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Research Article
The Use of Le Bail Method to Analyze
the Semicrystalline Pattern of a Nanocomposite Based on
Polyaniline Emeraldine-Salt Form and -Al2O3
Copyright 2015 Edgar A. Sanches et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.
Ceramic nanocomposites constituted by a matrix of -Al2 O3 microparticles reinforced by polyaniline emeraldine-salt form (PANI-
ES) nanoparticles were prepared by in situ polymerization and characterized structural and morphologically. Peaks related to both
materials were observed through XRD technique: PANI-ES presented peaks at 2 = 8.9, 14.9, 20.8, 25.3, 27.1, and 30.0 and in -Al2 O3
phase peaks were found at 2 = 25.6, 35.2, 37.9, 43.5, 52.6, 57.6, and 68.1 . Nanocomposite crystallinity percentage was estimated
around 70%. SEM showed a polymerization of PANI-ES over alumina plates. By Le Bail method it was observed that PANI-ES and
-Al2 O3 have crystallite average size around, respectively, 41 and 250 A.
By FTIR analysis characteristic absorption bands of both
materials were identified. Additional bands indicating new chemical bonds were not observed, suggesting that nanocomposite was
formed by physical deposition. Nanocomposite DC electrical conductivity was found around 0.24 S/cm (against 1.84 104 S/cm
for pure PANI-ES), showing an increase of about 1,300 times compared to the pure PANI-ES at room temperature. Thus, this
paper showed that both materials have kept its original structural characteristics and exhibited high electrical conductivity when
combined in nanocomposite form.
flexibility, and processability [32, 33]. A widely used mech- phases. The integration was carried out over the whole range
anism for improving its solubility and processability is the 2 = 5 to 55 , where is the Bragg angle. The estimated
introduction of polar functional and long flexible alkyl crystallinity (E.C.), given as a percentage, was obtained by
groups mainly bonded to the main chain [34]. Furthermore, E.C. = 100 /( + ), where and are, respectively,
PANI is one of the most promising industrial alternatives to the crystalline and noncrystalline integrated intensities [36].
obtain nanocomposites or blends. Then, one can combine the
electrical properties of PANI with mechanical properties of
2.4. Le Bail Method. The use of Le Bail whole powder pattern
the insulating matrix, such as alumina [35].
decomposition method [37] to obtain structural information
Nanocomposite constituted by -Al2 O3 microparticles
from semicrystalline patterns is not very common due to
reinforced by PANI-ES nanoparticles was prepared by in
the large overlapped peaks on diffractograms. Nevertheless
situ polymerization. Fourier-transform infrared spectroscopy
it has been used to characterize polyurethane, polyaniline,
(FTIR) was used for bonds of structural information; XRD
and substituted polyanilines [25, 38, 39]. Le Bail method
was used for the determination of cell parameters and
was performed using the software package FullProf [40].
crystallinity percentage estimative; Le Bail method was per-
All parameters were refined by the least-squares method
formed to refine cell parameters and to obtain crystallite size
[41]. The pseudo-Voigt function modified by Thompson-
and shape; SEM was carried out for the determination of solid
Cox-Hastings was used as peak profile function [42]. Instru-
nanocomposite morphology. These results were correlated
mental resolution function parameters were obtained from
with electrical properties. The crystal structure investigation
a lanthanum hexaborate standard, LaB6 . Aniline tetramer
of semicrystalline materials is an important research topic in
single crystal parameters obtained by Evain et al. [43] were
many areas and remains in full development. Understanding =
used as initial parameters for PANI phase ( = 5.7328 A,
the structure of semicrystalline nanocomposites constituted = 22.6889 A, = 82.7481 , = 84.5281 , and =
8.8866 A,
by polymer/ceramic materials is essential to the development
88.4739 ). Aluminum oxide structural parameters obtained
of new technological applications.
by Lutterotti and Scardi [44] were used as initial parameters
for alumina phase ( = 4.756 A, = 4.756 A,
= 12.9636 A, =
2. Experimental 90.0 , = 90.0 , and = 120.0 ). Anisotropic crystallite size
was determined using spherical harmonics (SHP) [4547].
2.1. Nanocomposite Synthesis. PANI-ES/-Al2 O3 synthesis
was performed based on Zhang (2006) [8] and Sanches
et al. (2013) [25], with some modifications. Aniline (ANI) 2.5. SEM Analysis and DC Conductivity Measurements. SEM
monomer was purchased from Sigma-Aldrich and further experiments were performed in equipment Supra 35, Carl
distilled. -Al2 O3 was obtained from Sapra, SA; Sao Carlos, Zeiss. Powder samples were deposited on a carbon tape and
SP, in December 2013. Two solutions were prepared. In the surface morphology was obtained at room temperature.
