Composites Science and Technology 159 (2018) 240e250

Contents lists available at ScienceDirect

Composites Science and Technology

journal homepage: http://www.elsevier.com/locate/compscitech

Multifunctional BiFeO3 composites: Absorption attenuation

dominated effective electromagnetic interference shielding and
electromagnetic absorption induced by multiple dielectric and
magnetic relaxations
Yong Li a, Ningning Sun a, Jia Liu c, Xihong Hao a, *, Jinhua Du a, Huijing Yang b, ***,
Xiaowei Li a, Maosheng Cao c, **
a
Inner Mongolia Key Laboratory of Ferroelectric-related New Energy Materials and Devices, School of Materials and Metallurgy, Inner Mongolia University
of Science and Technology, Baotou, 014010, China
b
Department of Physics, Tangshan Normal University, Tangshan, 063000, China
c
School of Material Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China

a r t i c l e i n f o a b s t r a c t

Article history: BiFeO3 (BFO) grains prepared by molten salt method were fabricated in paraffin wax based composite
Received 24 November 2017 structure to evaluate electromagnetic interference (EMI) shielding and electromagnetic (EM) absorption
Received in revised form in 2e18 GHz. In the composites, BFO750 paraffin wax composite exhibits excellent EMI shielding and EM
16 January 2018
absorption performance. The EMI shielding effectiveness of BFO750 paraffin wax composite surpasses
Accepted 10 February 2018
10 dB, and its reflection loss shows three absorption peaks which reach
17 dB. The absorption efficiency
Available online 6 March 2018
and attenuation constant are close to 80% and 70, respectively. The results demonstrate that absorption
attenuation is the dominant mechanism of EMI shielding and EM absorption. This is attributed to
Keywords:
BiFeO3
multiple dielectric and magnetic relaxations, where electric and magnetic dipoles coexisting in the
Multifunction composite can respond intensively to electromagnetic wave in the frequency range and thus cause high
Electromagnetic interference shielding electromagnetic loss. The work highlights BFO composites as promising multifunctional materials in
Electromagnetic absorption electromagnetic wave protection fields.
Relaxation © 2018 Elsevier Ltd. All rights reserved.

1. Introduction electromagnetic fields in the radiation. It is thus clear that the

materials as the shield tend to be electrically conducting [18]. For
The electromagnetic interference (EMI) shielding and electro- example, metals and carbon materials are good materials for EMI
magnetic (EM) absorption materials have attracted great attention shielding [19e22]. However, the using of conductive materials
due to their crucial role in blocking undesirable electromagnetic based on reflection mechanism may cause potential secondary
wave irradiation from the electronic devices and communication pollution of electromagnetic wave [23]. EM absorption is mainly
apparatus [1e12]. Generally, EMI shielding and EM absorption caused by absorption attention. Impedance matching is a crucial
involve the mechanisms: reflection and absorption attention which factor to enhance absorption for electromagnetic wave, which
includes absorption and multiple reflection [13e16]. The primary require a low conductivity for materials. Therefore, the EMI
mechanism of EMI shielding is usually reflection [14,17]. For shielding materials with high electrical conduction are not used in
reflection of electromagnetic wave irradiation by the shield, the EM absorption fields due to weak absorption capacity. For complex
shield must have mobile charge carriers which interact with the dynamic environment and various-field applications, it is desirous
to search for multifunctional materials that possess effective EMI
shielding and EM absorption simultaneously. Unfortunately, the
* Corresponding author. studies for the field have been rarely reported.
** Corresponding author. To achieve the multifunctionality, materials should have more
*** Corresponding author. intense absorption attention for electromagnetic wave. Therefore,
E-mail addresses: [email protected] (X. Hao), [email protected] (H. Yang),
the materials should possess electric and/or magnetic dipoles
[email protected] (M. Cao).

https://doi.org/10.1016/j.compscitech.2018.02.014
0266-3538/© 2018 Elsevier Ltd. All rights reserved.
 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250 241

