J Mater Sci (2015) 50:1201–1213

DOI 10.1007/s10853-014-8676-3

Synthesis and characterization of structural and magnetic

properties of graphene/hard ferrite nanocomposites
as microwave-absorbing material
Zehra Durmus • Ali Durmus • Huseyin Kavas

Received: 21 August 2014 / Accepted: 16 October 2014 / Published online: 25 October 2014
Ó Springer Science+Business Media New York 2014

Abstract In this study, barium hexaferrite nanoparticles Introduction

were synthesized via the citrate sol–gel combustion method
in a reaction medium consisting of various forms of Microwave-absorbing materials have attracted great tech-
graphene nanosheet, such as expanded graphite, expanded nical and scientific interests due to their swiftly increasing
graphite oxide, and reduced graphite oxide to prepare novel importance for the specific implementations such as silent
type graphene/hexaferrite nanocomposites as microwave- rooms, radar systems, and military applications and ability
absorbing material. The microstructural features and for reducing electromagnetic interference (EMI) and radar
physical properties of nanocomposites were characterized signatures for a long time. Electromagnetic (EM) waves
by X-ray diffraction, Raman spectroscopy, Fourier trans- can be shielded by either reflecting or absorbing of EM
form infrared spectroscopy, scanning electron microscopy, radiation. Various types of materials such as carbon, con-
and thermogravimetric analysis methods. Magnetic prop- ducting polymers, metal and metal particles, and alloys can
erties of the nanocomposites were studied by a vibrating be used to shield EM waves.
sample magnetometer, and the microwave-absorption and The magnetically hard hexagonal M ferrites, having the
-reflection properties of samples were also determined in general formula of MFe12O19 where the M designates Ba,
the frequency range of 8–12 GHz. It was found that the Sr, or Pb, are the most commercially used materials of
surfaces of the graphene nanosheets were successfully interest for the EM applications such as permanent mag-
decorated with the barium hexaferrite nanoparticles, and nets, magnetic recording media, and electric motors
the resulting layered nanocomposite structure showed the because they exhibit high coercivity and magnetic perme-
reflection loss value of -58 dB at 11.42 GHz. ability due to their unique structural property of high
magnetocrystalline anisotropy along the c-axis of the
hexagonal structure. Especially barium and strontium
hexaferrites (BaFe12O19 and SrFe12O19) have high satura-
tion magnetizations (Ms) of 72 emu g-1 and at least
74 emu g-1, respectively. Barium hexaferrite, also named
as magnetoplumbite, is the most widely used material
Z. Durmus (&)
Department of Pharmaceutical Biotechnology, Faculty of among the family of hard magnets for the EM applications
Pharmacy, Bezmialem Vakıf University, Fatih, 34093 Istanbul, due to its attractive magnetic properties, high magnetic
Turkey anisotropy field (1.7 T) which results in a high coercivity,
e-mail: [email protected]
remanence, and a ferromagnetic resonance at about
A. Durmus 50 GHz, high Curie temperature, excellent chemical sta-
Department of Chemical Engineering, Faculty of Engineering, bility, good corrosion resistance, and low cost [1].
Istanbul University, Avcilar, 34320 Istanbul, Turkey Nanocrystalline form of BaFe12O19 can be successfully
used for the absorption of microwave radiation in a wide
H. Kavas
Department of Engineering Physics, Istanbul Medeniyet frequency range, between 12 and 18 GHz [2]. The ferro-
University, Kadıköy, 34700 Istanbul, Turkey magnetic resonance coincides with large magnetic losses,

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1202 J Mater Sci (2015) 50:1201–1213

