[D002] Adsorptive Removal of Crystal violet (CV), a Carcinogenic Textile Dye, from Aqueous

Solution by Conducting Polyaniline/ Hollow Manganese Ferrite Nanocomposites

Rahmatollah Rahimi a, Hamed Kerdari b, Mahboubeh Rabbania

[email protected]
a
Chemistry Department, Iran University of Science and Technology, Tehran, Iran
b
Chemistry Department, Islamic Azad University, Saveh Branch, Saveh, Iran

Abstract:

The conducting protonated polyaniline/ hollow MnFe2O4 nanocomposite was successfully synthesized in
situ through self assembly polymerization. The core-shell of MnFe2O4 hollow spheres were fabricated by
template polymerization, at first, the ferrite nanoparticles were synthesized as the shell and coated on the
surface of functionalized polystyrene spheres as the core, subsequently, by calcination method the core
polymer was removed. The ferrite nanoparticles were combined with PANI by assisting of dodecyl benzene
sulfonic acid as doping agent under ultrasonic waves. The difference between the spectra of FT-IR for the
ferrite nanoparticles-coated PS spheres and MnFe2O4 hollow spheres show the elimination of organic
template after calcinations. The image of scanning electron microscopy (SEM) exhibit the ferrite spheres as
nanoporous with size holes of 40 nm approximately. Also the magnetic properties of the nanocomposite and
MnFe2O4 were characterized on a vibrant sample magnetometer (VSM) with maximum saturation
magnetization values of 1.59 emu/g and 66.7 emu/g respectively. X-ray diffraction (XRD) pattern of the
ferrite sample is well in agreement with the standard pattern of the cubic structure. Atomic force microscopy
(AFM) was used for surface morphology analysis. UV–Visible absorption spectroscopy recorded the
adsorption behavior of the solution after treatment with synthesized nanocomposite showing the adsorption
capacity of Crystal violet dye.

Keywords: “Polyaniline; Hollow ferrite; Surfactant; Adsorptive removal”

