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Integrated Composites Lab (ICL), Dan F. Smith Department of Chemical Engineering, Lamar University, Beaumont, Texas 77710,
United States
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Department of Chemistry and Biochemistry, Lamar University, Beaumont, Texas 77710, United States
Mechanical Engineering Department, University of WisconsinMilwaukee, Milwaukee, Wisconsin 53211, United States
Department of Physics and Astronomy, Louisiana State University, Baton Rouge, Louisiana 70803, United States
*
S Supporting Information
ABSTRACT: The conductive polypyrrole (PPy) polymer nanocomposites (PNCs) reinforced with dierent magnetite (Fe3O4)
nanoparticle loadings have been successfully synthesized by using a facile surface initiated polymerization (SIP) method. The
scanning electron microscope (SEM) is used to characterize the surface morphology of the as-received Fe3O4 nanoparticles
(NPs), pure PPy and Fe3O4/PPy PNCs. The high-resolution transmission electron microscope (HRTEM) is used to observe the
nanoparticle dispersion within the polymer matrix. The chemical structure of the PNCs is characterized by Fourier transform
infrared (FT-IR) spectroscopy. The thermal stability of the Fe3O4/PPy PNCs is assessed by thermogravimetric analysis (TGA).
X-ray diraction (XRD) results reveal that the addition of NPs has a signicant eect on the crystallization of PPy. The switching
frequency, at which the permittivity switches from negative to positive, is observed in the synthesized pure PPy and Fe3O4/PPy
PNCs. The optical band gap of Fe3O4/PPy PNCs is studied by ultravioletvisible diuse reectance spectroscopy (UVvis
DRS). The Fe3O4/PPy PNCs exhibit no hysteresis loop, indicating the superparamagnetic behavior. Temperature-dependent
resistivity indicates a quasi-3-dimensional variable range hopping (VRH) electrical conduction mechanism for the synthesized
samples. The positive magnetoresistance (MR) is observed in the synthesized pure PPy at room temperature and analyzed by the
wave function shrinkage model. Meanwhile, the negative MR is obtained in the synthesized magnetic PNCs at room temperature
and analyzed by the orbital magnetoconductivity theory (forward interference model).
2013 American Chemical Society 10191 dx.doi.org/10.1021/jp402236n | J. Phys. Chem. C 2013, 117, 1019110202
The Journal of Physical Chemistry C Article
materials, photovoltaic cells, coating materials, and corrosion studied by X-ray diraction (XRD). Scanning electron
inhibitors.2,6,7 microscope (SEM) and a high-resolution transmission electron
Fe3O4 is a mixed iron oxide with a cubic inverse spinel microscope (HRTEM) are used to depict the dispersion and
structure, AB2O4.8 In the AB2O4, the A site is occupied by Fe3+ morphology of the as-received Fe3O4 NPs, pure PPy, and
and the B sites have an equal mix of Fe3+ and Fe2+.9 Fe3O4 is a Fe3O4/PPy PNCs. The frequency-dependent permittivity,
half-metallic ferromagnetic material, in which the density state temperature-dependent resistivity, MR, optical properties, and
at the Fermi level N(EF) is completely polarized and the magnetic properties are systematically investigated as well. The
conductivity is determined by the metallic electron spin charge positive magnetoresistance (MR) observed in the synthesized
carriers because of the coexistence of metallic electron spin and pure PPy at room temperature is analyzed by the wave function
insulating electron spin.10 Because of the unique properties, shrinkage model and the negative MR obtained in the
such as catalytic, magnetic, and electrical properties,2,11 Fe3O4 synthesized magnetic PNCs at room temperature is analyzed
has been widely applied in many elds such as catalysis, by the orbital magnetoconductivity theory (forward interfer-
biomedicine, information storage, color imaging, cell separa- ence model), respectively.
tion, and environment remediation.12,13 Incorporating the
Fe3O4 NPs into polymer matrix can widen their deployments 2. EXPERIMENTAL SECTION
in electronic, biomedical, and optical elds.7,14 2.1. Materials. Pyrrole (C4H5N, 98%), ammonium
Recently, there have been many works on the study of persulfate (APS, (NH4)2S2O8, 98%), and p-toluene sulfonic
magnetic PPy PNCs. For example, Dey et al.15 have prepared acid (PTSA, C7H8O3S, 98.5%) were purchased from Sigma-
the Fe3O4/PPy PNCs with a very large dielectric constant using Aldrich. The Fe3O4 NPs were obtained from Nanjing Emperor
ammonium peroxodisulfate (APS) as oxidant. Chen et al.16 Nano Material Co., Ltd., China. All the chemicals were used as-
have synthesized Fe3O4/PPy using the common ion eect and received without any further treatment.
