Progress in Organic Coatings 77 (2014) 725732

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Progress in Organic Coatings
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Novel water based coatings containing some conducting polymers
nanoparticles (CPNs) as corrosion inhibitors
Noha Elhalawany
a,
, Michael A. Mossad
b
, Magdy K. Zahran
c
a
Polymers and Pigments Department, National Research Center, Cairo, Egypt
b
Eagle Chemicals Company, 6th October, Egypt
c
Helwan University, Cairo, Egypt
a r t i c l e i n f o
Article history:
Received 10 March 2013
Received in revised form
26 December 2013
Accepted 27 December 2013
Keywords:
Anticorrosive water-based paints
Conducting polymers nanoparticles
Paint formulations and miniemulsion
polymerization
a b s t r a c t
A new type of anticorrosive water-based paints containing some conducting polymers nanoparticles
(CPNs) such as poly anisidine (PAns), poly toluidine (PTol) and their copolymer (CCPNs) have been pre-
pared and evaluated. The CPNs and CCPNs have been synthesized via miniemulsion polymerization. The
prepared materials have been characterized by GPC, FTIR, TEM and DSC. The prepared CPNs and CCPNs of
different weight percentages (wt.%) have been incorporated into paint formulations. It has been found that
the presence of the prepared CPNs and CCPNs in the paint formulations highly enhanced the resistance
of the formed paint lms against washability, weathering and corrosion.
2014 Elsevier B.V. All rights reserved.
1. Introduction
Corrosion is considered as the silent enemy which threatens
the endurance of steel and infrastructures in all countries with-
out exception, leading to plant shutdowns, waste of valuable
resources, loss or contamination of products, reduction in ef-
ciency, costly maintenance, and expensive over design. In addition,
it also jeopardizes safety and inhibits technological progress, and
this involves annual losses of billion dollars worldwide. The con-
ventional anticorrosive coatings which are based on heavy metals
such as chromium, zinc and copper are toxic to the environment.
So there has been a need to nd suitable coatings which are envi-
ronmentally friendly and effective to inhibit corrosion of steels.
Environmentally friendly nature and high effectiveness make con-
ducting polymers a suitable replacement of conventional coatings
to combat corrosion in different environments. Conducting poly-
mers can interact with the metal substrate and form a passive
oxide layer to inhibit corrosion process due to their redox proper-
ties. Among these polymers is polyaniline which has been widely
studied due to its lowcost, ease of process, high conductivity, envi-
ronmental stability and redox properties [1,2]. Polymeric coatings
containing polyaniline, polypyrrole and polythiophene have been
usedto protect steel against corrosion[3,4]. Corrosionprotectionof

Corresponding author. Tel.: +20 2 33371499; fax: +20 2 33370931.

