In this context, conducting composite based on waterborne epoxy system and polypyrrole (PPy) was investigated. The polypyrrole was synthesized by chemical oxidation polymerization. Its morphology and chemical structure were confirmed by using field emission scanning electron microscopy (FESEM) and Fourier transform infrared spectroscopy (FTIR). Then, PPy was well-dispersed in the epoxy coating and had a good compatibility with the matrix. The effects of PPy on dielectric, electrical and mechanical properties of epoxy/PPy composites was examined. The dielectric constant and electrical conductivity of the coatings increased with addition of PPy fillers. Over to 15 wt. % of PPy loading, the volume resistivity of samples slightly decreased from 6.7 × 1010 to 1.5 × 1010 Ω cm. In contrast, the presence of PPy diminished both impact and abrasion resistance of the epoxy/PPy composites, down to 160 kg cm and 10.2 L/mil, respectively, but they stayed acceptable for the coatings. The results reveal that the epoxy containing polypyrrole is suitable for various electrical and dielectric applications

Nguyen, Anh Son

Nguyen, Thi Thu Trang

Nguyen, Thuy Duong

Pham, Gia Vu

Thai, Thu Thuy

Tran, Dai Lam

English

Vietnam Academy of Science and Technology: Journals Online

Communications in Physics, Vol. 30, No. 1 (2020), pp. 11-18
DOI:10.15625/0868-3166/30/1/14582
EFFECT OF POLYPYRROLE ON THE ELECTRICAL, DIELECTRIC AND
MECHANICAL PROPERTIES OF WATERBORNE EPOXY COATINGS
THAI THU THUY, NGUYEN THUY DUONG, NGUYEN THI THU TRANG,
PHAM GIA VU, TRAN DAI LAM AND NGUYEN ANH SON†
Institute for Tropical Technology, Vietnam Academy of Science and Technology
18 Hoang Quoc Viet, Cau Giay District, Hanoi, Vietnam
†E-mail: nason@itt.vast.vn
Received 4 November 2019
Accepted for publication 2 December 2019
Published 28 February 2020
Abstract. In this context, dissipative composite based on waterborne epoxy system and polypyr-
role (PPy) was investigated. PPy was synthesized by chemical oxidation polymerization. Its
morphology and chemical structure were confirmed by using field emission scanning electron
microscopy (FESEM) and Fourier transform infrared spectroscopy (FTIR). Then, PPy was well-
dispersed in epoxy coating and had a good compatibility with the matrix. The effects of PPy on
dielectric, electrical and mechanical properties of epoxy/PPy composites were examined. The
dielectric constant and electrical conductivity of coatings increased with addition of PPy fillers.
Over 15 wt.% PPy loading, the volume resistivity of samples slightly decreased from 6.7 × 1010
to 1.5 × 1010 Ω cm. In contrast, the presence of PPy diminished both impact and abrasion re-
sistance of the epoxy/PPy composites, down to 160 kg cm and 10.2 L/mil, respectively, but they
stayed acceptable for the coatings. The results reveal that the epoxy containing PPy is suitable
for various electrical and dielectric applications.
Keywords: polypyrrole, waterborne epoxy, dielectric, volume resistivity, impact strength, abrasion
resistance.
Classification numbers: 81.40.pq; 83.80.-k; 77.84.Lf.
I. INTRODUCTION
In recent years, the polymer composites of an insulating polymer incorporated conduct-
ing additives have attracted plenty of attention. The new materials can present desired properties
c©2020 Vietnam Academy of Science and Technology
12 EFFECT OF POLYPYRROLE ON THE ELECTRICAL, DIELECTRIC AND MECHANICAL PROPERTIES...
for various electrical and electromagnetic applications to avoid electrostatic charges and electro-
magnetic aggression phenomena [1, 2]. Commonly used conducting fillers to make insulating
matrix conductive are carbon black (CB), carbon nanotube (CNT), graphene, metallic powders,
flakes and intrinsically conductive polymers (ICPs) [3–7]. Due to the good electrical conductivity,
lightweight and facile synthesis, the conducting polymers replace step by step the organic and
expensive inorganic fillers. PPy is one of the most intensively studied ICPs. In addition to the
outstanding characteristics of ICPs, it displays the environmental/chemical stability [8], and its
electrical conductivity can be controlled by doping method [9, 10]. However, in literature, some
works reported that the PPy is very brittle and cannot carry any mechanical load [11].
Epoxy is well-known a thermosetting resin having excellent mechanical, thermal proper-
ties, good adhesion and chemical resistance. Combining PPy with epoxy resin is a good strategy
to resolve the poor mechanical properties of PPy. Moreover, the obtained composite can present
a better dielectric and electrical properties than that of neat epoxy. Zhang et al. reported that the
