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Progress in Organic Coatings 77 (2014) 725732

Contents lists available at ScienceDirect

Progress in Organic Coatings

j ournal homepage : www.elsevier .com/ locate /porgcoat

Novel water based coatings containing some conducting polymersnanoparticles (CPNs) as corrosion inhibitors

Noha Elhalawany a,, Michael A. Mossad b, Magdy K. Zahran c

a Polymers and Pigments Department, National Research Center, Cairo, Egyptb EagleChemicals Company, 6th October, Egyptc 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 nanoparticle

(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. Th

prepared materials have been characterized by GPC, FTIR, TEM and DSC. The prepared CPNs and CCPNs o

different weight percentages (wt.%) have been incorporated into paint formulations. Ithasbeen found tha

the presence ofthe prepared CPNs and CCPNs in the paint formulations highly enhanced the resistanc

ofthe formed paint films 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 effi-

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 find 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

used to protect steel against corrosion[3,4]. Corrosionprotection of

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

E-mail addresses:[email protected], [email protected]

(N. Elhalawany).

steels using coating containingpolypyrrole/clay nanocomposite [5

and alkyd coatings containing polyaniline [6] has been well studied. The formation of coating on active metals is rendered difficul

by the general lack of solubility of conducting polymers. Thoug

a popular route, the electrodeposition of conducting polymer

is a difficult 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 factor

is the homogeneous distribution of conducting polymers in th

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 polymer

[10].

The present study reports the synthesis and characterization o

some CPNs based on polytoluidine, polyanisidine and their copoly

mer (CCPNs) using miniemulsion polymerization technique. Th

preparedCPNs and CCPNsdispersed inan aqueous mediahavebeen

incorporated into water based paint. The basic properties as wel

as anticorrosion studies of the blank paint films and paint film

containing the prepared CPNs and CCPNs have been investigated

and evaluated. No literature is available on the synthesis of Pol

toluidine, poly anisidine and their copolymer via miniemulsion o

their use as anticorrosive inhibitors in water based paints. Henc

an attempt has been made to synthesize them and to study thei

anticorrosion properties. Thus, this paper should pave the way fo

the development of new coating technologies based on the intro

duction of polytoluidine, poly anisidine and their copolymer a

anticorrosive additives.

0300-9440/$ seefrontmatter 2014 Elsevier B.V. All rights reserved.

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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 from SigmaAldrich 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), Sodiummetabisulfite (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 filler 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 pH stabilizers andsupplied from CHIMI

ART Chemicals Company, Cairo, Egypt. Tylose (under the trade

name Tylose H 30000YP2) has been used as thickening agent and

supplied from GmbH & 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, Eagle Chemicals Company,6th October,Egypt andEnergy

Chemical Company, China respectively. Anti-foaming agent and

antibacterial agent (Acticide HF) have been purchased from Mnz-

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 5 min to

form theminiemulsion.A 25ml of (1%)ammonium persulfate(APS)solution has been added dropwisely to the former miniemulsion

under continuous vigorous stirringat 10,000 rpm for further 10 min

at room temperature. A color change from white to brownish red

then to dark pink has been observed. At the final 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 below 25 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 dispersionof PAns has been cooled below 25C 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 10,000rpm for further 10min at room temperature.

A color change from white to pale brown then to dark brown has

been observed. At the final 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 below 25C

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 reflux condenser, a thermometer,

threedropping funnels anda mechanical stirrer. Only8% of thetotal

monomermixture hasbeen introduced at thebeginning of thereac-

tion at 65C and the remaining monomer mixture has been added

dropwisely at 802 during the remaining time. Redox system of

Tetra butyl hydroperoxide and Sodium metabisulfite (SMBS) have

been added after 30min from addition of monomers at 65C. Emul-

sion copolymerization has been carried out for 4 h under nitrogen

gas conditions according to the recipe shown in Table 1. The pro-

duced latex has been filtered, cooled below 30C and then keptfor

further use.

Fig. 2. Stabledark green PAns/DBSA colloidal dispersion.