making these materials suitable for use in the microwave that the Ms value of Cu-ferrite possessed a linear rela-
band as high-frequency absorbers. The resonance phe- tionship with both the crystallinity and the crystallite size.
nomena in ferrites can be explained by two different Chia et al. investigated the size- and crystallinity-depen-
mechanisms: spin resonance and domain-wall motion. dent magnetic properties of cobalt ferrite (CoFe2O4)
Permeability spectrum of polycrystalline ferrites is gener- nanocrystals synthesized by a wet chemical co-precipita-
ally explained by the combination of contributions by both. tion method [12]. They found that the degree of crystal-
However, the complex permeability in the high-frequency linity and mean crystallite size of CoFe2O4 nanocrystals
region is affected by the spin rotation component [3]. The increased with the increasing synthesis and subsequent
EMI shielding effectiveness of BaFe12O19 has also been calcinations temperature which improved the magnetic
extensively studied [4–8]. The EM properties of micro- properties of samples.
wave ferrites depend on the structural and physical features Carbon-based materials, e.g., single or multiwall carbon
of these materials such as chemical composition, crystal nanotubes, graphene, carbon fiber, and carbon black can
structure, crystallite size, particle size, etc. It is also well also be used as alternative conducting materials for the
known that the size of magnetic particles is influenced by EMI shielding applications. Magnetic functionalization of
the synthesis method employed (e.g., co-precipitation, sol– carbon materials has been considered as an innovative
gel, hydrothermal growth, citrate combustion, surfactant- alternative to create multifunctional carbon/magnetic
assisted decomposition, etc.) and thermomechanical hybrid materials for specific applications especially in
parameters during the preparation process (e.g., mixing shielding of EM waves in a wide range of frequency.
method, reaction time, temperatures of annealing, sinter- Preparation and characterization of such materials is also a
ing, and calcination). Pardavi-Horvath reviewed the effects rapidly expanding research area since the composite
of types and chemical composition of ferrites on the structure allows obtaining suitable candidates for EM wave
physical properties and related microwave applications of absorber with a low reflectivity at microwave frequencies.
such materials [9]. It has been pointed out that the most These studies have focused on the preparation and char-
significant magnetic properties of ferrite materials, namely acterization of carbon nanotube (CNT) decorated with
Ms, coercivity, magnetization, and loss, change dramati- various types of magnetic nanoparticles [14–18]. Zhao
cally when the particle size is reduced to nanoscale [3]. It is et al. prepared a nanocompound, uniformly coated CNT
generally considered that this property change is due to the with strontium ferrite nanoparticles, by the in situ sol–gel
fact that the size reduction in the magnetic materials yields reaction [19]. They reported that the coercive force of the
higher surface/volume ratio which leads to different prop- samples increased with the increasing CNT content into the
erties than the bulk materials. Decreasing in the particle structure. Correa-Duarte et al. magnetically functionalized
size results in reduction in the number of spins coopera- CNT with iron oxide (Fe3O4) nanoparticles via polymer
tively linked within the particle and surface effects wrapping and layer-by-layer assembly techniques [20].
becomes much more important on the magnetic properties Georgakilas et al. employed a carboxylic derivative of
of particles. Changes in the magnetic properties of particles pyrene as an interlinker for the attachment of capped
depending on the size of particles can be easily monitored magnetic nanoparticles on the CNT surfaces [21]. They
by hysteresis loops that provide information about the also reported that this route enhanced the solubility of
manipulation of microwave-absorption frequency. Peddis CNTs in organic solvents. He et al. investigated the
et al. investigated the effect of structural variations on the microwave-absorbing properties of single-wall carbon
magnetic properties of cobalt ferrite (CoFe2O4) nanopar- nanotube (SWCNT)/BaFe12O19 nanocrystalline composites
ticles and also discussed the effects of particle size on the in the frequency region of 2–18 GHz [22]. They found that
physical properties of these materials [10]. They also the maximum reflection loss (RL) of the SWCNT/
reviewed the structure–property relationships of the mag- BaFe12O19 composite with a thickness of 3 mm reached
netic nanoparticles in detail and concluded that the mag- 30.79 dB at 10.5 GHz and concluded that the microwave-
netic properties of nanoparticles were mostly influenced by absorption properties of composite are evidently improved
particles size, while the magnetic anisotropy and interpar- due to the multiple absorptive mechanisms. Ghasemi et al.
ticle interactions played a fundamental role in the physics prepared magnetic multiwalled carbon nanotube
of these systems. Crystallite size of magnetic nanoparticles (MWCNT) composites by the assembly of Mg–Ni–Ti-
is another important parameter on their magnetic properties substituted barium ferrite nanoparticles onto surface of
[11–13]. Deraz studied on the size- and crystallinity- MWCNT and examined the magnetic properties of the
dependent magnetic properties of copper ferrite (CuFe2O4) samples by the vibrating sample magnetometer (VSM)
nanoparticles prepared by a combustion route and reported technique at room temperature [23]. They reported that the
that the magnetization values of samples increased with the composites display a great potential application as wide-
increasing of particle size [11]. It was also shown by Deraz band EM wave absorbers based on the RL data. Li et al.