1. Introduction

Polyaniline (PANI) as a classic conducting polymer physico-chemical methods like adsorption [16-17],
and the low cost of its monomer has been centre of electrochemical coagulation [18] are popular now.
great attention recently. It is known that PANI has a Adsorption is one of the methods, which is obtaining
variety of oxidation states of which three of them are more attention because of its easy operations and
commonly referred to, in the literature [1–3]: versatility. It is a useful and simple technique and
leucoemeraldine base (LEB, fully reduced), emeraldine allows kinetic and equilibrium measurements without
base (EB, half-oxidized) and pernigraniline base (PNB, any highly complicated instruments [19]. In the present
fully oxidized). Therein, EB is the most attractive one, paper polyaniline/ hollow MnFe2O4 nanocomposite
because it can be doped with protonic acid to become was employed for removal of CV and used as an
emeraldine salt (ES) and the DC conductivity of the ES adsorbent in the wastewater treatment. The technique
is increased due to the charge delocalization on the was found to be useful and cost-effective for a removal
polymer backbone created by doping H+. Conducting of dye.
polymer composites with micro/nanostructures have
attracted significant academic and technological
attention because of their unique physical properties 2. Experimental
and potential applications in nanoelectronics,
electromagnetics, and biomedical devices [4]. Among Materials and Instrumentals
these conducting polymer composites, materials
decorated with inorganic nanoparticles are of particular
The monomers of aniline (Merck), styrene (Merck)
interest because possible interactions between the
were vacuum-distilled to remove the inhibitor prior to
inorganic nanoparticles and the polymer matrices may
use; Acrylic acid (Aldrich, analytical purity) was used
generate some unique physical properties upon the
as received. Other chemicals including metal salts,
formation of various micro/nanocomposites[5-8]. In
ethylene glycol (EG), potassium persulfate (KPS),
recent years, composites containing PANI and
Ammonium persulfate (APS), Hexamethylene
magnetic oxides exhibiting different nanostructures,
tetraamine (HMTA), potassium nitrate, dodecyl
such as nano-tubes, nanorods, or core-shell
benzene sulfonic acid (DBSA) and Crystal violet (CV)
nanostructures, have been extensively studied [9-12]
dye were generally reagent grade from commercial
but their investigation on hollow or porous composites
sources and used without further purification. Water
were seldom reported. Hollow inorganic spheres
was deionized and deoxygenated prior to use.
represent a special class of materials, which are of
interest in the fields of medicine, pharmaceuticals, The morphology of the particles was examinated by
materials science, and the paint industry. In particular, scanning electron microscopy (SEM, Vega II model,
the low densities of the hollow spheres are expected to Tescan). Fourier transform infrared spectroscopy
increase the stability of suspensions when compared to (FTIR) spectra were recorded on a PerkinElmer
their solid counterparts. This characteristic is highly spectrum FTIR using KBr pellets. Atomic force
advantageous for separation applications. Furthermore, microscopy (AFM, Nano Scope II from digital
there is growing interest in magnetic hollow spheres, Instruments Inc., CA, USA in contact mode) was used
which have remarkable application advantages in for surface morphology analysis of composite. Hollow
biomedicine especially in target drug delivery because particles of ferrite were examined by X-ray diffraction
of its magnetic properties and hollow structure. (XRD, Japan Jeol JDX-8030, operated at 30 kV and 20
Strategies to produce magnetic hollow spheres are mA). A vibrating-sample magnetometer (VSM,
mainly based on the sequential adsorption (layer-by- Lakeshore) was used to study the magnetic properties
layer self assembly) of magnetic nanoparticles onto of ferrite particles and composite. Conductivity
colloidal templates, normally silica or polystyrene (PS) changes were measured with four-probe device
spherical particles, and the further removal of the core (ASTM Standards, F 43-93). UV–Visible absorption
either with the addition of a solvent or high spectroscopy (Shimadzu- 1700 model, pharmaspec)
temperature [13-14]. Color is the first contaminant to was used to inscribe of adsorption behavior. pH meter
be recognized in wastewater. Dyes are used in different (Metrohm AG, CH-9101 Herisau, Switzerland) was
industries such as paper and plastics, leather, used to gain various pHs.
pharmaceutical, food, cosmetics, dyestuffs, textiles,
etc. to color the products. As a result, considerable 2.1. Experimental procedure
amount of colored wastewater is generated. The
presence of these dyes in water even at very low 2.1.1. Synthesis of polystyrene-acrylic acid
concentration is highly visible and undesirable [15]. A
copolymer
wide range of methods have been developed for the
removal of synthetic dyes from waters and wastewaters
to decrease their impact in environment. Among these
 Negatively charged PS spheres which were used as system for 10 minutes and added to above suspension,
core particles, were prepared by a free–emulsion and mixture was again sonicated for an extra 15
polymerization method, generally 5 ml of styrene minutes, and then was gently agitated by mechanical
stirrer for an additional 15 min, 10 ml of an aqueous
(0.044 mol), 1 ml of acrylic acid (0.015 mol) were
solution containing 5 g of APS (0.022 mol) as
added to the flask with 50 ml deionized water. To oxidizing agent was slowly added (during 15 min)
eliminate oxygen effects, the solution was purified while stirring mechanically to begin polymerization
with nitrogen for 15 minutes under gentle stirring then reaction. The resulting green precipitate (PANI/ hollow
process was initiated by adding 0.03 g KPS. The Mnfe2O4 nanocomposite) was filtered, washed with
mixture was heated to 72˚C under nitrogen stirring distilled water for two times and then dried overnight
with a magnetic stirrer. After 24 hr, the mixture was in an oven at 60˚C.
cooled to room temperature and the colloidal solution
2.1.5 Adsorption of CV
of functionalized PS spheres was prepared.
Adsorption studies were performed by adding 0.05 g
2.1.2 Coated particles nanocomposite to the 50mL solution of different
concentrations of CV in a beaker. The pH of the CV
In a typical process, 4 ml PS colloid solution was solution was adjusted at 7 using 0.01 mol L−1 HCl and
diluted 400 ml deoxygenated distilled water and then 0.01 mol L−1 NaOH and the solution was agitated by
mixed with 100 ml of metal salts solution which mechanical stirrer for 15 min. Then CV loaded
included 3.98 gr. Fecl2.4H2O (0.02 mol) and 1.62 gr. nanocomposite was separated with magnetic
MnCl2.2H2O (0.01 mol) and was agitated for 5 decantation and centrifugation at 3000 rpm for 5 min.
minutes, then flask was placed in ultrasonic system for The concentration of CV in the solution was measured
10 minutes, then 10 ml EG was poured in reaction spectrophotometrically at 590 nm. The concentration
solution and was dispersed for excess 15minutes by of CV decreased with time due to its adsorption by
ultrasonic, the mixture was incorporated with 8 gr. polyaniline/ hollow MnFe2O4 nanocomposite.
HMTA and 1gr potassium nitrate. Flask was heated to
85 ˚C immediately under gentle stirring. The mixture
color changed to black-brown gradually. After 3 hr, 3. Result and Discussion
system was cooled to room temperature and was
poured into excess distilled water then magnetic 3.1. Material characterization
particles were deposited by magnetic field. The
precipitate was washed with distilled water for several Figure.1 illustrates the FT-IR spectra of MnFe2O4
times and then dried in oven at 70˚C for 12 hr. the coated functionlized PS spheres
dried residue was grinded to improve calcination
process.