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N. Elhalawany et al. / Progress in OrganicCoatings77 (2014) 725732 72

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 outat

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 film testing

Paint film testing has been used to confirm some basic physical

properties of thecoatings afterit is applied anddried. The resistance

of the paint films to corrosion has been also examined.

2.4.1. Physical properties

The gloss, whiteness, and opacity of paint films 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 film

in accordance with AST M D 522-93a (2001). The hardness of

Table 1

Raw materials of emulsion copolymerization.

Raw materials 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

Sodium metabisulphite 0.5

paint has been evaluated in accordance with ASTM D 4366-9

with Pendulum Hardness Rocker tester; model 707 KONIG from

Sheen-Instruments. The adhesion power of paint film to the bas

substrates has been tested in accordance with ASTM D 3359-9

using the cross-cut test instrument-Sheen Company. CHOC Vari

able Impact Tester from Braive Instruments has been used t

measure resistance of organic coatings to theeffects of rapid defor

mation (Impact) in accordance with ASTM D 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 Weatherin

Tester, Model QUV/Spray with solar eye Irradiance control from Q

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 o

sunlight using special fluorescent UV lamps(Type: UVA 340)which

give the best simulation of sunlight in thecritical short wavelength

regionfrom365nm down tothe solarcut-offof 295 nm. Itsimulate

dew and rain with condensing humidity and/or water spray.

2.5. Corrosion studies

The corrosion study has been carried out with hand-mad

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 o

an aqueous solution of NaCl (3.5wt.%). The painted steel panel

have been scratched with a sharp blade to obtain X-cut through

thecoatingunder test.The panelshavebeen immersed inthe abov

solutionmedium (artificial seawater)for 28 days. At thistime, thes

panels have been washed with distilled water and dried.

3. Results and discussion

The prepared (CPNs) and their copolymer (CCPNs) should b

dissolved in water/alcohol mixture to be compatible and suitabl

for use in waterborne systems. Solubility of conducting polymer(CPs) has gained special importance, both scientifically and com

mercially. Cao et al. [11] in 1992 used functionalized protoni

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

surfactant in that the charged head group is ionically bound t

the oppositely charged protonated PANI chain, and the tail i

chosen to be compatible with nonpolar or weakly polar organi

liquids [1214]. This approach is also known as counter-ion

induced processability. In this manuscript, the polymerization o

aniline derivatives (toluidine and anisidine) and their copolyme

in presence of protonic acid such as DBSA has been described i

Schemes 1 and 2, respectively.

The molecular weight (M.wt) determination of the prepare(CPNs)and their copolymer(CCPNs) hasbeen done using GPC tech

nique. It has been found that the prepared PTol, Pans and thei

copolymer (CCPNs) have low molecular weight of (7307, 6878 an

8195) and a polydispersity index (Dw/Dn) of (1.9, 1.3 and 1.5)

respectively. WhereDwis the weight average particle diameter and

Dnis 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 thos

described in literature for poly aniline [15,16]. The peaks charac

teristic of PTol and PAns can be assigned as follows: C C stretchin

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Scheme 1. Polymerizationof toluidine and/oranisidine in presence of DBSA.

of benzene rings at 1400 and 1440cm1, C N stretching of aro-

matic amines at 1255cm1 and the bands at 1660 and 1661cm1

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 1497cm1 are assigned to CH3 and

OCH3groups of PTol and PAns, respectively. FT-IR spectrum of 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 TEM micrograph of the prepared PTol, Pans

and their copolymer, respectively. It is clearly seen from themicro-graphs 5a and 5b 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 5chas confirmed 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 thepreparedCPNs and their copolymer.

3.1.3. Differential scanning calorimetric analysis (DSC)

Fig. 6 shows the DSC analysis of CE containing the preparedCCPNs.It is well knownfrom the literature that theDSC 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. The DSC dia-

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.

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Fig. 5. TIM of thestable colloidal dispersions of (a)PToL, (b)PAns and (c) P(Ans-co-ToI).