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J Mater Sci (2015) 50:1201–1213 1203

prepared polyaniline/strontium ferrite/MWCNT compos- exhibited an outstanding and improved microwave-

ites by synthesizing strontium ferrite particles by sol–gel absorption performance, and the electrochemical properties
method and self-propagating synthesis followed by in situ compared to the pristine graphene and CFA. It was also
polymerization [24]. They declared that the EM properties declared that the introduction of PANI into the structure
of composites were excellent in the frequency range of improved the microwave absorption and specific capaci-
2–18 GHz, which mainly depend on the dielectric loss in tance of the composites.
the range of 2-9 GHz, and mainly on the magnetic loss in In this study, barium hexaferrite nanoparticles were
the range of 9–18 GHz. synthesized onto various types of graphene sheets such as
Another unique structure of carbon is graphene, the expanded graphite (EG), expanded graphite oxide (EGO),
‘‘thinnest material in our universe’’ [25] and a flat mono- and reduced expanded graphite oxide (rEGO) by the citrate
layer of hexagonally arrayed sp2-bonded carbon atoms sol–gel combustion method. In this method, nano-thick
tightly packed into a two-dimensional (2D) crystal of graphene sheets were efficiently decorated with barium
hybridized carbon with honeycomb lattice. Graphene is the hexaferrite nanoparticles to prepare novel nanocomposites
basal building block in all graphitic materials [26]. which possibly exhibit the microwave-absorbing perfor-
Graphene nanolayers can be prepared from the graphite mance. Structural properties and microwave absorption
particles by chemical and/or physical treatments [27–30]. performances of the samples were characterized, in detail.
The unique structural features and geometric advantages of
layered carbons make the graphene an ideal, alternative,
and high-performance supporting material to prepare novel Experimental section
functional nanomaterials. Especially, graphene sheets
decorated with magnetic nanoparticles could exhibit good Materials
magnetic, electrical,, and dielectric performance and great
application potential in the fields of EM and radio-fre- Iron (III) nitrate nonahydrate, Fe(NO3)39H2O, barium nitrate
quency interference (RFI) materials, electrochromic devi- (Ba(NO3)2), citric acid (C6H8O7), sulfuric acid (H2SO4 fum-
ces, Li ion batteries, sensors, actuators, and field-effect ing), hydrogen peroxide (30 % H2O2), potassium permanga-
transistors [31]. nate (KMnO4), ammonia solution (28 % NH3), sodium nitrate
Syntheses of soft ferrites onto various types of nano- (NaNO3), hydrazine hydrate (N2H4.H2O), and hydrochloric
sized graphitic templates such as graphene [32–35], acid (37 % HCl) were all purchased from Merck and Sigma-
graphite [36–38], and graphene oxide [39–42] have been Aldrich. All the chemicals employed in the study were of
studied. Bai et al. prepared magnetic reduced graphene analytic grade and used as-received without a purification.
oxide–ferrite hybrids according to one-pot solvothermal The EG was a commercial grade, thermally expanded product
synthesis method and used the resulting hybrids for the (TIMREXÒ BNB90), kindly provided by TIMCAL (Swit-
removal of organic dyes, rhodamine B (RhB), and meth- zerland). The density, surface area, average particle size (d90),
ylene blue (MB) [43]. They showed that monodispersed and the oil adsorption number (OAN) values of EG were
MFe2O4 microspheres with uniform size were homoge- reported as 2.24 g cm-3, 28 m2 g-1, 85.2 lm, and 150 ml
neously deposited on reduced graphene oxide nanosheets. 100 mg-1, respectively, by the producer.
They also reported that the hybrids possessed considerable
saturation magnetization, lower remanence, and coercivity, Graphite modification
and importantly they can be used as effective adsorbents
for dye removal. Chemical oxidation and reduction are the well-known
To the best of our knowledge, only a few studies have modification methods of layered carbon particles to obtain
been published on the preparation and characterization of graphene nanosheets. In the first step, EG was oxidized by
carbon/hard ferrite nanocomposites. Yang and Wang pre- the modified Hummers [46] method to prepare EGO. In
pared BaFe12O19/NanoG composite by the precipitation of this method, the EG powder was dispersed in H2SO4, and
barium hexaferrite on the surface of graphite nanosheets then the NaNO3 and KMnO4 were gradually introduced in
[44]. They reported that the RL values of the composite this suspension and vigorously stirred at the temperature
structure were found to be in the range of about 16–17 dB below 20 °C into an ice bath for 3 h. Then, the reaction
in the frequency range of 8–12 GHz. Bhattacharya et al. mixture was diluted with deionized water in an ice bath to
synthesized magnetic M-type hexaferrite, CuFe10Al2O19 keep the temperature below 100 °C. The H2O2 (30 wt%)
(CFA)/graphene and CFA/graphene/polyaniline (PANI) was slowly added into the suspension, and the mixture was
composites by facile chemical co-precipitation and in situ stirred for 2 h. It was observed that the brownish color of
methods by means of acid modified graphene [45]. They mixture turned into a brilliant yellow which indicates
reported that the prepared multifunctional composites strong oxidation. The mixture was centrifuged and washed

