diffraction (WAXD) was used to evalu- investigated. Table 1 shows the results of adhesion tests for
ate degree of exfoliation and d-spacing between clay platelets. prepared nanocomposite coatings and the sample with no clay
The WAXD study was performed with Philips PW 1840. Trans- content. These results show that the adhesion does not vary
mission electron microscopy was used for distinguishing the
dispersion of platelets in polymer matrix using Philips CM
200-FEG. Adhesion and salt spray tests were performed with
ERICHSEN equipments in accordance with ASTM D3359 and
ASTM B117. Electrochemical impedance spectroscopy (EIS)
test was performed with EG&G equipment.

3. Results and discussion

3.1. TEM and WAXD analysis

The WAXD patterns of cloisite 30B® , pure epoxy,

epoxy–organoclay mixture and epoxy–clay nanocomposite are
shown in Fig. 1. The patterns show a characteristic diffraction
peak at 18 Å for pure cloisite 30B and a peak with d-spacing of
36.8 Å for epoxy–organoclay mixture. The increase of the basal
spacing of clay platelets indicates that intercalation occurred
and epoxy resin diffused into galleries. After mixing resin and Fig. 2. TEM image of epoxy–clay nanocomposite.
 M.R. Bagherzadeh, F. Mahdavi / Progress in Organic Coatings 60 (2007) 117–120 119

Table 1 using nanoclay particles. The aspects of the surface samples are
Adhesion results of epoxy–clay nanocomposite coatings with varying clay con- shown in Fig. 3, indicating excellent anti-corrosive feature of C
tents using ASTM D3359
and D samples in contrast with the A sample which does not
Clay concentration (wt.%) Result contain any organoclay.
– 5B
1 5B 3.4. Electrochemical impedance spectroscopy testing (EIS)
3 5B
5 5B
EIS measurements of each sample were conducted over a fre-
quency range of 105 down to 10−2 Hz using a 10 mV amplitude.
with increase in clay concentration and all of the samples show The electrical capacitance of the coating (C), resistance polar-
excellent adhesion. ization (R) and water uptake values were evaluated from the
Bode curves and log|Z| values. Table 3 shows the log|Z| values.
3.3. Salt spray testing The water uptake values of samples shown in Table 4 and
Fig. 4 obtained from Brasher–Kingsbury equation:
Salt spray test method was used to evaluate performance log(Ct /C0 )
of the epoxy–clay nanocomposite coatings using ASTM B117. water uptake =
log 80
Table 2 shows the results of salt spray tests.
Last studies show that the water permeability in the com- where Ct is the electrical capacitance of the coating during t
pounds with a less powder volume due to decrease in the network time of immersion, C0 the electrical capacitance of the coating
density results in the swelling of the coating film, whereas the before immersion [14]. These results indicate that water uptake
water permeability in the compounds with a higher powder vol- of nanocoatings decreases as the clay concentration increases. In
ume performs through forming holes on the surface of coating the sample with no clay content the water uptake is three times
film as well as extending water distribution highways [13]. How- more than the nanocoating containing 1 wt.% of clay.
ever, the results of present work confirm that increase in the clay In the coating with no clay content, the free volume of poly-
concentration leads to reduction of degradation and blistering meric matrix is higher than in nanocomposite coating, so the
density. This property is one of the remarkable advantages of aggressive compounds can diffuse through microvoids easily.

Table 2
Salt spray results of epoxy–clay nanocomposites with varying clay contents in accordance with ASTM D 714
Clay concentration (wt.%) Results

– A lot of small blisters were observed on the surface (Blister size No. 8, Medium). There was trace of rust under the blisters, and
water penetration from the tracks was about 1 mm
1 Some small blisters were observed on the surface (Blister size No. 6, Few), but there was trace of rust under the blisters
3 There was no blister and water penetration
5 There was no blister and water penetration

Fig. 3. The surface aspect of the samples containing different amounts of clay after exposing to salt spray for 500 h. (A) 0 wt.%, (B) 1 wt.%, (C) 3 wt.%, and (D)
5 wt.% clay concentration.
120 M.R. Bagherzadeh, F. Mahdavi / Progress in Organic Coatings 60 (2007) 117–120

Table 3 Nanocomposite coating with 1 wt.% clay loading shows

log|Z| values of nanocomposite coatings with different amounts of clay about 70% reduction in water uptake. The salt spray and EIS
Clay concentration (wt.%) log|Z| (t = 0) log|Z| (t = 500 h) results show that the barrier properties increase as the clay con-
– 5.64 2.98
centration increases, so there is a significant difference between
1 7.54 6.84 anti-corrosive properties of nanocomposite coatings with 1 and
3 9.26 9.20 5 wt.% clay content. The best performance of the coating was
5 9.36 9.33 achieved at 3 and 5 wt.% clay concentrations.

4. Conclusion
Table 4
water uptake values of nanocomposite coatings with varying clay contents after
500 h exposure to salt spray Incorporating nanoclay particles into organic coatings
improves the anti-corrosive properties of coatings. As the
Clay concentration (wt.%) Water uptake
clay loading increases the barrier and anti-corrosive properties
– 140 increase, so in this work the best anti-corrosive performance of
1 39
coatings was obtained at 3 and 5 wt.% clay concentrations. The
3 3.2
5 1.1 EIS results with 3 and 5 wt.% clay concentration samples were
relatively similar but using 3 wt.% is economically preferred.

References

[1] T. Oh, C. Beatty, H. El-Shall, J. Appl. Polym. Sci. 100 (2006) 3456–
3473.
[2] H. Nalwa, Encyclopedia Nanosci. Nanotechnol. 8 (2004) 791–843.
[3] F. Mansfeld, M.W. kending, S. Tsai, Corrosion 38 (1982) 478–485.
[4] J.M. Yeh, H.Y. Huany, C.L. Chen, W.F. Su, Y.H. Yu, Surf. Coat. Technol.
200 (2006) 2753–2763.
[5] A. Yasmin, J.L. Abot, I.M. Daniel, Scrip. Mater. 49 (2003) 81–85.
[6] O. Becker, R. Varley, G. Simon, Euro. Polym. J. 40 (2004) 187–195.
[7] J.K. Kim, C. Hu, R.S.C. Woo, M.L. Sham, Compos. Sci. Technol. 65 (2005)
805–813.
[8] C. Chen, M. Khobaib, D. Curliss, Prog. Organ. Coat. 47 (2003) 376–383.
[9] X. Konmann, H. Lindberg, L.A. Berglund, Polymer 42 (2001) 4493–4499.
Fig. 4. The variation of water uptake as a function of clay content wt.% for [10] X. Kornmann, H. Lindberg, L.A. Berglund, Polymer 42 (2001) 1303–1310.
nanocomposite coatings containing different concentration of organoclay. [11] I. Chin, T. Albrecht, H. Kim, T. Russell, J. Wang, Polymer 42 (2001)
5947–5952.
[12] O. Becker, R. Varley, G. Simon, Polymer 43 (2002) 4365–4373.
The salt spray and EIS results indicate that degradation in sample [13] G.E. Zaikov, A.A. Iordanski, V.S. Mirkin, Diffusion of Electrolytes in
without any clay is more than for other samples, so incorporation Polymers, Khimiya, 1984, p. 296.
of clay platelets into epoxy matrix results in decrease of water [14] A.S.L. Castela, A.M. Simoes, M.G.S. Ferreia, Prog. Organ. Coat. 38 (2000)
permeability for nanocomposite coating. 1–7.