E-mail addresses: nohaelhalawany1@yahoo.com, elhalawany1970@hotmail.com
(N. Elhalawany).
steels using coating containing polypyrrole/clay nanocomposite [5]
and alkyd coatings containing polyaniline [6] has been well stud-
ied. The formation of coating on active metals is rendered difcult
by the general lack of solubility of conducting polymers. Though
a popular route, the electrodeposition of conducting polymers
is a difcult process involving a complicated mechanism [7].
The mechanism of protection of steels using conducting poly-
mers has been well described [8,9]. One of the important factors
is the homogeneous distribution of conducting polymers in the
coating material. In order to obtain the homogeneous dispersion
of conducting polymers inside of paint, a substituent is incor-
porated to facilitate the solubility of the conducting polymers
[10].
The present study reports the synthesis and characterization of
some CPNs based on polytoluidine, polyanisidine and their copoly-
mer (CCPNs) using miniemulsion polymerization technique. The
preparedCPNs andCCPNs dispersedinanaqueous mediahavebeen
incorporated into water based paint. The basic properties as well
as anticorrosion studies of the blank paint lms and paint lms
containing the prepared CPNs and CCPNs have been investigated
and evaluated. No literature is available on the synthesis of Poly
toluidine, poly anisidine and their copolymer via miniemulsion or
their use as anticorrosive inhibitors in water based paints. Hence
an attempt has been made to synthesize them and to study their
anticorrosion properties. Thus, this paper should pave the way for
the development of new coating technologies based on the intro-
duction of polytoluidine, poly anisidine and their copolymer as
anticorrosive additives.
0300-9440/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.porgcoat.2013.12.017
726 N. Elhalawany et al. / Progress in Organic Coatings 77 (2014) 725732
2. Experimental
2.1. Materials
O-toluidine (99.5%) (Tol) and dodecyl benzene sulfonic acid
(DBSA) have been supplied fromSigmaAldrich Company, USA. O-
anisidine (99.5%) (Ans) has been supplied from MERCK, Germany.
Styrene (St) has been supplied from (ARKEMA CANADA Inc.) and
used as essential monomer. Butyl acrylate monomer (BA), Sodium
metabisulte (SMBS) and Plurafac LF 901 (nonionic fatty acid
alkoxylate surfactant) have been supplied from BASF Company,
Germany. Emulsogen EPA 073 (Sodium alkyl ether sulfate surfac-
tant) has been supplied from Clariant International Ltd., Muttenz,
Switzerland. Ammoniumpersulphate (APS, 99%) has been supplied
from AKKIM Company, Turkey. Calcium carbonate ller has been
supplied from Al-Faltas Company, Cairo, Egypt. Titanium dioxide
(under the trade name rutile R-902), has been supplied from Du-
pont Company, Wilmington, USA and used as the main pigment.
Ammonia has been used as pHstabilizers and supplied fromCHIMI
ART Chemicals Company, Cairo, Egypt. Tylose (under the trade
name Tylose

H30000 YP2) has been used as thickening agent and

supplied fromGmbH & Co.KG Company, Kapfenberg, Austria. Tex-
anol, WD-EAGLE (AS 40/40) and Tetra potassium pyrophosphate
has been supplied from Eastman Chemical Company, Melbourne,
Australia, EagleChemicals Company, 6thOctober, Egypt andEnergy
Chemical Company, China respectively. Anti-foaming agent and
antibacterial agent (Acticide HF) have been purchased fromMnz-
ing Chemie, Germany and Clariant International Ltd., Muttenz,
Switzerland respectively.
2.2. Preparation of the CPs
2.2.1. Synthesis of poly toluidine (PTol)
Tol and DBSA of ratio (1:1) have been mixed in water and iso-
propanol (IPA) mixture of ratio (3:1) respectively under continuous
vigorous stirring using a homogenizer at 10,000rpm for 5min to
formthe miniemulsion. A25ml of (1%) ammoniumpersulfate (APS)
solution has been added dropwisely to the former miniemulsion
under continuous vigorous stirringat 10,000rpmfor further 10min
at room temperature. A color change from white to brownish red
then to dark pink has been observed. At the nal stage of polymer-
ization, a dark pink stable PTol/DBSA dispersion has been obtained
as shown in Fig. 1. The produced stable dispersion of PTol has been
cooled below25

C and then kept for further use.

2.2.2. Synthesis of polyanisidine (PAns)
The same procedure as previously mentioned has been made to
prepare a stable dark green colloidal dispersion of PAns. A color
change from white to pale green then to dark green has been
observed. Finally, a dark green stable PAns/DBSA dispersion has
been obtained as shown in Fig. 2. The produced stable dispersion
of PAns has been cooled below25

C and then kept for further use.

2.2.3. Synthesis of the conducting copolymer nanoparticles
(CCPNs)
(Tol) and (Ans) monomers of feed composition (1:1) have been
mixed in 1% DBSA surfactant dissolved in water and isopropanol
(IPA) mixture of ratio (3:1) respectively under continuous vigor-
ous stirring at 10,000rpm for 5min using a homogenizer to form
the miniemulsion. A 25ml of (1%) APS solution has been added
dropwisely to the former miniemulsion under continuous vigor-
ous stirring at 10,000rpmfor further 10min at roomtemperature.
A color change from white to pale brown then to dark brown has
been observed. At the nal stage of copolymerization, a brown sta-
ble P(Tol-co-Ans)/DBSA dispersion has been obtained as shown in
Fig. 1. Stable dark pink PTol/DBSA colloidal dispersion.
Fig. 3. The produced stable dispersion has been cooled below25