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several times with an aqueous solution of 5 % HCl. Then, Structural and physical characterizations of samples
it was washed repeatedly with deionized water until the pH
of the supernatant became neutral. A brown powder of The microstructural and morphological properties of EG,
EGO was obtain and dried in a vacuum oven at 60 °C. EGO, rEGO, and nanocomposite samples were character-
In the second step, EGO powder was dispersed in the ized by X-ray diffraction (XRD), Fourier transform infra-
deionized water in a flask, and a stable yellow–brown dis- red spectroscopy (FTIR), Raman spectroscopy, and
persion was obtained due to the hydrophilic nature of EGO. scanning electron microscopy (SEM) methods. The XRD
Hydrazine monohydrate, which is the most frequently used patterns of samples were obtained using a Rigaku Smart
reducing agent due to the simplicity of its application proce- Lab. XRD with Cu-Ka radiation at room temperature. FTIR
dure and the reduction efficiency to obtain graphene sheet spectra were recorded in transmission mode using a Perkin
having excellent physical properties [47], was then added to Elmer BX-FTIR infrared spectrometer using the KBr pel-
the EGO suspension. The flask equipped with a water-cooled lets of sizes in the range of 400–4000 cm-1 and with the
condenser was heated up to 100 °C in an oil bath and kept at resolution of 2 cm-1. The Raman spectra of graphitic
this temperature for 24 h. The EGO sheets were reduced to materials were also recorded in a Thermo-Fisher Scientific,
form graphene nanosheets or rEGO, and gradually precipi- DXR dispersive Raman instrument using laser excitation of
tated out as a black solid due to the hydrophobic nature of 532 and 780 nm and an InGaAs detector, in the range of
rEGO sheets. It is well known that the physical and chemical 400–3500 cm-1. One hundred scans were accumulated
properties of nanosheets such as the thickness, surface char- with the resolution of 4 cm-1 by means of a laser power of
acter, and surface area strongly depend on the experimental 100 mW. The morphological features of samples were
parameters of oxidation and reduction procedures. The rEGO investigated by a field emission SEM (FE-SEM, FEI
was isolated by filtration and washed with the excess of water Quanta FEG 450) operated at 30 kV. Powder samples were
and methanol and then dried in an air-circulating oven. directly imaged in the electron microscope after a proper
preparation of sample sputter-coated with gold.
Synthesis of graphene/BaFe12O19 nanocomposites Magnetic properties of the samples, all in powder form,
were characterized using a VSM (LDJ Electronics Inc.,
The synthesis process of graphene/BaFe12O19 nanocom- Model 9600) at room temperature, with an applied field of 15
posites is schematically illustrated in Fig. 1. The rEGO kOe. The thermal properties of EG, EGO, and rEGO were
powder was first dispersed in deionized water by sonication analyzed with a thermogravimetric analyzer (TGA), SII
for 1 h to transform the carboxylic acid groups to carboxylate Nanotechnology TG/DTA 6300, at the heating rate of 10 °C
anions. In this study, the citrate sol–gel combustion method min-1 in the temperature range of 30–800 °C, under the
was applied to synthesize BaFe12O19 nanoparticles. Stoi- nitrogen atmosphere with the gas flow rate of 50 ml min-1.
chiometric amounts of Fe(NO3)39H2O and Ba(NO3)2 (Fe/ Powder samples shaped as a rectangular sheet with the
Ba ratio of 11) were dissolved in a minimum amount of dimensions of 10.2 9 22.8 9 2 mm in length, width, and
deionized water by stirring at 50 °C. Citric acid was then thickness, respectively, by pressing using a metal mold for
added to the solution of Ba2? and Fe3? to chelate these ions the microwave-absorbing measurements. Microwave-
by adjusting the molar ratio of citric acid/metal ions as 1:1. absorption measurements were performed using a vector
This solution was added dropwise to the rEGO suspension at network analyzer (VNA), HP 8510C, in the frequency
room temperature, and the mixture was vigorously stirred range of 8–12 GHz. The scattering parameters of samples
under a nitrogen flow for 30 min. Then, ammonia was added for the reflection (S11 or S22) and absorption (S12 or S21)
to the mixture to adjust the pH value to 7. The suspension was were determined. Full two-port calibration was performed
slowly evaporated to form a viscous black gel by keeping the to remove some errors due to the directivity, source match,
temperature of mixture at 80 °C and stirring constantly. The load match, etc., in both forward and reverse directions.
precursor gel was transferred to an evaporating dish and the
heated up to temperature in the range of 140–150 °C. At this
step, the precursors gel was self-ignited and combusted Results and discussion
rapidly to form a brown powder as seen in Fig. 1. The
resulting self-standing fluffy powder of rEGO/BaFe12O19 Structural and morphological characterization
nanocomposite was pre-calcined at 450 °C for 4 h and then of samples
sintered at 1100 °C for an hour. The synthesis route was also
repeated by means of EG and EGO powders to prepare EG/ Figure 2a shows the XRD patterns of EG, EGO, and the
BaFe12O19 and EGO/BaFe12O19 nanocomposites to com- chemically reduced graphite oxide sheets with the dif-
pare the structural and microwave-absorbing performances fraction angle in the range of 5–40°. It is clearly seen that
of such material to the rEGO/BaFe12O19. the commercial EG exhibits a characteristic sharp and