Solution I, 20 mL of distilled aniline (ANI) was dissolved For DC conductivity measurements, samples processed into
in 500 mL of hydrochloric acid (HCl) 1.0 M, added to 167 g pellets were coated with silver ink on both sides in which
of -Al2 O3 powder under stirring. In Solution II, 11.5 g electrical connections were made. Measurements were per-
of ammonium persulfate (APS) was added to 200 mL of formed at room temperature (300 K) using a Keithley Model
hydrochloric acid (HCl) 1.0 M. Then, Solution II was rapidly 2612 A from 500 mV to 2 V.
added to Solution I allowing the polymerization. System
remained under stirring for 3 h. Then, the dispersion of green 3. Results and Discussion
color with -Al2 O3 particles was vacuum filtered and washed
with acetone. 3.1. FTIR Analysis. Figure 1 shows the FTIR spectra of the
nanocomposite (PANI-ES/-Al2 O3 ), PANI-ES, and -Al2 O3 .
2.2. Fourier-Transformed Infrared Spectroscopy (FTIR). In- For PANI-ES spectrum, bands were found between 1556 and
frared spectra were measured in Nanomed Inovaca o em 1457 cm1 (band 1), which were related to C=C double bonds;
Nanotecnologia in a spectrophotometer Bomem-MB Series- bands between 1300 and 1234 cm1 (band 2) are due to the C
Hartmann and Braun in the range of 4002000 cm1 . Sam- N stretching; a band located at 1132 cm1 (band 3) is attributed
ples were prepared in KBr pellet with mass ratio of 1 : 100. to vibration of CH bond and 794 cm1 (band 4) to the
out-of-plane angular vibration of CH aromatics. Regarding
the -Al2 O3 phase, bands between 649 and 457 cm1 corre-
2.3. X-Ray Diffraction and Crystallinity Percentage. XRD data
spond to the condensed AlO6 octahedra which compose the
were obtained at the Laboratory of X-ray Crystallography of
building blocks in -Al2 O3 structure [48]. Thus, in the FTIR
IFSC/USP, Sao Carlos, SP, using a Rigaku Rotaflex diffrac-
nanocomposite spectrum bands related to both materials
tometer equipped with graphite monochromator and rotat-
were observed. No additional bands related to new chemical
ing anode tube, operating with Cu K, 50 kV, and 100 mA.
bonds were found, suggesting that the nanocomposite was
Powder diffraction patterns were obtained in step scanning
formed by physical deposition.
mode, 2 = 555 , step of 0.02 , and 3 s/step. Using routine
software, crystallinity percentage was estimated using the
diffractogram pattern and separating and then measuring the 3.2. X-Ray Diffraction and Crystallinity Percentage. By XRD
integrated intensities from the crystalline and noncrystalline technique the diffraction pattern of the nanocomposite
Advances in Materials Science and Engineering 3
Transmittance
Intensity (a.u.)
1 2 3 4
2000 1800 1600 1400 1200 1000 800 600 400
Wavenumber (cm1 ) 10 20 30 40 50
2 (deg)
PANI-ES
-l2 O3 Semicrystalline pattern
Nanocomposite Amorphous area
(Semicrystalline-amorphous) pattern
Figure 1: FTIR of PANI-ES, -Al2 O3 , and nanocomposite.
Figure 3: Decomposition of the POEA-ES diffraction peaks.
Intensity (a.u.)
Figure 2: Nanocomposite X-ray diffraction pattern. nanosized particles with morphologies similar to intercon-
nected nanospheres were observed, which form the polymer
nanofibers. Figures 4, 5(a), and 5(b) show, respectively, the
morphologies of alumina and PANI-ES. In the nanocompos-
PANI-EB/-Al2 O3 was obtained. Peaks related to both mate- ite it was observed that polymerization of PANI-ES occurred
rials were observed in diffractogram. With respect to PANI- on the -Al2 O3 plates by physical deposition (as suggested
ES, peaks were found at 2 = 8.9, 14.9, 20.8, 25.3, 27.1, and by FTIR analysis), being possible to observe in Figures
30.0 [25] and for -Al2 O3 phase peaks were present at 6(a)6(c) the morphology of both materials combined in
2 = 25.6, 35.2, 37.9, 43.5, and 52.6 [44]. Figure 2 shows nanocomposite form.