2.1.3 Hollow ferrite spheres

Hollow ferrite nanoparticles were produced as the

particles calcined for 3 hr under nitrogen atmosphere at
500˚C [20].
The heating rate was 10˚C min−1 below 150˚C and 5 ˚C
min−1 between 150˚C to 500˚C.

2.1.4 Synthesis of PANI/hollow Mn-Fe2O4 Fig.1 FT-IR spectra of the MnFe2O4 coated on PS spheres
nanocomposite
The typical absorption peaks at 1443.20/1490.55,
4 ml aniline (0.044 mol) and 10 ml distilled water 697.13 cm−1 are attributed to benzene ring backbone
were mixed and agitated for 15 min, in another mode in PS, the out of plane bending vibration mode
container 5gr dodecyl benzene sulfonic acid (DBSA) of the mono subsituted benzene ring group of PS
was diluted with 10ml of deionized water to form respectively, and the peak at 1732.63 cm−1 is a
pulpy mixture, and then solution was poured into characteristic absorption of the vibration of C=O bond
prepared solution of aqueous aniline, this emulsion in acrylic acid, A wide band in the spectra of the
was entirely stirred for 1 hr by magnetic stirrer to form coated PS spheres can be seen at ~3450 cm−1, which is
homogenous phase. attributed to the hydroxyls groups in acrylic acid. The
−1
In the next step 5 ml of aqueous solution containing sharp peak at 564.31cm is corresponded to the Fe–O
0.6 g of hollow ferrite spheres was placed in ultrasonic stretching vibration of the ferrite.
 700

600

500

400

Intensity
300

200

100

0
5 15 25 35 45 55 65 75
2-Theta

Fig.2 FT-IR spectra of ferrite hollow spheres calcined at 500 ̊ c

Figure.4 X-ray diffraction pattern of hollow Mn-Fe2O4
Figure.2 illustrates the FT-IR spectra of calcined
hollow Mn-Fe2O4 nanoparticles. These picks at 697.13 Fig.4 demonstrates the XRD pattern of the hollow ferrite
cm−1/~750 cm−1, 1443.20/1490.55 cm-1 and 1732.63 spheres. The position and relative intensity of all
cm−1 are related to the charged polystyrene which diffraction peaks match well with those of Fe3O4 and
disappeared after calcinations at 500 ˚C and causing Mn-Fe2O4 according to standard cards No.: 19-0629, 10-
−1
the hollow spheres. The peak at 554.77 cm is 0319, 32-0637. While sharp peaks at 35.5˚, 30.2˚, 57.2˚,
sharpened after calcinations corresponding to the Fe–O
62.9˚ are attributed to magnetite and weak peaks at 18.1˚,
stretching vibration of the ferrite.
43.3˚, 47.7˚ belongs to manganese ferrite. The presence
of magnetite indicators are due to the lower molar
percentage of manganese chloride in the reaction
compared to iron chloride; Therefore the resulting
compound is a mixture of Mn-Fe2O4 and magnetite. The
device used is λ= 1.54 Ǻ and β= 0.30˚ which is the
equivalent of 0.005 radian. The average crystallite size of
Mn-Fe2O4 particles was estimated by the scherer formula
at 28.55 nanometers. Based on the results of the XRD
curve and the mentioned standard patterns, Mn-Fe2O4 is
expected to be in cubic system.