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Fig. 1 A simple synthesis route for the preparation of graphene/barium hexaferrite nanocomposites

intense peak at the diffraction angle of 26.5° which cor- species through intergallery spaces and expansion of
responds to the d001 planes of graphite. Intergallery dis- graphene layers by the oxidation in a strong acidic medium
tance between the graphene sheets was calculated by the according to the modified Hummer’s method. Chemically
Bragg’s equation as defined in the Eq. (1); reduced graphite oxide exhibited two broad peaks at the
diffraction angles of 12.2° and 24.8° which can be attributed,
k ¼ 2dSinh ð1Þ
respectively, to the d001 and d002 planes of graphene sheets.
where d is the spacing between sheets; k, the wavelength It is well known that the chemical reduction of GO removes
of X-ray (0.154 nm); and h, the angle of diffraction. The the organic species onto the graphene layers. A formation of
intergallery distance between the graphite sheets was cal- fully exfoliated, ‘‘house-of-card’’ structure consisting of
culated to be 0.336 nm for the EG. This value is the char- disordered graphene sheets might be expected by chemical
acteristic d001 space between the graphene layers in the treatment. Based on the XRD result given in Fig. 2a, it can
graphite. As clearly seen in the figure, the d001 peak shifted be concluded that the expansion of graphene stacks was
to the lower diffraction angle (2h = 11.3°) which corre- successfully achieved by the oxidizing agents, but, the
sponds to intergallery distance of 0.782 nm for the EGO. chemical reduction did not yield a fully exfoliated structure.
Another important issue is that the characteristic d001 peak The broad and small peaks observed in the XRD pattern of
of EGO is much broader and less intense than that of EG. rEGO can be attributed to the facts those the organic groups
This is obviously due to the intercalation of chemical did not completely removed from the sheets and but the

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Fig. 2 a XRD patterns, b FT-IR spectrum, c TGA thermograms, and d Raman spectrum of EG, EGO, and rEGO

resulting product probably formed highly exfoliated struc- asymmetric and symmetric stretchings of carbonyl groups
ture consisting of stacks with few layers of graphene sheets. –CO2, and stretching of C–O bonds, respectively. It can be
Figure 2b shows the FTIR spectra of EG, EGO, and seen in the figure that the stretching vibration of O–H at the
rEGO sheets in the wavenumber range of 400–4000 cm-1. wavenumber of 3400 cm-1 and the stretching vibrations of
As seen, no significant peak was observed in the FTIR C=O at the wavenumber of 1710 cm-1 were still observed
spectra of EG. On the other hand, the EGO and rEGO in the rEGO. However, these peaks were smaller than those
exhibited various peaks due to the presence of different observed in the FTIR spectra of EGO. These results
types of oxygen functionalities onto the surfaces. The pointed out that the chemical reduction of EGO with the
strong peak observed at 3400 cm-1 corresponds to the hydrazine hydride significantly reduced the oxygen spe-
stretching vibration of O–H. Peaks observed at 1710 and cies, but some carboxyl groups were still remaining onto
1614 cm-1 belong to the stretching vibration of C=O and the sheets.
the skeletal vibration of unoxidized graphitic domains TGA thermograms of EG, EGO, and rEGO are given in
(aromatic C=C), respectively. Furthermore, the character- Fig. 2c. TGA method analysis is another simple tool for
istic peaks observed at the wavenumbers of 1392, 1150, quantifying organic species between the graphene layers
1035, and 870 cm-1 correspond to the stretching of C–O, and probing the effectiveness of oxidation and reduction

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reactions. As seen in the figure, EG was highly stable up to