studied the inuence of concentration of oxidant FeCl3 solution 2.2. Fabrication of Fe3O4/PPy PNCs. Fe3O4/PPy PNCs
on the properties of PPy/Fe3O4 composites, which show the were fabricated by using the SIP method. First, the Fe3O4 NPs
electrical and ferromagnetic properties. Wang et al.17 have were dispersed in an aqueous solution containing PTSA (15
successfully encapsulated Fe3O4 with PPy via emulsion mmol) and APS (9 mmol) in 100 mL of deionized water by 1-h
polymerization using polyvinyl alcohol as a surfactant and sonication (Branson 8510) and mechanical stirring (SCILO-
studied the application of Fe3 O 4 /PPy in biomedicine GEX OS20-Pro LCD Digital Overhead Stirrer, 300 rpm) in an
application. Chen et al.18 have prepared the Fe3O4/PPy icewater bath. Second, the pyrrole solution (18 mmol, 25 mL
PNCs and investigated magnetic and electrical properties of deionized water) was mixed with the above Fe3O4 NPs
Fe3O4/PPy PNCs. However, the negative permittivity and suspension and mechanically and ultrasonically stirred con-
magnetoresistance (MR) of Fe3O4/PPy PNCs have been rarely tinuously for an additional 1.5 h in the icewater bath for
reported so far. further polymerization. The product was vacuum ltered and
Metamaterials formed from either periodic or random arrays washed with deionized water several times. The precipitant was
of scattering elements are articial materials.19,20 The two further washed with 1 mol L1 PTSA. The nal synthesized
macroscopic electromagnetic parameters (the electric permit- nanocomposites were dried at 60 C in an oven overnight. The
tivity , and the magnetic permeability ) are used to Fe3O4/PPy PNCs with a nanoparticle loading of 10, 20, 40, and
characterize the metamaterials.20 Compared with conventional 60 wt % were fabricated, respectively. The pure PPy was
materials, metamaterials can exhibit unique electromagnetic fabricated following the above procedures without adding any
behaviors due to the negative permittivity and negative NPs for comparison.
permeability at a certain frequency.21 The metamaterials can 2.3. Characterizations. The Fourier transform infrared
be used to design invisibility devices (such as invisibility cup),22 (FT-IR) spectra of the products were obtained on a Bruker Inc.
super lenses,21 and cloaking.23 Vector 22 (coupled with an ATR accessory) in the range of 500
MR is a phenomenon that reects the resistance change of a to 2200 cm1 at a resolution of 4 cm1. TGA analysis was
material under an external magnetic eld.24 The MR eect conducted by TA Instruments TGA Q-500 with a heating rate
observed in the organic materials is called organic magnetor- of 10 C min1 under an air-ow rate of 60 mL min1 from 25
sistance (OMAR),25 which is related to the formation of the to 700 C. XRD was measured by D/max-rB wide-angle X-ray
excitons and caused by the trapping of charge carrier at triplet diractometer at a Cu K wavelength of 0.154 nm. The
excitons.26 There are many studies on the MR eect of PPy scanning rate is 4 min1 from 10 to 80. The SEM was
polymer reinforced with dierent nanoparticles. For example, performed in a JEOL JSM-6510LV system after coating with
Abou-Elazab et al.27 have found the positive MR in the PPy, carbon. The HRTEM was performed on the Hitachi
which is prepared by electrochemical oxidation of pyrrole and H9000NAR. Dielectric properties were investigated by a LCR