C
and kept for further use.
2.2.4. Synthesis of (St/BA) emulsion
Semi-continuous emulsion copolymerization has been carried
out on a semi-pilot scale at Research and development depart-
ment, Eagle chemicals company, Egypt, in three Liters stainless
steel reactor equipped with a reux condenser, a thermometer,
three droppingfunnels anda mechanical stirrer. Only8%of the total
monomer mixturehas beenintroducedat thebeginningof thereac-
tion at 65

C and the remaining monomer mixture has been added

dropwisely at 802

during the remaining time. Redox systemof

Tetra butyl hydroperoxide and Sodiummetabisulte (SMBS) have
beenaddedafter 30min fromadditionof monomers at 65

C. Emul-
sion copolymerization has been carried out for 4h under nitrogen
gas conditions according to the recipe shown in Table 1. The pro-
duced latex has been ltered, cooled below30

C and then kept for

further use.
Fig. 2. Stable dark green PAns/DBSA colloidal dispersion.
N. Elhalawany et al. / Progress in Organic Coatings 77 (2014) 725732 727
Fig. 3. Stable dark brown P(Ans-co-Tol) DBSA colloidal dispersion.
2.3. Characterization of the prepared materials
FT-IR analysis of the prepared materials has been carried out
at Infra-Red unit, Central service labs, National Research Center
(NRC) using FT-IR-6100, Japan. The molecular weight determi-
nation has been made using GPC, Agilent 1100 series, Germany.
Thermal analysis for the prepared materials has been carried out at
Thermal Analysis unit, Central service labs, (NRC) using Diamond
DSC Perkin Elmer, USA. Samples have been measured using trans-
mission electron microscope TEM+DEM Joel-JEM 1230, Japan at
Electron Microscope Lab, Physics Department (NRC).
2.4. Paint lmtesting
Paint lmtesting has been used to conrmsome basic physical
properties of thecoatings after it is appliedanddried. Theresistance
of the paint lms to corrosion has been also examined.
2.4.1. Physical properties
The gloss, whiteness, and opacity of paint lms have been
measured in accordance with ASTM D 523-89 (1999) using
Spectromatch Gloss 45/0

from Sheen-Instruments Company.