600 °C, as expected. However, the EGO shows a slight
mass decrease from room temperature to 150 °C, which
can be primarily attributed to the evaporation of volatiles
and adsorbed water molecules, and a sharp, step-wise
weight loss from 150 °C to 200 °C. This major weight loss
was due to the rapid decomposition of the oxygen-con-
taining functional groups which indicated oxidation of
graphene layers sufficiently. The rEGO exhibited enhanced
thermal stability and much less weight loss compared to the
EGO, suggesting that the labile oxygen groups were highly
removed from the EGO sheets by the reduction with
hydrazine hydrate. Significant weight loss of rEGO started
at about 300 °C, and the total weight loss was found to be
about 10–12 wt% within the temperature range of
300–900 °C, which can be assigned to the presence of
some remaining organic species onto the rEGO sheets.
The Raman spectra of EG, EGO, and rEGO are depicted
in Fig. 2d. Raman spectroscopy is a fast and reliable
characterization method to understand the structural
transformations from graphite to graphite oxide and then to
graphene, by analyzing the in- and out-of-plane bondings
of hexagonal carbon framework. The starting material, EG,
exhibits a sharp G band at 1580 cm-1 and a weak D band,
while the EGO displays two distinct peaks at 1356 and
1602 cm-1. The G and D bands are attributed to the gra-
phitic crystal lattice vibration and defects and disorders in
graphitic crystal lattices in the carbon materials, respec-
tively. The intense D band observed in the EGO obviously
signified that the graphitic edges were successfully modi-
fied with the oxygen-containing groups. It was also found
that the rEGO shows less intense but clear D and G bands
at 1345 and 1584 cm-1, respectively, which pointed out
the organic species remaining onto the graphene sheets
after the chemical reduction. Raman specta results confirm
the previously mentioned structural characterization of
graphitic samples obtained by the other techniques: XRD,
FTIR, and TGA.
SEM micrographs of EG, EGO, and rEGO are shown in
Fig. 3a–c, respectively. In Fig. 3a, highly porous and lay-
ered structure of commercial EG having large stacks,
possibly consisting of hundreds of graphene nanosheets,
can be clearly seen. It should also be noted that the surfaces
Fig. 3 SEM micrographs of a EG, b EGO, and c rEGO nanosheets
of the EG sheets are quite flat and smooth. Figure 3b shows
the SEM micrograph of the oxidized counterpart, EGO. It
is worthy to observe that the lateral size of graphitic
nanosheets was not disrupted with the oxidation, but the of 5–10 lm were successfully obtained by the chemical
surface properties of modified product were strongly reduction.
affected. As seen in the Fig. 3b, the surfaces of EGO XRD patterns of nanocomposites are given in Fig. 4.
nanosheets are rough, and the edges are highly crumpled. These patterns indicate the formation and the crystal
On the other hand, the SEM image rEGO shown in Fig. 3c structure of BaFe12O19 synthesized onto the EG, EGO, and
clearly signifies that the very thin, wrinkled, and trans- rEGO sheets. The characteristic miller indices of (110),
parent graphene sheets having the lateral size in the range (008), (112), (107), (114), (200), (108), (203), (205), (118),

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BaM-EG

Transmittance (a.u.)
BaM-rEGO

BaM-EGO

1185
1118 1068

572
529 415

2000 1800 1600 1400 1200 1000 800 600 400

Fig. 4 XRD patterns of BaM-EG, BaM-EGO, and BaM-rEGO -1
Wavenumber (cm )
nanocomposites
Fig. 5 FT-IR spectrum of BaM-EG, BaM-EGO, and BaM-rEGO
nanocomposites