nanofibers PPy incorporated into epoxy resins give a higher tensile strength than that of neat epoxy
(90.36 MPa compared to 70.03 MPa) [12]. Furthermore, the presence of PPy conducted a better
electrical conductivity (about 3 × 1012 Ω cm) and real permittivity of the epoxy matrix. Besides,
the epoxy coatings containing PPy introduced also remarkable acid, corrosion and weathering re-
sistance [13–15]. The composites of PPy with an epoxy system were also examined to replace
metal compound in the isotropically conductive adhesives. The PPy doped dodecylbenzenesul-
phonic acid (DBSA) improved the electrical conductivity of epoxy resin up to 10-3 S/cm at 15
wt.% content with negligible effect of moisture and acceptable impact properties [16]. Today, for
safety, health and environmental regulations, the solvent-free epoxy resin has more and more been
required. However, there were a few works in literature that employed on the composites of PPy
and these epoxy systems.
The aim of this paper is to attempt to display the effect of PPy on the properties of wa-
terborne epoxy coatings. The PPy particles were synthesized with an oxidation polymerization
method with ferric chloride (FeCl3) as oxidant. Then, the waterborne epoxy coatings containing
PPy with varying concentration were prepared. The effects of PPy on the morphology, dielectric,
electrical and mechanical properties of epoxy matrix were examined by using field emission scan-
ning electron microscope (FESEM), complex dielectric permittivity measurement, I-V method,
impact and abrasion resistance.
II. EXPERIMENT
II.1. Materials
The coating was a commercial bicomponent water-based epoxy system. The base was a
bisphenol A epoxy resin (Epikote 828, Hexion, Thailand) that has equivalent weight of about
184-190 g/eq. A water-reducible amine adducts (Epikure 8537-wy-60, Momentive, Thailand)
consisted of 60 wt.% solids in water, 2-propoxyethanol and glacial acetic acid was used as a
hardener which has an amine value of 310-360 mg/g and an equivalent weight of 174 g/eg.
Pyrrole (Py, ≥ 97 % ) and reagent ferric chloride (FeCl3, used as an oxidizing agent) were
purchased from Sigma-Aldrich. The Py monomer was purified before polymerization
process. Hydrochloric acid (HCl) and acetic acid (CH3COOH) were provided by Merck and used
as received.
T. T.THUY, N. T. DUONG, N. T. T. TRANG, P. G. VU, T. D. LAM, AND N. A. SON 13
In this study, the metallic substrates were plates of carbon steel XC35 with size of 150×
100×1 mm. They were polished with SiC papers (400 and 600 grades) and cleaned with distilled
water and ethanol.
II.2. Sample preparation
PPy was synthesized by chemical oxidation polymerization as described elsewhere [16].
Briefly, fresh Py was added in a 1 M HCl solution and stirred for 30 mins. The oxidant (FeCl3)
was dissolved in another 1 M HCl solution with stoichiometry Py/FeCl3 ratio (1/2.33), then it
was poured slowly drop-wise in the Py solution. The polymerization process was kept at room
temperature for 24 h. The obtained black precipitation was filtered and washed several times with
distilled water to remove all residuals. The produces were dried at 80˚C overnight.
For the composite coatings, the synthesized PPy was incorporated into epoxy system with
various concentrations: 10, 15, 20, 25 and 30 wt.% , henceforth called Epo-PPy10, Epo-PPy15,
Epo-PPy20, Epo-PPy25 and Epo-PPy30, respectively. To obtain a well-dispersion of PPy in epoxy
matrix, in all cases, the conducting polymer was added in the hardener solution (water was adjusted
to receive a mixture with similar viscosity for all samples). These mixtures were then strongly
stirred by magnetic stirring and ultrasonicated by T10 IKA disperser, Ultra-Turrax for 4 h. The
obtained suspensions were added epoxy resin with stoichiometry ratio into and stirred for 1 h.
The epoxy/PPy composite coatings were applied onto the surface of carbon steel substrate by spin
coating technique. After drying a week in air, the samples were 25-30 µm thick.
II.3. Characterization
Field emission scanning electron microscope (FESEM) was used to observe the morphol-
ogy of synthesized PPy and epoxy/PPy composite coatings. The FESEM images were recorded
at 20 kV for powder and 2 kV for coatings. A thin layer of platinum had been sputtered onto
all samples. The chemical structure of synthesized PPy was characterized by Fourier-transform
infrared (FTIR) spectra by using a Nexus 670 Nicolet spectrometer with a resolution of 4 cm-1 in
the range from 400 to 4000 cm-1.
The complex dielectric constant of the epoxy/PPy composites were determined in the fre-