Mandrel-Bending tester from BYK-Gardner Company has been
used to measure a range of elongation of a dry paint lm
in accordance with ASTM D 522-93a (2001). The hardness of
Table 1
Rawmaterials of emulsion copolymerization.
Rawmaterials Wt. in grams
Initial reactor charge
De-ionized water 600
Plurafac LF901 10
Emulsogen EPA 073 4
Monomer mixture
Water 350
Plurafac LF901 35
Emulsogen EPA 073 32
Styrene 620
Butylacrylate 530
Initiator mixture
Tetra butyl hydroperoxide 0.7
Sodiummetabisulphite 0.5
paint has been evaluated in accordance with ASTM D 4366-95
with Pendulum Hardness Rocker tester; model 707 KONIG from
Sheen-Instruments. The adhesion power of paint lm to the base
substrates has been tested in accordance with ASTM D 3359-97
using the cross-cut test instrument-Sheen Company. CHOC Vari-
able Impact Tester from Braive Instruments has been used to
measure resistance of organic coatings to the effects of rapid defor-
mation (Impact) in accordance with ASTMD 2794 93 (1999).
2.4.2. Weathering resistance test
Weathering-resistance and light stability test has been mea-
sured in accordance with ISO 4892-3 by Accelerated Weathering
Tester, Model QUV/Spray with solar eye Irradiance control fromQ-
Lab Corporation, USA. To simulate outdoor weathering, the QUV
tester exposes materials to alternating cycles of UV light and mois-
ture at controlled elevated temperatures. It simulates the effects of
sunlight using special uorescent UVlamps (Type: UVA340) which
give the best simulation of sunlight in the critical short wavelength
regionfrom365nmdowntothesolar cut-off of 295nm. It simulates
dewand rain with condensing humidity and/or water spray.
2.5. Corrosion studies
The corrosion study has been carried out with hand-made
equipment developed in Research and Development Department,
Eagle Chemical Company, Egypt. Air bubbles have been allowed
to go through an aggressive solution medium which consists of
an aqueous solution of NaCl (3.5wt.%). The painted steel panels
have been scratched with a sharp blade to obtain X-cut through
the coating under test. The panels have beenimmersedinthe above
solutionmedium(articial seawater) for 28days. At this time, these
panels have been washed with distilled water and dried.
3. Results and discussion
The prepared (CPNs) and their copolymer (CCPNs) should be
dissolved in water/alcohol mixture to be compatible and suitable
for use in waterborne systems. Solubility of conducting polymers
(CPs) has gained special importance, both scientically and com-
mercially. Cao et al. [11] in 1992 used functionalized protonic
acids to convert polyaniline (PANI) into the metallic form and,
simultaneously, render the resulting PANI complex soluble in com-
mon organic solvents. The functionalized counter ion acts like a
surfactant in that the charged head group is ionically bound to
the oppositely charged protonated PANI chain, and the tail is
chosen to be compatible with nonpolar or weakly polar organic
liquids [1214]. This approach is also known as counter-ion-
induced processability. In this manuscript, the polymerization of
aniline derivatives (toluidine and anisidine) and their copolymer
in presence of protonic acid such as DBSA has been described in
Schemes 1 and 2, respectively.
The molecular weight (M.wt) determination of the prepared
(CPNs) and their copolymer (CCPNs) has been done using GPC tech-
nique. It has been found that the prepared PTol, Pans and their
copolymer (CCPNs) have lowmolecular weight of (7307, 6878 and
8195) and a polydispersity index (D