(209), (300), (217), (2011), (218), (220), and (2014) were

assigned on the patterns. All the characteristic peaks
indexed by the cubic structures of BaFe12O19 (JCPDS no. SEM images indicating the microstructural features of
84-0757) revealed that the highly pure hexaferrite phase BaM-EG, BaM-EGO, and BaM-rEGO nanocomposites are
were formed. As seen in the figure, diffraction peaks, shown in Fig. 6a–f, respectively. SEM micrograph of
which correspond to the structure of BaFe12O19, are very BaFe12O19 is also shown in Fig. 6g. All the micrographs of
sharp and intense, which indicates to small crystallite size. nanocomposites clearly indicated that the graphene sheets
In the XRD pattern of BaM-EGO, some peaks belong to were successfully decorated with the BaFe12O19 nanopar-
the BaO were also observed. However, it was found that ticles consisting of small and elongated grains. It was found
the diffraction peaks of BaO disappeared by using the that the average size of BaFe12O19 nanoparticles was in the
rEGO as the substrate material. range of 70–120 nm [Fig. 6g], and they showed a relatively
The average size of crystallites was determined by fit- broad size distribution due to the agglomeration. It is also
ting the diffraction patterns of the samples using the line noteworthy that the interactions between graphene sheets
profile fitting [48]. The average crystallite sizes of and BaFe12O19 nanoparticles are sufficiently strong. As
BaFe12O19 were calculated to be 16 ± 4, 20 ± 3, and seen in Fig. 6b, agglomerated hexaferrite nanoparticles
22 ± 5 nm for the nanocomposites synthesized onto the completely covered the surfaces of large graphene sheets,
EG, EGO, and rEGO sheets, respectively. These results and the size and shape of aggregate were led by the
represent that the BaFe12O19 nanoparticles were success- graphene template. It should also be noted that the mi-
fully synthesized onto the various types of graphene sheets. cropores between the graphene sheets were evenly filled up
It can also be concluded that the crystallite size of with the hexaferrite nanoparticles as clearly seen in the
BaFe12O19 is not dependent on the surface character and images of stack edges given in Fig. 6c, f. It can be con-
the thicknesses of graphene sheets. cluded that the microstructural properties of graphene/
FTIR spectra of nanocomposites are shown in Fig. 5, in BaFe12O19 nanocomposites encourage preparing the highly
the wavenumber range of 400–2000 cm-1. Characteristic porous, electromagnetically active, and structurally layered
bands of ferrite structure can be seen in the FTIR spectra of nanomaterials. It can also be concluded that such novel
all nanocomposite samples. The absorption bands observed nanocomposites can be considered as promising material
at 415, 529, and 572 cm-1 correspond to typical M–O showing high microwave-absorbing performance, and the
bonds in the BaFe12O19 structure [49, 50]. Absorption resulting ‘‘magnetic/conductive/magnetic’’-layered struc-
bands seen in the spectrum of BaM-EGO at the wave- ture of such nanocomposites could lead to multiple
number range of 1050–1200 cm-1 can be attributed to the reflection–absorption mechanism. Figure 6h illustrates the
little amount of organic species, mainly carbonyl and car- energy dispersive spectroscopy (EDS) analysis of BaM-
boxyl groups, formed onto the graphene sheets as previ- rEGO sample, which is a semi-quantitative microchemical
ously mentioned. However, no peak was observed in this analysis. It was found that the graphene amount into the
region for the BaM-rEGO sample. composite structure was about %12. The Ba, Fe, and O

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Fig. 6 SEM micrographs of a–

b BaM-EG, c–d BaM-EGO, e–
f BaM-rEGO, g BaFe12O19, and
h EDS analysis of BaM-rEGO
nanocomposite

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1210 J Mater Sci (2015) 50:1201–1213

2,5 0,25

2,0 0,20

1,5 0,15

1,0
BaM_EG BaM_EG 0,10
BaM_EGO BaM_EGO
0,5 BaM_rEGO BaM_rEGO 0,05

0,0 0,00
1,0 1,0
0,8 0,8
0,6 0,6
0,4 0,4
0,2 0,2
0,0 0,0
8 9 10 11 12 13
Frequency (GHz)

Fig. 8 The complex dielectric permittivity (e0 top-left axis with solid
symbols and e00 top-right axis with open symbols) and complex
Fig. 7 Magnetic hysteresis loops of BaM-EG, BaM-EGO, and BaM-
magnetic permeability (l0 bottom-left axis with solid symbols and l00
rEGO nanocomposites recorded at room temperature. The inset of
bottom-right axis with open symbols) curves of the nanocomposites
photographs represents the response of BaM-rEGO suspension into
water to a magnet