doped with tetraethylammonium toluene-4-sulfonate. Long et meter (Agilent, E4980A) equipped with a dielectric test xture
al.28 have studied the negative MR of multiwalled carbon (Agilent, 16451B) at the frequency of 20 to 2 106 Hz at room
nanotube/PPy synthesized using an in situ chemical oxidative temperature. Pure PPy and Fe3O4/PPy PNCs were pressed in a
polymerization method. However, there are no reports form of disc pellet with a diameter of 25 mm by applying a
regarding the negative MR of the Fe3O4/PPy PNCs. pressure of 50 MPa in a hydraulic presser and the average
In this work, Fe3O4/PPy PNCs are synthesized by using the thickness of the samples was about 0.6 mm. The same samples
surface initiated polymerization (SIP) method. The Fourier were also used to measure the resistivity, MR, and ultraviolet
transform infrared (FT-IR) spectroscopy is used to characterize visible diuse reectance spectroscopy (UVvis DRS). The
the chemical structure of the as-received Fe3O4 NPs, pure PPy, resistivity was measured by a standard four-probe method from
and Fe3O4/PPy PNCs. The thermal stability of the Fe3O4/PPy 100 to 290 K. The temperature-dependent resistivity was used
PNCs is performed by thermogravimetric analysis (TGA). The to determine the electrical conduction mechanism in the pure
eects of Fe3O4 NPs on the crystallization of the PPy are also PPy and Fe3O4/PPy PNCs. UVvis DRS of pure PPy and
10192 dx.doi.org/10.1021/jp402236n | J. Phys. Chem. C 2013, 117, 1019110202
The Journal of Physical Chemistry C Article
Figure 1. SEM micrographs of (a) as-received Fe3O4 NPs, (b) pure PPy, and Fe3O4/PPy PNCs with a Fe3O4 nanoparticle loading of (c) 20 and (d)
60 wt %, respectively.
Figure 2. HRTEM images of (a) as-received Fe3O4 NPs, (b) Fe3O4/PPy PNCs with a Fe3O4 nanoparticle loading of 40 wt %, and (c) selected area
electron diraction (SAED) of Fe3O4/PPy PNCs with a Fe3O4 nanoparticle loading of 40 wt %.
to be relatively loosely packed compared to the Fe3O4/PPy CN stretching vibration, respectively.2,6,7 The CC
PNCs, Figure 1c,d. The surface of the as-received Fe3O4 NPs is vibration is reected at a peak of 1132 cm1.32 The peaks at
smooth. However, the surface of the Fe3O4/PPy PNCs 1276 and 1007 cm1 are assigned to the CH in-plane and
becomes rougher due to the polymerization that occurred on out-of-plane deformation vibration, respectively.32 The small
the surface of Fe3O4 NPs. The HRTEM images of the as- band located at 960 cm1 is assigned to the CC out-of-plane
received Fe3O4 NPs and the Fe3O4/PPy PNCs with a Fe3O4 deformation vibration.32 These characteristic peaks (1521,
nanoparticle loading of 40 wt % are shown in Figure 2a,b. The 1431, 1276, 1132, 1007, and 960 cm1) of the pure PPy are also
HRTEM image of the as-received Fe3O4 NPs, Figure 2a, shows observed in the Fe3O4/PPy PNCs, Figure 3cf. However, these
that the average diameter of Fe3O4 NPs is about 11.14 nm characteristic peaks have some shifts (about 716 cm1)
measured by Nano measure software. However, this result is compared with those of the pure PPy, indicating the interaction
dierent from that observed in the SEM (59.61 nm), Figure 1a, between the Fe3O4 NPs and the polymer matrix.8 These results
in which some of the Fe3O4 NPs agglomerate together because indicate that the Fe3O4/PPy PNCs have been successfully
of the magnetic dipoledipole interactions (also called dipolar synthesized.