w
/D
n
) of (1.9, 1.3 and 1.5),
respectively. Where D
w
is the weight average particle diameter and
D
n
is the number average particle diameter.
3.1. Characterization of the prepared materials
3.1.1. FT-IR spectra of the prepared CPs
Fig. 4 shows the FT-IR of the prepared CPNs and their CCPNs.
It shows the main peaks characteristic of PTol and PAns as those
described in literature for poly aniline [15,16]. The peaks charac-
teristic of PTol and PAns can be assigned as follows: C C stretching
728 N. Elhalawany et al. / Progress in Organic Coatings 77 (2014) 725732
Scheme 1. Polymerization of toluidine and/or anisidine in presence of DBSA.
of benzene rings at 1400 and 1440cm
1
, C N stretching of aro-
matic amines at 1255cm
1
and the bands at 1660 and 1661cm
1
assigned to the non-symmetric benzene ring stretching mode (the
ring stretching in quinoid unit and ring stretching in benzenoid
one). The bands at 2926 and 1497cm
1
are assigned to CH
3
and
OCH
3
groups of PTol and PAns, respectively. FT-IR spectrumof the
copolymer has shown the same characteristic peaks as previously
mentioned but they are slightly shifted due to copolymerization.
3.1.2. Transmission electron microscope (TEM) of the prepared
CPs and their copolymer
Fig. 5ac shows the TEMmicrograph of the prepared PTol, Pans
and their copolymer, respectively. It is clearly seen fromthe micro-
graphs 5
a
and 5
b
that the morphology of the prepared PTol has
nano-sphere structure in the size ranging from 62nm to 115nm
and the morphology of the prepared PAns has nano-rod structure
in the size ranging from 96nm to 114nm. Finally, micrograph 5
c
has conrmed that the morphology of the prepared copolymer has
both the nanosphere and nano-rod structures at the same time
indicating the formation of the copolymer.
Fig. 4. FT-IR spectra of the prepared CPNs and their copolymer.
3.1.3. Differential scanning calorimetric analysis (DSC)
Fig. 6 shows the DSC analysis of CE containing the prepared
CCPNs. It is well knownfromthe literature that the DSC exothermic
peak corresponding to decomposition temperature of the tradi-
tional styrene/butylacrylate copolymer is low [17]. As a result of
the presence of the conducting copolymer nanoparticles (CCNs)
higher decompositiontemperaturehas beenobtained. TheDSCdia-
gram shows one exothermic peak indicating the compatibility of
the St/BA emulsion with the present CCPNs.
Scheme 2. Copolymerization of toluidine (Tol) and anisidine (Ans) in presence of DBSA.
N. Elhalawany et al. / Progress in Organic Coatings 77 (2014) 725732 729
Fig. 5. TIMof the stable colloidal dispersions of (a) PToL, (b) PAns and (c) P(Ans-co-ToI).
Fig. 6. DSC diagramof CE containing CCPNs.
3.2. Water based paint formulations
The binder used here is the St/BA emulsion (solid content
50%). St/BA latex specication is shown in Table 2. St/BA emulsion
has been simply blended with the prepared PTol, PAns and their
copolymer (1:1 composition) to give the corresponding compos-
ite emulsions CE
1
, CE
2
and CE
3
, respectively. Blank, CE
1
, CE
2
and
CE
3
samples have been incorporated into paint formulations. Each
composite emulsion consists of four different samples having four
different concentrations (1.5%, 3%, 6% & 9%) of total paint formula-
tion respectively. The detailed paint formulations of the blank, CE
1
,
Table 2
St/BA latex specications.
Latex specication
State Liquid
Color Milky white
Av. (M.wt.) 289,360g/mol
Non-volatile content by weight (%) 50% 1
Viscosity (Brookeld) Spindle4 at 23