which interact with the electromagnetic fields. In addition, it is also with peculiar physical characteristics may achieve a balance between
desired for the presence of a large surface area or interface area in EMI shielding and EM absorption, which is a potential material for
the materials, which cause multiple reflection [15]. Therefore, a the multifunctional application. However, the combined study and
material that meets these conditions may be a candidate as a comprehensive evaluation on EMI shielding and EM absorption of
multifunctional electromagnetic protection material. BFO have not been carried out, particularly in a wider frequency
BiFeO3 (BFO) is a classic multiferroic material with electric and range (including S, C, X and Ku band). In addition, by material design,
magnetic orderings at room temperature [24,25]. Based on our pre- BFO grains as discontiguous medium can be dispersed in the matrix
vious studies, BFO possesses intrinsic polarization, defect dipole materials. The strategy can help to form multiple reflection of elec-
polarization and ferromagnetic resonance which induce dielectric tromagnetic wave among BFO grains. Here, BFO paraffin wax com-
loss and magnetic loss, leading to strong attenuation for electro- posites were fabricated, and their performances of EMI shielding and
magnetic wave at X-band [26,27]. Reshi et al. reported that BFO EM absorption were investigated at 2e18 GHz. The related mecha-
nanomaterials with electric and magnetic dipoles can perform as an nisms for EMI shielding and EM absorption based on structure and
EMI shielding material at X-band [28]. These studies reveal that BFO electromagnetic properties were discussed.

Fig. 1. (a) XRD patterns of the BFO samples sintered at different temperature and SEM images: (b) the BFO700, (c) BFO750, (d) BFO800 and (e) EDS of the BFO750.
242 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250

2. Experiment (Fout ¼ 7.03 mm; Fin ¼ 3.00 mm).

The phase structure of BFO was measured by X-ray diffraction
BFO was prepared by molten salt method. Stoichiometric (XRD, Bruker, D8 Advanced Diffractometer). The morphology of
amount of Bi2O3 (99%) and Fe2O3 (99%) were milled in alcohol for BFO and the composites were examined by using a field-emission
24 h. The mixture was dried at 80  C for 12 h. The dried powders scanning electron microscopy (FE-SEM, Zeiss, Supra 55). The
and NaCl (1:1 in weight ration) were mixed in a mortar for 30 min. oxidation state of elements was confirmed by using a X-ray
Then they were sintered at 700  C, 750  C, 800  C and 830  C for photoelectron spectroscopy (XPS, Thermo Scientific, Escalab 250
30min, respectively. The resultants were washed by distilled water XI). The relative S parameters, complex permittivity and complex
until no precipitate was detected by AgNO3 solution. The powders permeability were measured on vector network analyzer (VNA,
were dried at 80  C for 24 h. The obtained samples with different Anritsu 37269D) by the coaxial method.
sintering temperature were abbreviated as BFO700, BFO750,
BFO800 and BFO830. 3. Results and discussion
BFO700, BFO750 and BFO800 paraffin wax composites (abbre-
viation: BFO700-PW, BFO750-PW and BFO800-PW) were prepared 3.1. Structure and morphology
by ultrasound mixing method. BFO (80 wt%) and paraffin wax
(20 wt%) were added into pre-heated ether solution at 70  C. BFO The XRD patterns of the BFO samples with different sintering
was dispersed in wax by ultrasound. After the ether was completely temperature are shown in Fig. 1a. The main peaks of BFO700 are
evaporated, the mixture was cooled to room temperature. A portion identified by the structure of BFO (PDF#71-2494), which exhibits
of the resulting mixture was pressed into toroidal shape rhombohedral perovskite structure [29]. However, a little impurity

Fig. 2. High-resolution XPS spectra of (a-c) Fe 2p and (d-f) O 1s core levels for the BFO samples.
 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250 243

Fig. 3. (a,b)SEM images and (c,d) element maps of the BFO750-PW.