coupling, which means direct interaction between two magnetic 3.3. Thermogravimetric Analysis. Figure 4 shows the
dipoles) between Fe3O4 NPs.29 The clear lattice fringes TGA curves of the as-received Fe3O4 NPs, pure PPy, and
presented in Figure 2a indicate the highly crystallized as-
received Fe3O4 NPs. The lattice fringe d-spacing value
(interplanar distance) of the as-received Fe3O4 NPs is about
0.29 nm, which corresponds to the (2 2 0) crystallographic
plane (which examines the arrangement of atoms in solids) of
Fe3O4.30 Figure 2b shows the microstructure of the Fe3O4/PPy
PNCs with a Fe3O4 nanoparticle loading of 40 wt %, which
consists of the crystalline Fe3O4 inside and the amorphous PPy
polymer layer outside. The crystal structure of the Fe3O4/PPy
PNCs with a Fe3O4 loading of 40 wt % is identied by the
selected area electron diraction (SAED), Figure 2c. The
calculated d-spacing values of 2.94, 2.56, 2.08, 1.61, and 1.49
correspond to the (2 2 0), (3 1 1), (4 0 0), (4 2 2), and (4 4 0)
crystallographic planes of Fe3O4.31 Figure S1 shows the acid
dissolubility of the as-received Fe3O4 NPs and the synthesized
Fe3O4/PPy PNCs with a Fe3O4 loading of 60 wt %. The Fe3O4
NPs are observed to dissolve in the 1.0 mol L1 hydrochloric
acid (HCl) solution and the color changes to yellow. However,
the Fe3O4/PPy PNCs are observed not to dissolve in the same Figure 4. TGA curves of as-received Fe3O4 NPs, pure PPy, and
Fe3O4/PPy PNCs with a Fe3O4 nanoparticle loading of 10, 20, 40, and
acid solution, which indicates that Fe3O4 NPs have been 60 wt %.
successfully protected by the PPy matrix.
3.2. FT-IR Analysis. Figure 3 shows the FT-IR spectra of
the as-received Fe3O4 NPs, pure PPy, and Fe3O4/PPy PNCs Fe3O4/PPy PNCs with a Fe3O4 nanoparticle loading of 10, 20,
with dierent Fe3O4 nanoparticle loadings. For the as-received 40, and 60 wt %. For the as-received Fe3O4 NPs, the weight has
Fe3O4 NPs, Figure 3a, the peak around 529 cm1 is due to the only a slight change within the measured temperature range
vibration of the FeO band.8 For the pure PPy, Figure 3b, the from 35 to 700 C.13 Two weight loss regions are observed in
peaks located at 1521 and 1431 cm1 are due to the CC and the TGA curves of pure PPy and its Fe3O4 PNCs. The steady
weight loss from 30 to 240 C is due to the elimination of the
moisture and dopant anions in the samples.8 The major weight
loss of all the synthesized samples from 240 to 650 C is due to
the decomposition of PPy.1 The 10% weight loss decom-
position temperature for the pure PPy and Fe3O4/PPy PNCs
with a Fe3O4 nanoparticle loading of 10, 20, 40, and 60 wt %
are 254, 257, 272, 287, and 300 C, respectively. This result
indicates that the thermal stability of the Fe3O4/PPy PNCs is
improved by the addition of Fe3O4 NPs and increases with
increasing Fe3O4 nanoparticle loading, which is also observed in
the -Fe2O3/PPy PNCs system.7 Interestingly, it is found that
the TGA curves of Fe3O4/PPy PNCs reach a plateau at a
certain temperature. The temperature to reach the plateau
decreases with increasing nanoparticle loading. The higher the
nanoparticle loading, the lower the PPy weight percentage
obtained, thus the PNCs with high nanoparticle loadings would
reach the plateau at low temperature. At high temperature, the
Fe3O4 NPs get oxidized to form hematite (-Fe2O3).33 The
Figure 3. FT-IR spectra of (a) Fe3O4 NPs, (b) pure PPy, and Fe3O4/ weight residue of pure PPy at 700 C is about 1.83 wt % arising
PPy PNCs with a Fe3O4 nanoparticle loading of (c) 10, (d) 20, (e) 40, from the carbonized PPy, which indicates that PPy cannot
and (f) 60 wt %, respectively. easily become completely decomposed in the air even at a
10194 dx.doi.org/10.1021/jp402236n | J. Phys. Chem. C 2013, 117, 1019110202
The Journal of Physical Chemistry C Article
higher temperature.2 The weight residue for the -Fe2O3 is average crystallite size of the Fe3O4/PPy PNCs with a Fe3O4
calculated to be 11.39, 25.28, 42.42, and 60.47 wt % for the loading of 60 wt % are about 0.25 and 11.5 nm, respectively.