3.2 Morphology Analysis

Fig.3 FT-IR spectra of PANI/ Hollow MnFe2O4 Nanocomposite A scanning electron microscopy (SEM) image of
porous or hollow MnFe2O4 nanospheres is displayed in
Fig.3 Shows the FT-IR spectra of PANI/hollow figure.5. As it can be seen, there are numerous uniform
MnFe2O4 nanocomposite, the weak peak at ~505 cm-1 spherical particles containing holes in the center of some
is attributed to SO3H group of DBSA surfactant [21]. spheres with diameter of about 40 nm and the hollows
Absorption band at 598.83 cm-1 is corresponding to Fe- were generated by removing organic template during
O stretching vibration. There are characteristic peaks calcinations process.
of PANI-DBSA at 1133.82/1297.40, 1399.52/1625.01,
3420.13 cm-1 which are attributed to the C-N stretching
vibration band, the C=C stretching vibration in the
aromatic ring, the N-H bond vibration respectively,
indicating the existence of the main chain structure of
the conductive doped PANI in this composite [22].
 Figure.7 AFM image of the top surface PANI/ hollow ferrite
Figure.5 SEM image of hollow MnFe2O4 nanospheres. nanocomposite

Fig.6 shows the AFM image of surface structure as- Figure.8 the AFM image indicates the height of Mn-
prepared of PANI-DBSA/hollow Mn-Fe2O4 Fe2O4 particles. According to the picture the height of
nanocomposite film containing 0.25 gr of nanoparticles were estimated at 23/655.
nanocomposite dissolved in 5 ml NMP solution.
Numerous bumps were seen of the surface of the
composite as seen in the image, which indicates the
presence of Mn-Fe2O4 magnetic nanoparticles in the
polymer. Agglomerations can be seen in some areas
which indicate the accumulation of magnetic particles
resulting from much attraction between the
nanoparticles.

Figure.8 AFM image of the height of ferrite nanoparticles in

PANI/ hollow ferrite nanocomposite

Figure.9 the AFM image indicates the width of Mn-

Fe2O4 particles. According to the picture the width of
nanoparticles were estimated at 175.78

Figure.6 AFM image of surface PANI/hollow ferrite

nanocomposite

Figure.7 the AFM image is of the top perspective of

the nanocomposite which contains numerous dots. This
indicates the even distribution of magnetic
nanoparticles in the composite. The purple color
indicates the size 200 nm for the composite
accumulation.
Figure.9 AFM image of the width of ferrite nanoparticles in
PANI/ hollow ferrite nanocomposite
Figure.11 Magnetization curve of hollow ferrite
Figure.10 the AFM image indicates the roughness of
PANI/hollow MnFe2O4 nanocomposite. According to Figure.12 shows clear saturation between -8.2≤H≤8.2
the image, the maximum amount of unevenness in the kOe with saturation magnetization (Ms) about 1.59
composite surface is estimated at 94/927 nm. emu/g and the remnant magnetization (Mr) about 0.35
emu/g for nanocomposite which is lower than pure
manganese ferrite nanoparticles, so the magnetization
curve of the sample shows weak ferromagnetic
behavior, with slender hysteresis. Magnetic properties
of nanocomposites containing magnetite or ferrite
particles have been believed to be highly dependent on
the sample shape, crystallinity, and the value of
magnetic particles, so that they can be adjusted to
obtain optimum property.

Figure.10 AFM image of the roughness of PANI/ hollow ferrite

nanocomposite

3.3. Magnetic properties

The magnetic properties of the hollow ferrite were

analyzed by room temperature VSM with an applied
field -8.2≤H≤8.2 kOe field, the value of saturation
magnetization (Ms) is about 66.7 emu/g, the remnant
Figure.12 Magnetization curve of PANI/hollow MnFe2O4
magnetization (Mr) and coercivity field are 17.81 nanocomposite
emu/g and 110 Oe respectively.

3.4. Conductivity properties

Conductivity of PANI/hollow MnFe2O4

nanocomposite doped with DBSA surfactant was
assessed using four probe conductivity assessing
device and the average of the assessments were at 1/10
S/cm. This reveals that acidic hydrogen of -SO3H
0.5
group in DBSA has a well ability of doping the PANI.
0.4
3.5. Effect of pH
0.3 pH=5
The effect of pH in the range 5–9 on the removal of