phase is observed which may be Bi25FeO40. As the sintering tem- adsorbed surface H2O as well as the presence of oxygen vacancies,
perature increases, the impurity phase disappears. BFO750 shows respectively [31]. Similarly, the concentration of oxygen vacancies
single rhombohedral structure. When the sintering temperature is of BFO750 is the lowest among these three BFO samples. It is known
800  C, a little amount of impurity phase appears in BFO800 again. that oxygen vacancies and Fe2þ appear simultaneously for charges
The sample sintered at 830  C has an obvious mixed phase struc- compensation in BFO [32]. The results illustrate a fact that appro-
ture which consists of BFO, Bi25FeO40 and Bi2Fe4O9 (Fig. S1), and the priate sintering temperature can suppress the forming of anion
main reason for formation of impurity phase is that a lot of bismuth vacancies in BFO, which is favorable to decreasing the leakage
volatilizes around the Curie temperature of BFO. Therefore, current of BFO. The result is confirmed by the current density of the
BFO700, BFO750 and BFO800 are chosen as the materials investi- BFO samples (Fig. S3).
gated in this study. Fig. 1bed shows the SEM images of the BFO The paraffin wax-based composites were fabricated via com-
samples. It is observed that the grains of the BFO samples show pressing at room temperature. Fig. 3a,b show the SEM images of
random shapes. The size of the grains is in submicron or micro- BFO750-PW. It is found that the BFO grains were dispersed evenly
meter scale, and it increases with the increase of the sintering in paraffin wax. In addition, the element maps of Fe from BFO and C
temperature. The EDS of BFO750 demonstrates that it just consists from paraffin wax are shown in Fig. 3c,d. Fe element and C element
of Bi, Fe and O elements (Fig. 1e). display homogeneous distribution in the measured region, indi-
The elemental components of BFO750 are identified by XPS cating that the BFO grains and wax are mixed uniformly.
spectrum (Fig. S2). BFO750 is completely composed of Bi, Fe and O
elements. No other elemental signals are detected. The ionic
valence is identified by the high-resolution XPS spectra in Fig. 2.
Fig. 2aec shows the XPS spectra of Fe 2p for the BFO samples. The
dominant Fe 2p peaks are at around 710.6 eV and 724.3 eV binding, 3.2. EMI shielding
respectively [8]. The splitting of Fe 2p is 13.7 eV, which obviously
arises from Fe3þ. Two high-binding energy shoulders are present at EMI shielding effectiveness (SETot) refers to the logarithm of the
717.8 eV and 731.6 eV, indicating that Fe2þ exists in these three BFO ratio of the incident wave PI to the transmitted wave PT [33],
samples [30]. The percentage of Fe2þ in BFO750 is significantly
lower than that of the other two BFO samples. The XPS spectra of O SETot ¼ 10 logðPI =PT Þ (1)
1s are shown in Fig. 2def. Three peaks appear in the spectra. The
main peak at 529.4 eV corresponds to the cation-oxygen bonds. The The SETot consists of the reflection (SER) and absorption (SEA),
higher-energy peaks at 532.4 eV and 531.6 eV are assigned to involving the contribution of multiple-reflections. The SER and SEA
can be achieved by the equations [34,35]:
244 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250

Fig. 4. (a) Total EMI SE, (b) reflection, (c) absorption effectiveness and (d) the comparing of the properties of the BFO paraffin wax composites.

SER ¼
10 logð1
RÞ (2) R ¼ jS11 j2 (4)

SEA ¼
10 log½T=ð1
RÞ (3) T ¼ jS21 j2 (5)

where R is reflection coefficient. Fig. 4 shows the EMI ES perfor- A¼1
R
T (6)
mance of the composites. It is observed that the EMI ES shows
obvious frequency dependence. The SETot of BFO750-PW is bigger The R, T and A of the BFO paraffin wax composites in 2e18 GHz
than that of BFO700-PW and BFO800-PW in the entire frequency are shown in Fig. 5aec. BFO750-PW has the largest A among these
range, and the maximum value of the SETot surpasses 10 dB, three composites, and the R and T are smaller compared with the
exhibiting an efficient EMI shielding. In Fig. 4b, the SER of BFO700- other composites. Fig. 5d shows the average value of EMI power in
PW is the highest among these three composites. For the SEA, the 2e18 GHz. For BFO750-PW, the amount of energy blocked by ab-
value of BFO750-PW is obviously higher compared with that of sorption is higher than that blocked by reflection.
BFO700-PW and BFO800-PW (Fig. 4c). In the measurement fre-
quency range, the proportion of the SEA in the SETot exceeds 50% for
3.3. EM absorption
BFO750-PW. The comparison of the EMI ES performance for these
three composites at 10 GHz is shown in Fig. 5d. It can be directly
The EM absorption is another issue for electromagnetic atten-
found that BFO750-PW has the highest SETot, and the SETot is mainly
uation, which is evaluated based on the complex permittivity and
from the contribution of the SEA.
permeability [38]. The reflection loss (RL) of single absorb layer can
To verify further contribution of reflection and absorption to the
be calculated as follow [39e41]:
shielding of the BFO paraffin wax composites, the EMI power data is
analyzed. The EMI power coefficients including reflection coeffi- jZin
1j
cient (R), transmission coefficient (T) and absorption coefficient (A) RL ¼ 20 log (7)
jZin þ 1j
are determined by S parameters (S11 and S21), which are calculated
by the equations [33,36,37]: Here the normalized input impedance Zin of the electromagnetic
 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250 245

Fig. 5. (a) EMI reflection coefficient, (b) transmission coefficient, (c) absorption coefficient and (d) their average value of BFO paraffin wax composites.