Fe3O4/PPy PNCs with a Fe3O4 loading of 10, 20, 40, and 60 wt Obviously, the Fe3O4/PPy PNCs have the diraction peaks of
%, respectively. The weight percentage of Fe3O4 is calculated to the Fe3O4 NPs, Figure 5be, and the intensity of the peaks
be 11.01, 24.44, 41.01, and 58.45 wt %, respectively. becomes stronger with increasing the Fe3O4 nanoparticle
3.4. X-ray Diraction Analysis. Figure 5 shows the XRD loading. However, the broad peak of pure PPy at 2 = 15.2
patterns of the as-received Fe3O4 NPs, pure PPy, and Fe3O4/ 27.9 shows a reduced intensity with increasing the Fe3O4
nanoparticle loading, indicating a strong eect of the Fe3O4
NPs on the crystallization of PPy. This is also observed in the
Fe3O4/PANI PNCs.8
3.5. Dielectric Properties. Figure 6 shows the real
permittivity (), imaginary permittivity (), and dielectric
loss tangent (tan , where tan = /) as a function of
frequency at room temperature for pure PPy and its Fe3O4
PNCs with a Fe3O4 nanoparticle loading of 10, 20, 40, and 60
wt %, respectively. In Figure 6a, the for pure PPy and its
Fe3O4 PNCs switches from negative to positive and increases
with increasing the frequency from 102 to 104 Hz. This
frequency-dependent property is contributed to the interfacial
polarization,1 where the charge carriers are accumulated at the
internal interfaces arising from the MaxwellWagnerSillars
polarization eect (which occurs on a mesoscopic scale either at
the inner dielectric boundary layers or at the external
electrodesample interface).35 The inset of Figure 6a shows
Figure 5. The XRD patterns of (a) pure PPy, and the Fe3O4/PPy the positive value within the frequency range from 104 to 2
PNCs with a nanoparticle loadings of (b) 10, (c) 20, (d) 40, and (e) 106 Hz. The decrease of at high frequency is induced by the
60 wt %, respectively, and (f) as-received Fe3O4 NPs. well-known dielectric relaxation phenomena,23 which is usually
caused by the delay of molecular polarization in an external
PPy PNCs with dierent Fe3O4 nanoparticle loadings. Only a alternative electric eld.36 The Fe3O4/PPy PNCs with a Fe3O4
broad diraction peak located at 2 = 15.227.9 is observed in nanoparticle loading of 60 wt % have the highest value of
the pure PPy,31 Figure 5a, indicating the amorphous behavior compared with the Fe3O4/PPy PNCs with other loadings of
of the pure PPy. The diraction peaks at 2 = 18.0, 30.3, 35.6, Fe3O4 at high frequency (>2 104 Hz), Figure 6a. Figure 6b
43.3, 54.0, 57.2, 62.9, and 74.6 in the XRD curve of Fe3O4 shows the of pure PPy and its Fe3O4 PNCs with a Fe3O4
NPs, Figure 5f, correspond to (1 1 1), (2 2 0), (3 1 1), (4 0 0), nanoparticle loading of 10, 20, 40, and 60 wt %, respectively.
(4 2 2), (5 1 1), (4 4 0), and (5 3 3) crystallographic planes of The of pure PPy shows the large negative values (about the
the spinel phase of Fe3O4, respectively.31 The XRD patterns of order of 107) and increases with increasing frequency at low
the crystallite structure can be used to estimate the lattice plane frequency (<103 Hz), then decreases monotonically after 103
d-spacing and average crystallite size.34 Generally, the lattice Hz. For the Fe3O4/PPy PNCs, the also shows a switch from
plane d-spacing is calculated based on the Bragg formula, eq negative to positive at certain frequency. The of the Fe3O4/
1:34 PPy PNCs with a Fe3O4 nanoparticle loading of 10 and 20 wt
% exhibits a similar trend as that of pure PPy. The value of
= 2d sin (1)
the 40 wt % Fe3O4/PPy PNCs increases with increasing
where is the X-ray wavelength ( = 0.154 nm) and is the frequency from 102 to 2 103 Hz, and then decreases with
diraction angle. The average crystallite size can be estimated increasing frequency (>2 103 Hz). The of the Fe3O4/PPy
by the XRD pattern, using the Scherrer formula,8 eq 2: PNCs with a Fe3O4 nanoparticle loading of 60 wt % also shows
large negative values (about the order of 107) and increases
k
L= with increasing frequency from 102 to 104 Hz, and then
cos (2) decreases with increasing frequency (>104 Hz). Generally,
where = 0.154 nm, L is the average crystallite size, is the according to the DrudeLorentz model, the dielectric
full-width at half-maximum, and is the diraction angle; the permittivity of the conductive materials can be expressed as
shape factor k, depending on the miller index of the reection eq 337
plane and the shape of the crystal, is normally 0.89. The peak of
the as-received Fe3O4 NPs at 2 = 35.6 is chosen to calculate p2
() = 1
the lattice plane d-spacing and average crystallite size. The ( + i ) (3)
obtained lattice plane d-spacing and average crystallite size of
the as-received Fe3O4 NPs are about 0.25 (which corresponds where p is the plasma frequency, is the damping constant,
to the (3 1 1) crystallographic plane of Fe3O4) and 10.28 nm, and is the angular frequency. When < p, the real
respectively. The obtained average crystallite size (10.28 nm) of permittivity is negative; while > p, the is positive.