graphene layers of such sample. Furthermore, it is obvious

that the Ms depends on the mass fraction of magnetic
ratios confirmed the formation of barium hexaferrite component into the structure; thus, it can be inferred that the
structure. amount of active magnetic component, BaFe12O19, in the
BaM-EGO was less than those in other nanocomposites due
VSM analysis to the formation of BaO phase in this sample as previously
mentioned based on the XRD patterns of the samples. The
The magnetic properties of BaFe12O19 and graphene/ squareness (Mr/Ms) values of nanocomposites were deter-
BaFe12O19 nanocomposites were investigated at room mined to be about 0.46 [51].
temperature (300 K) with an applied field being between
-1.5 T and 1.5 T. Figure 6 shows the magnetic hysteresis Microwave properties of nanocomposites
loops of samples. As seen in Fig. 7, all samples show hard
ferromagnetic property, implied with the area of the static The complex dielectric permittivity (e = e0 -je00 ) and
magnetic hysteresis curve, and the high saturation mag- magnetic permeability (l0 = l-jl00 ) of nanocomposites
netization (Ms) values. The Ms value can be obtained from were measured via Transmission Reflection Line method
the M versus 1/H curve when H goes to infinity, while with the waveguide technique at X band. These parameters,
coercive field (Hc) and the remanent magnetization values shown in Fig. 8, were obtained from an Agilient 85071E
are directly obtained from the magnetic hysteresis curves. Materials Measurement Software. As seen in the figure, the
The Ms value of BaFe12O19 was found to be about 65 measured permittivity and permeability values are almost
emu g-1 which is very close to the theoretical value of this constant in the frequency range employed. The BaM-EG
material, 72 emu g-1. The high Ms values of samples make and BaM-rEGO nanocomposites showed approximately
these materials get easily separated from the aqueous dis- same dielectric permittivity of e & 2.4-j0 and l & 1-j0.
persion by a magnet as seen in the figure inset. One should note that the complex part of permittivity and
It is seen in the figure that the BaM-EG and BaM-rEGO permeability are nearly zero which is possibly due to using
nanocomposites display very similar hysteresis and mag- of small amount of powder sample in the measurements.
netic properties to the pristine BaFe12O19. The Ms, Mr, and The weight ratio of composite powder into the paraffin-
Hc values of BaM-EG were found to be 69.4, 32.4 based test specimen was 1:9. The technical reason for
emu g-1, and 4920 Oe, respectively. The magnetic param- employing small amounts of sample powder in the
eters were Ms = 68.5, Mr = 31.2 emu g-1, and Hc & 4435 microwave measurements is to avoid the impedance-
Oe for the BaM-rEGO. On the other hand, BaM-EGO matching problems arising from dense strong magnetic and
yielded the lowest Ms, Mr, and Hc values of 40.4, 18.5 emu dielectric materials. The e0 and l0 equations of BaM-EGO
g-1, and Hc & 4548 Oe, respectively. The lower magneti- are defined as e & 1.7-j0.1 and l & 0.4-j0.7. The BaM-
zation of BaM-EGO than other nanocomposites is possibly EGO sample yielded lower e0 and l0 but higher e00 and l00
due to the presence of less amount of free-charge in the values compared to the BaM-EG and BaM-rEGO

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J Mater Sci (2015) 50:1201–1213 1211

nanocomposites. This result is due to the fact that the with the results as reported by Bhattacharya et al., con-
graphene sheets were decorated with less amount of sidering that the active component (composite) ratio is
BaFe12O19 nanoparticle which is very consistent with the 10 % in the present study. The less filling ratio reduces
magnetization measurements. Similar relationship between permittivity and permeability according to the Maxwell–
the dielectric and magnetic parameters of graphene-hex- Garnett effective medium theory.
agonal M-type ferrites doped with Cu and Al and the active The microwave-absorption properties of samples were
component amount in the test specimens were reported by properties were obtained from the well-known reflection
Bhattacharya et al. [45]. They found the complex dielectric loss (RL) relation given in the Eq. (2):
permittivity and magnetic permeability values of such  
Zin  1
materials embedded into a thermoplastic polyurethane RL ¼ 20 log   ð2Þ
Zin þ 1
matrix with the graphene/hexagonal M-type ferrite ratio of
20 wt% as e & 5.25-j0.15 and l & 1.21-j0.1 at the where Zin is the normalized input impedance given by the
frequency of 8.2 GHz. It can be concluded that the com- following equation:
plex permittivity and permeability values are consistent rffiffiffiffiffi  
lr 2pdf pffiffiffiffiffiffiffiffi
Zin ¼ tanh j lr er ð3Þ
er c
where f, d, c, er, and lr are the frequency, thickness,
velocity of light, complex relative permittivity, and per-
meability, respectively. The RL curves of nanocomposite
samples are shown in Fig. 9. As seen in the figure, the RL
curves of BaM-EG and BaM-rEGO showed a broad peak
with the maxima of -58 dB at 11.42 GHz. On the other
hand, the RL curve of BaM-EGO did not vary much within
the frequency range employed. The RL peaks of BaM-EG
and BaM-rEGO reduced to below -20 dB when the fre-
quency value was of 10.14 GHz, which pointed out that the
reflection was less than 1 % up to the 12.4 GHz with
2.26 GHz frequency width. The RL values below the
-10 dB for the BaM-EG and BaM-rEGO signifies that such
nanocomposites are promising candidates as microwave-
Fig. 9 The Reflection Loss curves of nanocomposites absorbing material since they can absorb 90 % of the wave.

Fig. 10 The thickness- and

frequency-dependent Reflection
Loss curves of BaM-rEGO
nanocomposite (bottom figure)
and the corresponding RL curve
measured with the sample
thickness of 3 mm (top figure)

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1212 J Mater Sci (2015) 50:1201–1213

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