C ( CPs) 1000-5000
pH 7-8
MFFT, (

C) (minimumlmforming temperature) 18
Specic gravity (g/ml) 1.06
Particle size (m) 0.1
Water solidication temperature 0 C
Water vapor temperature 100 C
Table 3
Blank paint formulation.
Composition Weight (g)
Water 200
Tetra potassiumpyrophosphate 2
WD-EAGLE (AS4/40) 3
Texanol 4
Antifoaming agent 6
Tylose H30,000 3
Ammonia 2
Titaniumdioxide 150
CaCo
3
25
Binder 50% 600
HF antibacterial agent 5
Total 1000
CE
2
and CE
3
samples are represented in Tables 36, respectively.
Each paint has been applied on steel, tin and glass panels and dried
at roomtemperature for 1 week before the measurements.
3.3. Physico-mechanical tests
The physico-mechanical test results of the paint lms of blank,
CE
1
, CE
2
and CE
3
samples after one week from dryness have been
measuredandtabulatedinTables 79. The data showninthe tables
indicate that the presence of CPNs and CCPNs in the lm paints
has not affected too much the basic properties of the resultant
Table 4
Emulsion paint formulations of CE
1
samples.
Composition CE
1
A
1
A
2
A
3
A
4
Water 185 170 140 110
Tetra potassiumpyrophosphate 2 2 2 2
WD-EAGLE (AS4/40) 3 3 3 3
Texanol 4 4 4 4
Antifoaming agent 6 6 6 6
Tylose H30,000 3 3 3 3
Ammonia 2 2 2 2
Titaniumdioxide 150 150 150 150
CaCo3 25 25 25 25
St/BA emulsion 600 600 600 600
HF antibacterial 5 5 5 5
Poly toluidine (PTol) 15 30 60 90
Total 1000g 1000g 1000g 1000g
730 N. Elhalawany et al. / Progress in Organic Coatings 77 (2014) 725732
Table 5
Emulsion paint formulations of CE
2
samples.
Composition CE
2
B
1
B
2
B
3
B
4
Water 185 170 140 110
Tetra potassiumpyrophosphate 2 2 2 2
WD-EAGLE (AS4/40) 3 3 3 3
Texanol 4 4 4 4
Antifoaming agent 6 6 6 6
Tylose H30,000 3 3 3 3
Ammonia 2 2 2 2
Titaniumdioxide 150 150 150 150
CaCo
3
25 25 25 25
St/BA emulsion 600 600 600 600
HF antibacterial agent 5 5 5 5
Poly anisidine (PAns) 15 30 60 90
Total 1000g 1000g 1000g 1000g
Table 6
Emulsion paint formulations of CE
3
samples.
Composition CE
3
C
1
C
2
C
3
C
4
Water 185 170 140 110
Tetra potassiumpyrophosphate 2 2 2 2
WD-EAGLE (AS4/40) 3 3 3 3
Texanol 4 4 4 4
Antifoaming agent 6 6 6 6
Tylose H30,000 3 3 3 3
Ammonia 2 2 2 2
Titaniumdioxide 150 150 150 150
CaCo
3
25 25 25 25
St/BA emulsion 600 600 600 600
HF antibacterial agent 5 5 5 5
Poly(toludiene-co-anisidine) (1:1) 15 30 60 90
Total 1000g 1000g 1000g 1000g
Table 7
Physico-mechanical properties of paint lms of the blank and CE
1
samples.
Test Blank A
1
A
2
A
3
A
4
Adhesion 4B 5B 5B 5B 5B
Hardness 60 65 73 76 79
Bending Pass Pass Pass Pass Pass
Impact 100/15 100/15 100/15 100/15 100/15
Gloss 51.3 50.5 49 51.8 50
Opacity 93.8% 95.3 96% 98% 98.1%
Whiteness 79.3 70.1 66.9 64.5 62.1
Washability 1100 1350 2500 3500 3450
Table 8
Physico-mechanical properties of paint lms of CE
2
samples.
Test B
1
B
2
B
3
B
4
Adhesion 5B 5B 5B 5B
Hardness 68 77 82 80
Bending Pass Pass Pass Pass
Impact 100/15 100/15 100/15 90/9
Gloss 49 47 47 45
Opacity 94% 94% 95% 96.2%
Whiteness 75.6 68.7 67.2 66.7
Washability 1750 3000 3700 3750
Table 9
Physico-mechanical properties of paint lms of CE
3
samples.
Test C
1
C
2
C
3
C
4
Adhesion 5B 5B 5B 5B
Hardness 75 78 80 80
Bending Pass Pass Pass Pass
Impact 100/15 100/15 100/15 100/15
Gloss 49 48 49 47
Opacity 94% 95.2% 94.5% 95.2%
Whiteness 70.7 62.1 61 60.2
Washability 2100 2800 3500 3300
Table 10
Weathering test results of the tested lmpaints.
Sample After 250h After 500h
E E
Blank 2.44 7.73
A
1
4.1 6.84
A
2
1.36 4.84
A
3
1.65 3.9
A
4
1.9 6.84
B
1
3.87 7.2
B
2
0.84 2.3
B
3
0.64 1.82
B
4
0.75 3.12
C
1
1.69 2.87
C
2
1.19 2.66
C
3
1.03 1.92
C
4
1.75 3.45
nal paint. In addition, washability is highly increased due to the
presence of the prepared CPNs and CCPNs.
3.4. Weathering resistance test
Most weathering damage is caused by three factors: light, high
temperatureandmoisture. Anyoneof thesefactors may causedete-
rioration. Together, they often work synergistically to cause more
damage than any one factor alone.
Weathering test results of the paint lms of blank, CE
1
, CE
2
and
CE
3
samples are shown in Table 10. It is obvious fromTable 10 that