as-received Fe3O4 NPs is consistent with the results obtained in Figure 6c shows the frequency-dependent tan for pure PPy
HRTEM (11.14 nm). The peaks of the Fe3O4/PPy PNCs with and its Fe3O4 PNCs with a Fe3O4 nanoparticle loading of 10,
a Fe3O4 nanoparticle loading of 60 wt % at 2 = 35.6 are also 20, 40, and 60 wt %, respectively. The tan for all the samples
chosen to calculate the lattice plane d-spacing and the average increases from the frequency of 102 Hz and then reaches a peak
crystallite size. The calculated lattice plane d-spacing and value at dierent frequencies depending on the ller loading,
10195 dx.doi.org/10.1021/jp402236n | J. Phys. Chem. C 2013, 117, 1019110202
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after that the tan decreases with increasing frequency. The Figure 7. UVvis DRS of pure PPy and Fe3O4/PPy PNCs with a
appearance of the peak in the tan is due to the resonance Fe3O4 nanoparticle loading of 10, 20, 40, and 60 wt %.
eect, in which the system tends to oscillate with greater
amplitude than others at certain frequencies, especially for the DRS of pure PPy and its Fe3 O 4 PNCs with a Fe 3 O 4
negative permittivity values.38 The tan is very low at high nanoparticle loading of 10, 20, 40, and 60 wt %, respectively.
frequency (>105 Hz) for all the samples. The materials with a The edge is related to the * transition in the polymer chain
very low energy loss have a potential to be applied in the of PPy.49 The edge of pure PPy calculated by the onset of the
microelectronic devices.39 UVvis DRS in Figure 7 is 480 nm and the Eopt g of pure PPy is
3.6. Optical Properties. Bad gap, which is also called 2.58 eV, which is estimated according to eq 4. The calculated
energy gap, E(t), is the energy range between the conduction Eopt
g of pure PPy is consistent with the results investigated
band and the valence band.40,41 The conduction band is the previously in the HCl acid doped PPy (2.54 eV)48 and in the
electron energy range for the electron to move freely within the iodine doped PPy (2.86 eV).47 The edge and Eopt g of the Fe3O4/
3.7. Magnetic Properties. Magnetization is a phenomen- obtained from the intercept of MH1 at high magnetic
on that describes the response of magnetic materials to an eld.54 The Ms of the as-received Fe3O4 NPs is 63.45 emu g1,
applied external magnetic eld.50 Application of a magnetic which is smaller than that of the bulk Fe3O4 (92 emu g1).55
eld can make the direction of magnetic moment of the NPs The obtained Ms values of Fe3O4/PPy PNCs with a Fe3O4
the same as the eld direction, and the magnetization increases nanoparticle loading of 10, 20, 40, and 60 wt % are 7.32, 15.7,
with increasing magnetic eld until it reaches the saturation 28.81, and 43.11 emu g1, respectively.
magnetization (Ms).51 When the diameter of the magnetic NPs The best t to eq 8 is obtained by nonlinear tting of M and
is around 10 nm, according to the materials, the coercive force H, using Polymath software. The a for the as-received Fe3O4
(Hc) reaches zero, then the NPs will be in the super- NPs and Fe3O4/PPy PNCs with a Fe3O4 nanoparticle loading
paramagnetic state. The magnetic properties of a super- of 10, 20, 40, and 60 wt % is 3.24 103, 3.20 103, 3.28
paramagnetic system can be described on the basis of the 103, 3.22 103, and 3.31 103 T1, respectively. According
Langevin eq 6:52 to eq 9, the magnetic moment m can be calculated from a. The
mH m of the pure PPy and Fe3O4/PPy PNCs with a Fe3O4
M= 0 L f (m ) d m nanoparticle loading of 10, 20, 40, and 60 wt % is 1.40, 1.38,
kBT (6) 1.42, 1.39, and 1.43 B, respectively. The m is almost the same
1 for all the samples, indicating that the polymer has little eect
where M is magnetization (emu g ) in H (Oe), kB is the on the magnetic moment of the Fe3O4 NPs.
