Professional Documents
Culture Documents
, 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 epoxyclay nanocomposite was synthesized using a quaternary ammonium-modied 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
Polymerclay nanocomposites (PCNs) are compounds in
which nanoclay particles are distributed in a polymer matrix.
In recent years, such substances have attracted interest in engi-
neering and scientic aspects of coating due to their excellent
properties, such as high-dimensional stability, heat deection
temperature, reduced gas permeability, optical clarity, ame
retardancy and enhanced mechanical properties [1,2].
The barrier, adhesion and inhibiting features have an impor-
tant role in lifetime of coatings. The strength of coating/metal
system is in proportion with contact time of system with the
corrosive medium, changes in adhesion, barrier and inhibiting
properties. Aging and diffusion of corrosive agents such as H
2
O,
O
2
and H
+
into coating/substrate interface can lead to blister-
ing, reduce stability of the adhesion bond, increase the speed of
cathodic reaction and degradation of coating and substrate [3].
Recently many efforts have been done to improve anti-
corrosive properties of epoxy coatings such as: modifying
formulation of organic epoxy resins through introduction of
, 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.
2.2. Preparation of epoxyclay nanocomposite coating
The desired amount of resin and nanoclay were mixed
together. The mixing process was performed in an oil bath
(5070
, pure epoxy,
epoxyorganoclay mixture and epoxyclay nanocomposite are
shown in Fig. 1. The patterns show a characteristic diffraction
peak at 18
A for pure cloisite 30B and a peak with d-spacing of
36.8
A for epoxyorganoclay 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. 1. WAXD patterns of cloisite 30B, epoxyorganoclay, epoxyclay
nanocomposite and pure epoxy.
organoclay, the clay attracts polar epoxy molecules due to its
high surface energy. Also the presence of alkyl ammonium
cations with the strong polarity of the NHgroups in the primary
and secondary amines catalyze the epoxy homopolymerization
[911].
When the hardener was mixed with epoxyorganoclay mix-
ture the peak shifted to the lower angle with d-spacing of 40.7
A,
again indicating an increase in spacing of clay platelets. The
appropriate balance between inter- and extra-gallery reactions,
together with the resin and amine diffusion, are the key fac-
tors to control the organoclay exfoliation [12]. TEM image
of epoxyclay nanocomposite, indicate 34 nm gallery spacing
(Fig. 2), and demonstrates that an intercalated nanocomposite
has been formed.
3.2. Adhesion analysis
Adhesion of coating lms on metallic substrates was also
investigated. Table 1 shows the results of adhesion tests for
prepared nanocomposite coatings and the sample with no clay
content. These results show that the adhesion does not vary
Fig. 2. TEM image of epoxyclay nanocomposite.
M.R. Bagherzadeh, F. Mahdavi / Progress in Organic Coatings 60 (2007) 117120 119
Table 1
Adhesion results of epoxyclay nanocomposite coatings with varying clay con-
tents using ASTM D3359
Clay concentration (wt.%) Result
5B
1 5B
3 5B
5 5B
with increase in clay concentration and all of the samples show
excellent adhesion.
3.3. Salt spray testing
Salt spray test method was used to evaluate performance
of the epoxyclay nanocomposite coatings using ASTM B117.
Table 2 shows the results of salt spray tests.
Last studies show that the water permeability in the com-
pounds with a less powder volume due to decrease in the network
density results in the swelling of the coating lm, whereas the
water permeability in the compounds with a higher powder vol-
ume performs through forming holes on the surface of coating
lmas well as extending water distribution highways [13]. How-
ever, the results of present work conrmthat increase in the clay
concentration leads to reduction of degradation and blistering
density. This property is one of the remarkable advantages of
using nanoclay particles. The aspects of the surface samples are
shown in Fig. 3, indicating excellent anti-corrosive feature of C
and D samples in contrast with the A sample which does not
contain any organoclay.
3.4. Electrochemical impedance spectroscopy testing (EIS)
EIS measurements of each sample were conducted over a fre-
quency range of 10
5
down to 10
2
Hz using a 10 mVamplitude.
The electrical capacitance of the coating (C), resistance polar-
ization (R) and water uptake values were evaluated from the
Bode curves and log|Z| values. Table 3 shows the log|Z| values.
The water uptake values of samples shown in Table 4 and
Fig. 4 obtained from BrasherKingsbury equation:
water uptake =
log(C
t
/C
0
)
log 80
where C
t
is the electrical capacitance of the coating during t
time of immersion, C
0
the electrical capacitance of the coating
before immersion [14]. These results indicate that water uptake
of nanocoatings decreases as the clay concentration increases. In
the sample with no clay content the water uptake is three times
more than the nanocoating containing 1 wt.% of clay.
In the coating with no clay content, the free volume of poly-
meric matrix is higher than in nanocomposite coating, so the
aggressive compounds can diffuse through microvoids easily.
Table 2
Salt spray results of epoxyclay 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) 117120
Table 3
log|Z| values of nanocomposite coatings with different amounts of clay
Clay concentration (wt.%) log|Z| (t =0) log|Z| (t =500 h)
5.64 2.98
1 7.54 6.84
3 9.26 9.20
5 9.36 9.33
Table 4
water uptake values of nanocomposite coatings with varying clay contents after
500 h exposure to salt spray
Clay concentration (wt.%) Water uptake
140
1 39
3 3.2
5 1.1
Fig. 4. The variation of water uptake as a function of clay content wt.% for
nanocomposite coatings containing different concentration of organoclay.
The salt spray and EISresults indicate that degradation in sample
without any clay is more than for other samples, so incorporation
of clay platelets into epoxy matrix results in decrease of water
permeability for nanocomposite coating.
Nanocomposite coating with 1 wt.% clay loading shows
about 70% reduction in water uptake. The salt spray and EIS
results show that the barrier properties increase as the clay con-
centration increases, so there is a signicant difference between
anti-corrosive properties of nanocomposite coatings with 1 and
5 wt.% clay content. The best performance of the coating was
achieved at 3 and 5 wt.% clay concentrations.
4. Conclusion
Incorporating nanoclay particles into organic coatings
improves the anti-corrosive properties of coatings. As the
clay loading increases the barrier and anti-corrosive properties
increase, so in this work the best anti-corrosive performance of
coatings was obtained at 3 and 5 wt.% clay concentrations. The
EIS results with 3 and 5 wt.% clay concentration samples were
relatively similar but using 3 wt.% is economically preferred.
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