Absorption
pH=6

CV was investigated using 0.01 mol L−1 HCl or NaOH 0.2

pH=7
pH=8
solutions for pH adjustment, with the initial CV
pH=9
concentration fixed at 5 ppm. As Fig. 12 shows, the 0.1 Blank 5ppm
percent adsorption increased by raising of pH and
reached maximum (75.6%) at pH 7 and then decreased 0
400 500 600 700 800
at higher pHs. Generally at higher pHs, the amine sites
of polyaniline chain were deprotonated and polyaniline -0.1

did not prefer the adsorption of CV due to electrostatic pH

repulsion. Likewise at lower pHs, the amine groups of
Fig.13. UV-Vis Spectra of CV in various pHs (after and before
CV were protonated and could not be adsorbed on the adsorption). Conditions: 0.025 g nanocomposite, 10 ml of 5ppm
surface of polyaniline with positive charges. According CV, Agitation time of 15 min.
to Fig.13 the minimum absorption was observed at pH
7, which reveals the maximum adsorption of CV on 3.7. Adsorption behavior in various concentrations
composite happened in the neutral condition by
comparing of the initial CV concentration. Adsorption studies were carried out with different
initial concentrations of CV (1–50 mgL−1) at 25◦C and
3.6. Mechanism of the adsorption pH 7. As fig.14 and fig.15 show, the percent removal
of the CV dye with raise of solution concentration
The surfaces of conducting polyaniline/ hollow increased, which the maximum adsorption was at the
MnFe2O4 nanocomposite are positively charged that 50 ppm CV. Also, these peaks obviously show that the
vary in forms at different pHs. As the pH of the CV curve gradient grows at 1-20 ppm much sharper than
solution reached to basic condition, a proportional 20-50 ppm does. Therefore 0.05 g of the
decrease in adsorption took place due to the successive nanocomposite was approximately saturated at 20 ppm
deprotonation of on the adsorbent and electrostatic of the solution.
repulsion between electron pair sites of amine groups
on the adsorbent and dye’s amine electron pairs. There 60
was also competition between OH− (at high pH) and
dye’s amines electron pairs for adsorption of positively 50

charged sites on adsorbent.

Removal Efficiency %

40

100
30
90

80 20
Removal Efficiency(%)

70
10
60

50
0
40 0 10 20 30 40 50 60

CV- Concentration (ppm)

30

20 Fig.14. Removal of CV in various concentrations. Conditions:

10
0.05 g nanocomposite, 50 ml of 1-50 ppm CV solutions, Agitation
time of 15 min.
0
4 5 6 7 8 9 10

pH

Fig.12. Removal CV in various pHs. Conditions: 0.025 g

nanocomposite, 10 ml of 5ppm CV, Agitation time of 15 min.
 CV-nanocomposite [6] J. Zhang, A.L. Barker, D. Mandler, P.R. Unwin,
“Effect of Surface Pressure on the Insulator to Metal
2
Transition of a Langmuir Polyaniline Monolayer” J.
Am. Chem. Soc. 125 (2003) 9312-9313.
1.5
[7] G.V. Kurlyandskaya, J. Cunanan, S.M. Bhagat, J.C.
1ppm adsorption
1ppm blank Aphesteguy, S.E. Jacobo, Field-induced microwave
1
absorption in Fe3O4 nanoparticles and
Adsorption