Boltzmann constant, m is the magnetic moment, T is the 3.8. Temperature-Dependent Resistivity and Electri-
absolute temperature, and f(m) is the distribution function of cal Conduction Mechanism. The temperature-dependent
magnetic moments related to the saturation magnetization resistivity of pure PPy and its Fe3O4 PNCs with dierent Fe3O4
(Ms) as described by eq 7: nanoparticle loadings is measured at temperatures ranging from
100 to 290 K to determine the electrical conduction
Ms = 0 f (m ) d m
(7) mechanism. In Figure 9a, the resistivity of all the synthesized
samples decreases with increasing temperature, which is a
According to eq 6 and 7, the relationship between M and Ms typical behavior of the semiconductor.6 The resistivity of pure
can be described by eq 8: PPy decreases from 4.60 to 1.58 ohmcm within the measured
M 1 temperature scale. The resistivity of the Fe3O4/PPy PNCs with
= coth x dierent Fe3O4 nanoparticle loadings varies from 2.15 to 30.01
Ms x (8)
ohmcm within the temperature scale 100290 K. The Fe3O4/
where, x = aH; the parameter a is related to the electron spin PPy PNCs exhibit higher resistivity than that of pure PPy over
magnetic moment m of the individual molecule as described in the whole temperature range and the resistivity of the Fe3O4/
eq 9: PPy PNCs increases with increasing the Fe3O4 nanoparticle
m loading.
a= To better understand the charge transport in pure PPy and
kBT (9)
its Fe3O4 PNCs, the Mott variable range hopping (VRH)
Figure 8 shows the magnetization curves of the as-received model, eq 10, is used to describe the electrical conduction
Fe3O4 NPs, pure PPy, and Fe3O4/PPy PNCs with a Fe3O4 mechanism:2,7,23
nanoparticle loading of 10, 20, 40, and 60 wt % at room
T 1/1 + n
temperature, respectively. All the samples show no hysteresis
= 0 exp 0 ; n = 1, 2, 3
loop, which means that the Hc is zero Oe, indicating a T (10)
superparamagnetic behavior.53 The magnetization of all the
samples did not reach saturation at the measured magnetic where the pre-exponential factor 0 is a constant, which
eld. Thus, the Ms is determined by the extrapolated Ms represents the conductivity at innite low temperature limit.
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measured magnetic eld range and decreases with the Thus, the density of states at the Fermi level N(EF) can be
increasing magnetic eld. The negative MR is also observed calculated from eq 19 according to eq 11:
in the Fe3O4/PPy PNCs with Fe3O4 nanoparticle loadings of
10, 20, and 40 wt %, respectively. N (E F) = 24/[kBT0a0 3] (19)
Generally, the orbital magnetoconductivity theory (forward
interference model) and wave function shrinkage model can be The obtained N(EF) is 1.12 1034 1.50 1032, 1.60 1035
used to describe the MR of highly disorderedly localized 2.16 1033, and 5.61 1035 7.54 1033 (J cm3)1 at a0 of
systems in the VRH regime.63 In the temperature-dependent 130.60, 42.67, and 28.07 nm, respectively. The calculated
resistivity section, the pure PPy and Fe3O4/PPy PNCs exhibit N(EF) increases with decreasing a0. Generally, the hopping
the quasi-3-d Mott VRH electrical conduction mechanism. probability between the localized states increases with
Therefore, these two models can be applied to the pure PPy increasing N(EF), indicating that the higher N(EF), the more
and 60 wt % Fe3O4/PPy PNCs. The wave function shrinkage hopping probability of charge carriers. The average hopping
model is used to describe the positive MR eect of the pure length Rhop can be obtained from eq 20 by T0, T, and a0:66
PPy. In the wave function shrinkage model, the R(H,T)/R(0,T) R hop = (3/8)(T0/T )1/4 a0
can be expressed as eq 14:64 (20)
R(H , T )/R(0, T ) = exp{C(0)[C(H )/(0) 1]} (14) The obtained Rhop is 1.72 102 0.58, 0.56 102 0.19, and
0.37 102 0.12 nm at a0 of 130.60, 42.67, and 28.07 nm,
where C(0) = (T0/T)1/4 for the 3-d Mott VRH charge respectively. These results indicate that the Rhop decreases with
transport mechanism, C(H)/C(0) is the normalized hopping increasing H and the increased MR accompanies with the
probability parameter and is a function of H/PC for the Mott reduced Rhop.