quency ranged from 1.43 MHz to 1000 Hz with 1 V AC voltage on an Agilent E4980A instrument
equipment with 16451B test figure. The volume resistivity of coatings was measured by I-V
method according to ASTM D257.
The impact strength of epoxy/PPy composite coatings was determined according to ASTM
D2794. The values of impact resistance were obtained with maximum height of standard weight
(2 kg) dropped on the surface of samples, and no fracture were observed at the contact zone. The
abrasion resistance of samples was measured by Falling Sand method according to ASTM D968.
The coated substrates were set up at an angle of 45˚, then the sand falls from the height of 90 cm
onto the surface of samples. The tests were conducted in increment of 1 L of sand.
III. RESULTS AND DISCUSSION
Fig. 1 shows the FESEM image of synthesized PPy. It illustrates the typical spherical mor-
phology of PPy with size of about 800 nm and porosity [17]. The PPy particles were agglomerated
to form larger globules with the granules overlapped over each other, which looks like the mor-
phology observed on carbon black [18] due to the existence of an attractive force between the
14 EFFECT OF POLYPYRROLE ON THE ELECTRICAL, DIELECTRIC AND MECHANICAL PROPERTIES...
individual polymer chains. So, depending on the interaction of polymer chains, the size of PPy
agglomeration can present various levels.
Fig. 1. FESEM micrograph of synthesized PPy.
Fig. 2. FTIR spectra of synthesized PPy.
To confirm the chemical structure of synthesized PPy, the FTIR spectroscopy was per-
formed. The FTIR spectrum of synthesized PPy is shown in Fig. 2. It displays the characteristic
T. T.THUY, N. T. DUONG, N. T. T. TRANG, P. G. VU, T. D. LAM, AND N. A. SON 15
bands for PPy as reported in the literature [19]. The peaks at 1521 and 1437 cm-1 are attributed
to C=C stretching and conjugated C-N stretching in the PPy ring, respectively. The absorption
bands at 1328, 1154 and 1039 cm-1 are assigned to C-H bending, C-H in-plane stretching and C-H
vibration of 2,5-substituted Py, respectively [20]. Furthermore, the FTIR spectrum also shows a
vibration band at 786 cm-1 belonging to the C-H wagging vibration.
The morphology of epoxy composite coatings containing PPy with different proportions
was then investigated. To observe the compatibility and the dispersibility of the PPy in the wa-
terborne epoxy matrix, the FESEM micrographs were recorded at the cross-section of the films
(Fig. 3). For the neat epoxy coatings, the analyzed area is smooth and uniform as expected
(Fig. 3a). At the fracture section of coatings containing PPy (Fig. 3b-f), it appears many bro-
ken marks in not the same direction as seen in the case of neat epoxy coating. The micrographs
reveal a good dispersion of PPy in the epoxy matrix. As seen in Fig. 3, the broken marks are more
and more crowded with the increase of PPy content in the epoxy system. In addition, it cannot be
observed the phase separation between the PPy spheres and the matrix for all coatings containing
the PPy indicating a good compatibility of two polymers.
Fig. 3. FESEM micrographs at cross-section of epoxy (a); Epo-PPy10 (b); Epo-PPy15
(c); Epo-PPy20 (d); Epo-PPy25 (e) and Epo-PPy30 (f).
Fig. 4 displays the dielectric permittivity complex of composites via the variation of real
(relative dielectric, ε ′) and imaginary (dielectric loss factor, ε ′′ ) parts as a function of frequency.
As well-known insulating material, the neat epoxy shows the lowest value of dielectric constant
and loss factor in the analyzed frequency range (1000 Hz - 1.4 MHz), ε ′ = 3.2 and ε ′′ = 0.1
at 10 kHz. By adding PPy powder to the epoxy matrix, the relative dielectric of composites
increased to high value, up to 18.7 at 1000 Hz and 14.3 at 10 kHz (for Ep-PPy30). This behavior
reveals that the system exhibits a strong interfacial polarization [21]. For all coatings, the value
dielectric permittivity complex increased with decreasing frequency. This behavior is due to the
reorientation of dipolar groups which can easily orient themselves at lower frequency, but hardly
16 EFFECT OF POLYPYRROLE ON THE ELECTRICAL, DIELECTRIC AND MECHANICAL PROPERTIES...
orient themselves at higher frequency [22]. On the other hand, at lower frequency (around 10
kHz), a plateau is observed for all epoxy/PPy composites due to the contribution of direct current
(DC) process.
Fig. 4. Real part (a) and imaginary part (b) of complex permittivity versus applied electri-
cal frequency for the coatings containing different PPy contents (indicated in the figure),
compared to neat epoxy coating.