Fig. 6. DSC diagram of CE containing CCPNs.

3.2. Water based paint formulations

The binder used here is the St/BA emulsion (solid content

50%). St/BA latex specification 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 CE1, CE2 and CE3, respectively. Blank, CE1, CE2 and

CE3 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 formulationsof the blank,CE1

,

Table 2

St/BA latex specifications.

Latex specification

State Liquid

Color Milky white

Av. (M.wt.) 289,360 g/mol

Non-volatile content by weight (%) 50% 1

Viscosity (Brookfield) Spindle4 at 23 C ( C Ps) 1000-5000

pH 7-8

MFFT, (C) (minimum film forming temperature) 18

Specific gravity (g/ml) 1.06

Particle size (m) 0.1

Water solidification temperature 0 C

Water vapor temperature 100 C

Table 3Blank paint formulation.

Composition Weight (g)

Water 200

Tetra potassium pyrophosphate 2

WD-EAGLE (AS4/40) 3

Texanol 4

Antifoaming agent 6

Tylose H30,000 3

Ammonia 2

Titanium dioxide 150

CaCo3 25

Binder 50% 600

HF antibacterial agent 5

Total 1000

CE2 and CE3 samples are represented in Tables 36, respectively

Each paint has been applied on steel, tin and glass panels and dried

at room temperature for 1 week before the measurements.

3.3. Physico-mechanical tests

The physico-mechanical test results of the paint films of blank

CE1, CE2 and CE3samples after one week from dryness have been

measured and tabulatedin Tables 79. The data shownin thetable

indicate that the presence of CPNs and CCPNs in the film paint

has not affected too much the basic properties of the resultan

Table 4

Emulsion paint formulationsof CE1samples.

Composition CE1

A1 A2 A3 A4

Water 185 170 140 110

Tetra potassium pyrophosphate 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

Titanium dioxide 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 1000 g 1000 g 1000 g 1000 g

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Table 5

Emulsion paint formulationsof CE2 samples.

Composition CE2

B1 B2 B3 B4

Water 185 170 140 110


WD-EAGLE (AS4/40) 3 3 3 3

Texanol 4 4 4 4


Tylose H30,000 3 3 3 3

Ammonia 2 2 2 2


CaCo3 25 25 25 25


HF antibacterial agent 5 5 5 5

Poly anisidine (PAns) 15 30 60 90

Total 1000 g 1000 g 1000 g 1000 g

Table 6

Emulsion paint formulationsof CE3 samples.

Composition CE3

C1 C2 C3 C4

Water 185 170 140 110


WD-EAGLE (AS4/40) 3 3 3 3

Texanol 4 4 4 4


Tylose H30,000 3 3 3 3

Ammonia 2 2 2 2


CaCo3 25 25 25 25


HF antibacterial agent 5 5 5 5

Poly(toludiene-co-anisidine) (1:1) 15 30 60 90

Total 1000 g 1000 g 1000 g 1000 g

Table 7

Physico-mechanical properties of paint films of theblank and CE1samples.

Test Blank A1 A2 A3 A4

Adhesion 4B 5B 5B 5B 5BHardness 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 films of CE2samples.

Test B1 B2 B3 B4

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 45Opacity 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 films of CE3samples.

Test C1 C2 C3 C4

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 thetested film paints.

Sample After 250 h After 500 h

E E

Blank 2.44 7.73

A1 4.1 6.84

A2 1.36 4.84

A3 1.65 3.9

A4 1.9 6.84

B1 3.87 7.2B2 0.84 2.3

B3 0.64 1.82

B4 0.75 3.12

C1 1.69 2.87

C2 1.19 2.66

C3 1.03 1.92

C4 1.75 3.45

final 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.Anyoneofthesefactorsmay causedete-rioration. Together, they often work synergistically to cause more

damage than any one factor alone.

Weathering test results of the paint films of blank, CE1, CE2and

CE3samples are shown in Table 10. It is obvious from Table 10 that

the color differencesEincrease as thetime of exposure increases.