VRH charge transport mechanism, H is the magnetic eld, and The orbital magnetoconductivity theory is used to investigate
PC is the tting parameter, which is the normalizing the negative MR eect of the Fe3O4/PPy PNCs. The eect of
characteristic eld that must be extracted from one set of MR interference among various hopping paths was concerned in
ratio data points and can also be given by eq 15 for the Mott this theory. These hopping paths include a sequence of
VRH charge transport mechanism:60,64,65 scattering of tunneling electrons by the impurities located
within a cigar-shaped domain of length rh (hopping distance)
PC = 6/[ea0 2(T0/T )1/4 ] (15) and width (rha0)1/2.63 The ratio R(H,T)/R(0,T) caused by
where e is electron charge, and is the reduced Plancks interference eects is described by empirical eq 21:67
constant. In the low magnetic eld limit, eq 14 is simplied to
R(H , T )/R(0, T ) 1/{1 + Csat[H /Hsat]/[1 + H /Hsat]}
eq 16:63
(21)
H T 2 1/4
R(H , T )/R(0, T ) 1 + t 2 2 0 where the tting parameter Csat is constant and also called the
PC T (16) temperature-independent tting parameter and Hsat is called
the eective saturation magnetic eld. As for the Mott VRH
And MR is dened as eq 17: electrical conduction mechanism, Hsat is calculated by eq
R(H , T ) R(0, T ) 22:63,68,69
MR =
R(0, T )
8 3/2 1 h T
3/8
H2 T0
1/4 Hsat 0.7
3 a0 2 e T0 (22)
t2
PC 2 T
where h is the Plancks constant, and T0 is the Mott
e 2a 4 T 3/4 characteristic temperature (K). In the low-eld limit, eq 21
= t 2 0 2 0 H2
36 T (17) can be simplied to eq 23:
where the numerical constant t2 = 5/2016. From eq 17, it is R(H , T )/R(0, T ) 1 Csat[H /Hsat] (23)
found that the MR value obtained from the wave function
shrinkage model will always be positive, hence it is used to Substituting eq 22 into eq 23 and rearranging, the MR can be
explain the positive MR value. According to eq 17, the obtained from eq 24:
localization length a0 can be expressed from the slope of the
R(H , T ) R(0, T )
curve by plotting MRH2 (a04 = ((362MR)/(t2e2))(T0/ MR =
T)(3/4)H2), Figure S2. In Figure S2, the slope of the curve R(0, T )
MRH2 for the pure PPy is observed to decrease with Csat[H /Hsat]
increasing H2, which means that the localization length a0 is
reduced with the increasing H. The a0 can also be calculated H
= Csat 3/8
from eq 18: 8 3/2
0.7() 3 ( 1
a0 2 )( he )( TT )
0 (24)
362MR T0
3/4
a04 = H 2 The calculated a0 are 0.440, 0.169, and 0.129 m at H of 0.3, 4,
t 2e 2 T (18)
and 8.5 T, respectively. The obtained a0 for the negative MR
The a0 is 130.60 0.97 106, 42.67 0.03 106, and 28.07 value is larger than that of the positive MR value, which is also
0.02 106 nm at H of 0.3, 4, and 9 T, respectively. From observed in the carbon nanotube (CNT) lms, mat, and pellets
the obtained results, the a0 is observed to decrease with at weak magnetic eld and interpreted by the quantum
increasing H, which is consistent with results in Figure S2. interference eect.70
10199 dx.doi.org/10.1021/jp402236n | J. Phys. Chem. C 2013, 117, 1019110202
The Journal of Physical Chemistry C Article
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