the nanocomposite XRD pattern. Crystallinity percentage An increasing about 1,300 times in nanocomposite DC
was estimated from the whole nanocomposite XRD pattern. electrical conductivity (0.24 S/cm) was verified when com-
Figure 3 shows the superposition of the diffraction pattern pared to the pure sample of PANI-ES [25]. This is surprising
of nanocomposite (PANI-ES/-Al2 O3 ) (black), the supposed since alumina is an electrical insulator with DC electrical con-
profile related to the noncrystalline phase (red), and the ductivity about 1014 S/cm. The pure PANI-ES conductivity
corresponding profile of the supposed crystalline phase (dark was found around 1.84 104 S/cm for Sanches et al. [25], as
blue). Nanocomposite crystallinity percentage was estimated expected.
around 70%. We suggest that the most compact PANI-ES interface
between the -Al2 O3 plates contributed significantly to
3.3. SEM Analysis and DC Conductivity Measurements. increasing the nanocomposite DC electrical conductivity.
Scanning electron microscopy (SEM) technique revealed The conductive polymer over the -Al2 O3 plates surface
that the ceramic material has particles with a range of (percolation threshold) might promoted easier paths for
micrometric sizes with plates-like morphology. For PANI-ES the charge carriers. Zhang [8] obtained a conductive value
4 Advances in Materials Science and Engineering
(a) (b)
Figure 5: SEM image of PANI-ES with increase of (a) 31,000 and (b) 100,000 times.
(a) (b)
(c)
of 0.17 S/cm for core-shell structured alumina-polyaniline 3.4. Le Bail Method Analysis. A process using iteratively the
particles. Michalek et al. [49] studied the electrical conduc- Rietveld decomposition formula for whole powder pattern
tivity in alumina/multiwall carbon nanotubes (MWCNT) decomposition (WPPD) purposes was first applied in 1988
that obtained an increase from 1014 S/cm (pure alumina) to [37] and called much later the Le Bail method or Le Bail
2.7 103 S/cm for composites. However, the DC electrical fit, or pattern matching as well as profile matching in
conductivity can decrease in the case of a better interaction the FullProf Rietveld program [40]. In the original computer
between the composite components: Teoh et al. [50] syn- program first applying that method, arbitrarily all equal
2
thesized nanofibers composite by oxidative polymerization (calc) values are first used, instead of using structure factors
of aniline with alumina nanofibers and the DC electrical calculated from the atomic coordinates, resulting in (obs)
2
conductivity decreased with increasing alumina nanofibers which are then reinjected as new (calc) values at the next
from 0.18 S/cm to 103 S/cm for alumina loading from 0% to iteration, while the usual profile and cell parameters (but
20%. not the scale) are refined by least squares. Equipartition of
Advances in Materials Science and Engineering 5
Table 1: Comparison between the values found by Evain et al. (2002) [43] and Lutterotti and Scardi (1990) [44] with those found by PANI-ES
and -Al2 O3 , respectively, through Le Bail method.
a b c
c a b
(a)
a b c
c a b
(b)
FTIR technique revealed that nanocomposite has char- conductivity around 1,300 times when compared to pure
acteristic absorption bands related to both materials, sug- sample of PANI-ES. To explain this increasing in conduc-
gesting that nanocomposite has preserved the original struc- tivity, we suggested that the interface between PANI-ES/-
tural characteristics of its constituents. Conducting poly- Al2 O3 probably created easier paths for charge carriers in
mer/inorganic nanocomposite can be classified into two nanocomposite. We hope that the structural information
types: physical deposition, in which the polymer is absorbed provided in this study may be useful in the area of mate-
on the surface of inorganic particles, and chemical deposi- rials science and, more specifically, in several technological
tion, in which there is a covalent bond between them [11]. So, applications that require conducting nanocomposites with
FTIR analysis showed that there was no chemical interaction electrical conductivity in the obtained range.
between PANI-ES and -Al2 O3 .
The great contribution of this work is to obtain struc-
tural information using the Le Bail whole powder pattern Conflict of Interests
decomposition method applied to a semicrystalline system The authors declare that there is no conflict of interests
consisting of semicrystalline polymeric/highly crystalline regarding the publication of this paper.
ceramic materials. The purpose of this work is also to promote
this important structural characterization tool, which can be
properly applied for semicrystalline materials. This method Acknowledgment
allowed the determination of cell parameters and crystallite
size/shape for all phases. The refined cell parameters, so The authors are grateful to the Brazilian Agency FAPEAM
closed to the original values, showed that all phases have (Fundacao de Amparo a` Pesquisa do Estado do Amazonas)
kept its structural characteristics after synthesis. For PANI- for the financial support to this work based on the Edital
ES and -Al2 O3 there were, respectively, average crystallite Papac 020/2013.
sizes around 41 and 250 A.
With respect to conductivity measurements, this work
showed that it is possible to increase the conductivity of
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