Fig. 5. Volume resistivity of epoxy/PPy composites coatings as a function of PPy con-
tents in the epoxy system.
The DC electrical conductivity of the samples was measured by using I-V method. Fig. 5
shows the variation of volume resistivity as a function of PPy loading. The neat epoxy as insulating
material has very high volume resistivity, 1.1 × 1013 Ω cm. For epoxy composites containing
conducting polymer, the value of resistivity decreased with increasing the PPy contents. Between
0 and 15 wt.% PPy loading, the conductivity of composites epoxy/PPy is strongly enhanced, the
resistivity decreased from 1.1 × 1013 to 6.7 × 1010 Ω cm. The samples with 15 wt.% PPy loading
T. T.THUY, N. T. DUONG, N. T. T. TRANG, P. G. VU, T. D. LAM, AND N. A. SON 17
became a dissipated material (according to ANSI/ESD S541-2003). Over this content of PPy,
the resistivity of composites slightly decreases with increase of loading PPy, from 6.7× 1010 to
1.5×1010 Ωcm (corresponding to 30 wt.% PPy loading). It can be explained that, at the content
lower than 15 wt.%, the PPy particles were well dispersed and filled in the epoxy matrix, but after
that, they began to be saturated in the system. However, as seen in Fig. 3d, e, f, it has no important
agglomeration of PPy detected in the cross-section of epoxy containing from 20 to 30 wt.% PPy
loading composites.
Fig. 6 displays the effects of PPy loading on the mechanical properties of waterborne epoxy
system. It shows that, up to 15 wt.% PPy loading, the composites have excellent impact resistance
with measured value of 200 kg cm. With the higher PPy loading in the matrix, the impact re-
sistance properties of epoxy/PPy composites slightly decreased to 160 kg cm, corresponding to
Epo-PPy30. Despite PPy is a brittle material [11], the impact resistance of epoxy/PPy compos-
ites stayed high. It can be explained by the insertion and/or penetration of epoxy resin into the
PPy structure (overlapped sphere with high porosity) that reduce not much the impact resistance
of epoxy system. However, Fig. 6 shows a decrease of abrasion resistance with the increase of
PPy loading for the epoxy/PPy composites, from 16.2 to 10.1 L/mil. At 15 wt.% PPy loading, the
composite presents an abrasion resistance of 12.7 L/mil, 22 % lower than that of neat epoxy.
Fig. 6. Impact strength and abrasion resistance of epoxy/PPy composite coatings as a
function of PPy content in the epoxy system.
The results demonstrate that in spite of the good compatibility between PPy and epoxy
matrix, the interaction at interface of two components is not as good as the reticular network
of epoxy. We can conclude that the increase of PPy content in the epoxy systems can enhance
the electrical properties of the insulating epoxy, but it reduces the mechanical properties of the
composites, especially epoxy/PPy composites with over 15 wt.% of PPy loading.
IV. CONCLUSIONS
In this work, the effects of PPy particles on the dielectric, electrical and mechanical proper-
ties of the waterborne epoxy coating were studied. The homogenous dispersion and compatibility
of PPy in the epoxy resin with different amounts were demonstrated by FESEM. The dielectric
18 EFFECT OF POLYPYRROLE ON THE ELECTRICAL, DIELECTRIC AND MECHANICAL PROPERTIES...
constant increased with addition of PPy loading, and it was high at low frequency. It can reach
up to 18.7 for Epo-PPy30 at 1000 Hz. With over 15 wt.% PPy content, the epoxy/PPy composite
became dissipative materials with the volume resistivity down to 1.5 × 1010 Ω cm. It was found
that the impact resistance of the composites slightly decreased with the presence of PPy in the
composition. Below to 20 wt.% PPy loading, the coatings had excellent impact strength (200 kg
cm), but with 30 wt.% PPy loading, the Epo-PPy30 could reach only 160 kg cm. However, the
abrasion resistance of epoxy/PPy coatings decreased with increasing of PPy content, down to 10.2
L/mil. In combination with their electrical and mechanical properties, the epoxy/PPy coatings
with 15 or 20 wt.% of PPy loading can meet the requirements for low loss dielectric and antistatic
materials.
ACKNOWLEDGEMENT
The authors gratefully acknowledge the financial support of Vietnam Academy of Science
and Technology under project DLTE00.05/18-19.
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Effect of Polypyrrole on the Electrical, Dielectric and Mechanical Properties of Waterborne Epoxy Coatings

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Effect of Polypyrrole on the Electrical, Dielectric and Mechanical Properties of Waterborne Epoxy Coatings

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