10ppm blank
10ppm -adsorption
15ppm blank Fe3O4/polyaniline composites synthesized by different
0.5 15pm -adsorption
20ppm blank
methods, J.Phys. Chem. Solids 28 (2007) 1527-1532.
20ppm -adsorption [8] S.K. Pillalamarri, F.D. Blum, A.T. Tokuhiro, M.F.
0 Bertino, One-Pot Synthesis of Polyaniline−Metal
400 450 500 550 600 650 700 750
Nanocomposites Chem, Mater. 17 (2005) 5941-5944.
-0.5 [9] Zhiming Zhang, Meixiang Wan, Nanostructures of
wavelenght (nm)
polyaniline composites containing nano-magnet Synth.
Fig.15. UV-Vis spectra of different concentrations CV (after and Met. 132 (2003) 205-212.
before adsorption on nanocomposite) amount of adsorbent is [10] Q.L. Yang, J. Zhai, L. Feng, Y.L. Song, M.X.
0.05 g and pH of the solutions is 7. Wan, L. Jiang, W.G. Xu, Q.S. Li, Synthesis and
Characterization of Conducting Polyaniline/γ-Fe2O3
4. Conclusion Magnetic Nanocomposite, Synth. Met. 135–136
(2003) 819.
In summary, the PANI/ MnFe2O4 nanocomposite [11] J. Deng, X. Ding, W. Zhang, Y. Peng, J. Wang, X.
containing hollow ferromagnetic nanoparticles has Long, P. Li, A.S.C. Chen, Magnetic and conducting
been synthesized. This report is a helpful method to Fe3O4–cross-linked polyaniline nanoparticles with
improve mixability of inorganic particles with an core–shell structure, Polymer 43 (2002) 2179-2184.
organic phase. The results of AFM image indicate the [12] E. Jacobo, C. Aphesteguy, R. Lopez Anton, N.N.
even distribution of MnFe2O4 in the PANI base and Schegoleva, G.V. Kurlyandskaya, Influence of the
this proves the effectiveness of DBSA and ultrasonic preparation procedure on the properties of polyaniline
devices in mixing two nonhomogenious phases. UV based magnetic composites, European Polymer
spectra display that the prepared naoncomposite has a Journal 43 (2007) 1333–1346.
suitable ability to remove the group of textile dyes with [13] F. Caruso, M. Spasova, A. Susha, M. Giersig,
the similar structure to CV containing amine groups at R.A. Caruso, Magnetic Nanocomposite Particles and
the ends of dye molecules. As 75.6 % of 5 ppm CV Hollow Spheres Constructed by a Sequential Layering
solution (10 ml) was adsorbed by mentioned Approach, Chem. Mater. 13 (2001) 109-116.
nanocompoiste, removal efficiency might be increased [14] Y.H. Zhu, H. Da, X.L. Yang, Y. Hu, Preparation
by using of more weights adsorbent in the proportional and characterization of core-shell monodispersed
volumes of various concentrations. magnetic silica microspheres, Colloid Surf., A 231
(2003) 123-129.
[15] R. Jain, S. Sikarwar, Photocatalytic and
adsorption studies on the removal of dye Congo red
References from wastewater, Int. J. Environ. Pollut. 27 (2006)
158–178.
[1] J. Stejskal, R.G. Gilbert, Polyaniline Preparation of
[16] V.K. Gupta, A. Mittal, L. Krishnan, V. Gajbe,
a Conducting Polymer, Pure Appl. Chem. 74 (2002)
857-867. Adsorption kinetics and column operations for the
removal and recovery of malachite green from
[2] J.E. Albuquerque, L.H.C. Mattoso, D.T. Balogh,
wastewater using bottom ash, Sep. Purif. Technol. 40
R.M. Faria, J.G. Masters, A.G. Mac Diarmid, A
(2004) 87–96.
simple method to estimate the oxidation state of [17] A. Mittal, L. Kurup (Krishnan), V.K. Gupta, Use
polyanilines, Synth. Met. 113 (2000) 19-22. of waste materials—bottom ash and de-oiled soya, as
[3] B. Lesiak, A. Jablonski, J. Zemek, M. Trchova, potential adsorbents for the removal of Amaranth from
“Determination of the Inelastic Mean Free Path of aqueous solutions, J. Hazard. Mater. 117 (2005) 171–
Electrons in Different Polyaniline Samples” J. 178.
Stejskal, Langmuir 16 (2000) 1415-1423. [18] C.L. Yang, J. McGarrahan, Electrochemical
[4] J. Lei, V.P. Menon, C.R. Martin, Polym. coagulation for textile effluent decolorization, J.
Adv.Technol. 4 (1992) 124-132. Hazard. Mater. 127 (2005) 40–47.
[5] J.G. Deng, X.B. Ding, Y.X. Peng, Magnetic and [19] K.E. Noll, G. Vassilios, W.S. Hou, Adsorption
conducting Fe3O4 cross-linked polyaniline Technology for Air and Water Pollution Control,
nanoparticles with core-shell structure, Polymer 43 Lewis Publishers, Chelsea, MI, USA, 1992.
(2002) 2179-2184.
[20] Y. Zhang, Z. Huang, F. Tang, Ferrite hollow
spheres with tunable magnetic properties, Thin Solid
Films 515 (2006) 2555–2561
[21] K.G. Neoh, M.Y. Pun, E.T.K. Kang, K.L. Tan,
Synth. Met. 73 (1995) 209.

[22] M.X. Wan, M. Li, J.C. Li, Z.X. Liu, J. Appl.

Polym. Sci. 53 (1994) 131.