the color differences E increase as the time of exposure increases.
It is also obvious that the best results are for the paint formu-
lations of samples A
3
, B
3
and C
3
where the color differences E
between the tested sample and the standard sample are the least.
This conrms that incorporationof the preparedCPNs andCCPNs in
the blank paint formulation makes the paint lms acquire higher
weathering resistance than those of paint formulations based on
St/BA emulsion alone.
3.5. Corrosion resistance test
To examine the corrosion resistance, different steel panels have
been painted with different paint formulations based on the blank,
CE
1
, CE
2
and CE
3
samples. After drying for one week, they have
been immersed in articial seawater for 28 days. The results are
given in Table 11. The painted metal plates have been detected for
blistering resistance of coating lms and degree of rusting of metal
surface under paint lms. Corrosion progress on metal plates under
paint lms of the blank, CE
1
, CE
2
and CE
3
samples is represented
photographically in Figs. 711, respectively. As shown fromthe g-
ures and data given in Table 11, the corrosion resistance of the steel
panels painted with all the tested samples increases as the concen-
tration of the CPNs and CCPNs in the paint increases up to (6%)
and after that the corrosion resistance starts to decrease. Coatings
containing the CPNS and CCPNs function as both a barrier and an
oxidant for the steel substrate, i.e. formation of passive oxide lm
on the steel surface results from redox reaction at the steel and
polymer interface [18].
When the concentrations of the CPNs and CCPNs reach the max-
imumof 9%, the anticorrosion properties decrease and this may be
attributed to the formation of intermolecular crosslinks between
the polymeric chains which hinder the owof electrons and conse-
quentlythe redoxreactionat the steel andpolymer interface. When
the paint contains 6%of the prepared CPNs and/or CCPNs corrosion,
resistance maximizes. This explains why the steel panels have lit-
tle tarnished surface, while the other paint formulations especially
with lower concentrations (1.5, 3%) of CPNs and CCPNs showweak
corrosion resistance as shown in Figs. 8 and 9. Maximumfailure is
N. Elhalawany et al. / Progress in Organic Coatings 77 (2014) 725732 731
Table 11
Corrosion resistance tests of the painted steel panels.
Test Blank Group CE
1
Group CE
2
Group CE
3
A
1
A
2
A
3
A
4
B
1
B
2
B
3
B
4
C
1
C
2
C
3
C
4
Degree of rusting
a
2.5 5.5 6 9.8 9 6.5 7.5 9.8 8 6.5 8 9.9 9.5
Degree of blistering
b
D MD 4MD 9F MD 7F 9F 9F 7F 6MD 8F 9F 8.5F
Total anticorrosion efciency (%) 25 55 60 98 90 65 75 98 80 65 80 99 95
a
It is rating of rust as area percentage; it is graded on a scale from10 to 0, where 10<0.01% and 0, 100% according to ASTMD 610 (2001).
b
It is graded on a scale from10 to 0, where 10 no blistering and 0 for largest blisters and frequently denoted by F, M, MD, and D (few, medium, mediumdense and dense)
according to ASTMD 714-87 (2000).
Fig. 7. Corrosion test of steel panel painted with blank paint sample.
obviously obtained with the blank paint sample, where severe cor-
rosion (rating 2.5) and D blisters have been observed as seen from
Fig. 7 and Table 11.
With respect to the panels painted with A
3
, B
3
and C
3
samples,
the results showthat maximumcorrosion resistance is for the pan-
els painted with sample C
3
. They have very little tarnished surface
(rating9) withnegligibleblisters of 9F degree, as shownfromFig. 10
and data in Table 11.
It is worth mentioning that all panels painted with the sam-
ples containing the CCPNs have much better corrosion resistance
than those painted with samples containing the neat PAns or neat
PTol nanoparticles. The enhanced corrosion protection effect of the
CCPNs in the form of coating on steel surface is attributed to the
greater barrier performance and the more involvement of CCPNs
in the oxide formation due to combination of the redox catalytic
property of PAns and PTol at the same time. The porosity of the
coating is another important factor that affects the initiation and