It is also obvious that the best results are for the paint formu-

lations of samples A3, B3 and C3 where the color differences E

between the tested sample and the standard sample are the least.

This confirms that incorporationof theprepared CPNs and CCPNs in

the blank paint formulation makes the paint films 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,

CE1, CE2 and CE3 samples. After drying for one week, they have

been immersed in artificial seawater for 28 days. The results are

given in Table 11. The painted metal plates have been detected for

blistering resistance of coating films and degree of rusting of metal

surface under paint films. Corrosion progress on metal plates under

paint films of the blank, CE1, CE2 and CE3 samples is represented

photographically in Figs.711, respectively.As shown from the fig-

ures and data given in Table 11, the corrosionresistance of thesteel

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. Coatingscontaining the CPNS and CCPNs function as both a barrier and an

oxidant for the steel substrate, i.e. formation of passive oxide film

on the steel surface results from redox reaction at the steel and

polymer interface [18].

When theconcentrations of theCPNs andCCPNs reach themax-

imum of 9%, the anticorrosion properties decrease and this may be

attributed to the formation of intermolecular crosslinks between

thepolymeric chains which hinder the flowof electrons and conse-

quently the redox reaction at the steeland polymer interface. When

thepaint contains 6% of thepreparedCPNs and/orCCPNscorrosion,

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 show weak

corrosion resistance as shown in Figs. 8 and 9. Maximum failure is

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Table 11

Corrosion resistance tests of thepainted steel panels.

Test Blank Group CE1 Group CE2 Group CE3

A1 A2 A3 A4 B1 B2 B3 B4 C1 C2 C3 C4

Degreeof rustinga 2.5 5.5 6 9.8 9 6.5 7.5 9.8 8 6.5 8 9.9 9.5

Degree of blisteringb D MD 4MD 9F MD 7F 9F 9F 7F 6MD 8F 9F 8.5F

Total anticorrosion efficiency (%) 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 from 10 to 0, where 10< 0.01% and 0, 100% according to ASTM D 610(2001).

b Itis gradedon a scale from10 to0, where 10 noblistering and 0 for largest blistersand frequently denoted byF, M, MD, andD (few, medium, medium dense and denseaccording to ASTM D 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 A3, B3and C3samples

theresults show that maximum corrosion resistance is forthe pan

els painted with sample C3. They have very little tarnished surfac

(rating9) withnegligibleblistersof 9F degree, as shown fromFig.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 resistanc

than those painted with samples containing the neat PAns or neaPTol nanoparticles. The enhanced corrosion protection effect of th

CCPNs in the form of coating on steel surface is attributed to th

greater barrier performance and the more involvement of CCPN

in the oxide formation due to combination of the redox catalyti

property of PAns and PTol at the same time. The porosity of th

coating is another important factor that affects the initiation and

progress of corrosion under the coating [19]. The enhanced barrie

performance of the CCPNs coatings is attributed to the dense film

of the CCPNs coating on the steel substrate.

Fig. 8. Corrosion test of the steel panelspainted with CE samples. ((a) Ai, (b) Bi and (c) Ci having thesame concentration of 1.5%.)

Fig. 9. Corrosion test ofthe steel panels painted with the CE samples. ((a) A, (b) B and (c) C having the same concentration of 3%.)

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Fig. 10. Corrosion test ofthe steel panels painted with the CE samples. ((a) Ai, (b) B3 and (c) C3 having the sameconcentration of6%.)

Fig. 11. Corrosion testof 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 figures that incorporation of CPNs

and their CCPNs in the blankpaintformulation make the paintfilms

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 films containing

the CCPNs have given the best results due to their enhanced bar-

rier effect and greater involvement in oxide film formation which

results from dual redox catalytic effect of the CCPNs. It is expected

that such a newtype of emulsion paint containing CPNs andCCPNs

is to be used as an architectural paint to reducethe consumption of

the petroleum resources in the field 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

compositeemulsions containing PTolor PAnsnanoparticles 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.

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