progress of corrosion under the coating [19]. The enhanced barrier
performance of the CCPNs coatings is attributed to the dense lm
of the CCPNs coating on the steel substrate.
Fig. 8. Corrosion test of the steel panels painted with CE samples. ((a) Ai, (b) Bi and (c) Ci having the same concentration of 1.5%.)
Fig. 9. Corrosion test of the steel panels painted with the CE samples. ((a) A, (b) B and (c) C having the same concentration of 3%.)
732 N. Elhalawany et al. / Progress in Organic Coatings 77 (2014) 725732
Fig. 10. Corrosion test of the steel panels painted with the CE samples. ((a) Ai, (b) B3 and (c) C3 having the same concentration of 6%.)
Fig. 11. Corrosion test of the steel panels painted with the CE samples. ((a) A4, (b) 64 and (c) C4 having the same concentration of 9%.)
4. Conclusion
In this work, a new type of anticorrosive water-based paints
has been prepared by incorporation of the prepared (CPNs)
and their (CCPNs) in the blank paint formulation based on
styrene/butylacrylate emulsion as a binder. It has been found from
the data given in the tables and gures that incorporation of CPNs
andtheir CCPNs inthe blank paint formulationmake the paint lms
acquire higher resistance against washability, weathering and cor-
rosion than those of paint formulation based on St/BA emulsion
alone. The anticorrosion properties of the painted lms containing
the CCPNs have given the best results due to their enhanced bar-
rier effect and greater involvement in oxide lm formation which
results fromdual redox catalytic effect of the CCPNs. It is expected
that such a newtype of emulsion paint containing CPNs and CCPNs
is to be used as an architectural paint to reduce the consumption of
the petroleum resources in the eld of paint industry and to pave
the way for the development of new coating technologies. As far
as we know, none of the commercial paints developed up to date
has achieved any of these characteristics and no applied usage of
composite emulsions containingPTol or PAns nanoparticles or their
CCPNs has been reported.
Acknowledgement
The authors wish to thank Research and development depart-
ment, Eagle Chemicals Company, 6th October City, Egypt for
generous and sincere assistance in carrying out some of the nec-
essary investigations and analysis in this work.
References
[1] A. Tale, P. Passiniemi, O. Forsn, S. Ylsaari, Synthetic Metals 85 (1997)
13331334.
[2] W.S. Araujo, P. Margarit, M. IFerreira, O.R. Mattos, P.L. Neto, Electrochimica Acta
46 (2001) 13071312.
[3] E. Armelin, R. Pla, F. Liesa, X. Ramis, J.I. Iribarren, C. Alemn, Corrosion Science
50 (2008) 721728.
[4] C. Ocampo, E. Armelin, F. Liesa, C. Alemn, X. Ramis, J.I. Iribarren, Progress in
Organic Coatings 53 (2005) 217.
[5] J.M. Yeh, C.P. Chin, S. Chang, Journal of Applied Polymer Science 88 (14) (2003)
3264.
[6] G.S. Goncalves, Synthetic Metals 161 (2011) 313323.
[7] M.A. Lucio Garca, M.A. Smit, Journal of Power Sources 158 (2006)
397402.
[8] A. Cook, A. Gabriel, D. Siew, N. Laycock, Current Applied Physics 4 (2004)
133136.
[9] R.M. Torresi, S.D. Souza, J.E.P. Silva, S.I.C. Torresi, Electrochimica Acta 50 (2005)
22132218.
[10] L.G. Xu, S.C. Ng, H.S.O. Chan, Synthetic Metals 123 (2001) 403410.
[11] Y. Cao, P. Smith, A.J. Heeger, Synthetic Metals 48 (1992) 9197.
[12] A.J. Heeger, Angewandte Chemie International Edition 40 (14) (2001)
2591.
[13] L. Shao, J. Qiu, M. Liu, H. Feng, L. Lei, G. Zhang, Y. Zhao, C. Gao, L. Qin, Synthetic
Metals 161 (2011) 806811.
[14] N.R. Elhalawany, Y. Maximenko, Z. Yamani, S.T. Yau, M.H. Nayfeh, Journal of
Materials Research 28 (2) (2013) 28.
[15] B.J. Kim, S.G. Oh, M.G. Han, S.S. Im, Synthetic Metals 122 (2001) 297.
[16] S.T. Selvan, A. Mani, K. Athinarayanasamy, K.L. Phani, S. Pitchumani, Materials
Research Bulletin 30 (1995) 699.
[17] H.J. Nagash, A. Karimzadeh, A.R. Momeni, A. Reza, M.H. Alian, Turkish Journal
of Chemistry 31 (2007) 257269.
[18] J. Alam, U. Riaz, S. Ahmad, Current Applied Physics 9 (2009) 8086.
[19] N. Tanveer, M. Mobin, Journal of Minerals & Materials Characterization & Engi-
neering 10 (8) (2011) 735753.