attenuation layer is given by materials [44]. In Fig. 7, it is observed that the frequency of these
three absorption peaks is consistent with that of d/lD ¼ 1/4, 3/4, 5/
 
pffiffiffiffiffiffiffiffiffiffiffi 2pfd pffiffiffiffiffiffiffiffiffi 4. This result demonstrates that the multiple absorption is from the
Zin ¼ mr =εr tanh j mr εr (8) contribution of quarter-wavelength attenuation.
c

Where c is the light velocity, f is the electromagnetic wave fre-

quency, d is the thickness of the absorber, and mr and εr are the
relative permeability and permittivity of the composite medium,
respectively. The RL of these three composites with different 3.4. Discussion
thickness of absorption layer is shown in Fig. 6. Compared with
BFO700-PW and BFO800-PW, BFO750-PW has larger attenuation Generally, the mechanisms of EMI shielding and EM absorption
capability, and its maximum RL reaches up to
22.5 dB at d ¼ 4 mm, are reflection and absorption attenuation which includes absorp-
which is larger than that of other BFO samples prepared by sol-gel tion and multiple reflection caused by dipoles and interfaces
method (
11 dB) and solid solution method (
17 dB) [42,43]. respectively. For the BFO paraffin wax composites, according to the
Furthermore, it is observed that the composites have three ab- results of EMI shielding and EM absorption, it is obvious that part of
sorption peaks located in around 2e8 GHz, 8e13 GHz and the electromagnetic wave is dissipated by absorption attenuation.
13e18 GHz respectively. Particularly, all the three absorption peaks Particularly, for BFO750-PW, absorption attenuation is the main
of BFO750-PW exceed
17 dB at d ¼ 8 mm, which represents high- contribution. To investigate the origin of absorption attenuation,
efficiency multiple absorption. In order to understand the multiple the electromagnetic properties of the composites are measured.
absorption behavior, the mode based on quarter-wavelength Fig. 8 shows the complex permittivity (ε0 - jε00 ) and complex
attenuation is presented in Fig. 7. According to electromagnetic permeability (m0 - jm00 ) of the composites in the frequency range of
wave theory, the electromagnetic wave absorption occurs in the 2e18 GHz. Among these three composites, the BFO750-PW has the
neighboring positions of d/lD ¼ 1/4, 3/4, 5/4, 7/4 …, where d is the biggest ε0 and ε00 (Fig. 8a,b). Moreover, the polarization contribution
thickness of the absorber, lD ¼ l/n is the wavelength in a dielectric, and conductance contribution to dielectric properties can be
l is the wavelength in a vacuum and n is the refractive index of explicated by the Debye theory. The ε00 is shown as follow [13]:
246 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250

Fig. 6. The reflection loss of (a) BFO700-PW, (b) BFO750-PW, (c) BFO800-PW and (d) the compare of the reflection loss at d ¼ 8mm.

responses to electromagnetic wave of 2e18 GHz, which causes loss

00 εs
ε∞ s for electromagnetic wave consequently.
ε ¼ ut þ (9)
1 þ u2 t 2 ε0 u In spite of the existing of electric dipoles and magnetic dipoles, it
does not mean that the composites possess strong attenuation for
where s is the electrical conductivity, ε0 the vacuum permittivity. electromagnetic wave. The intensity of attenuation depends on
Based on the electrical conductivity, the conduction part (εc00 ) and magnitude of loss and electromagnetic matching level. Fig. 9 shows
the polarization part (εp00 ) of imaginary permittivity are obtained, the dielectric loss (tande) and magnetic loss (tandm) of the BFO
as shown in Fig. S4. The εc00 is much smaller than the εp00 . Therefore, paraffin wax composites. The composites show a relative balance
the main contribution to the ε00 of the composites is polarization between the tande and tandm. This indicates that the BFO paraffin
rather than conductance. It is found that three dielectric relaxation wax composite possesses high level in electromagnetic matching
peaks exist in the ε00 for the composites, presenting dielectric multi- [46]. However, the values of tande and tandm for BFO750-PW are
relaxation behavior. It is suggested that these three relaxations higher than those of BFO700-PW and BFO800-PW. This result
should be induced by different polarization modes from various represents that electric dipoles and magnetic dipoles of BFO750-
electric dipoles. Based on frequency response of dipoles, it is pro- PW have strong response to electromagnetic wave, leading to a
posed that the two relaxations at low frequency may be induced by bigger absorption attenuation.
intrinsic and defect polarization from the lone pair of Bi ions and It is known that the attenuation contribution of EMI power and
oxygen vacancies respectively, and the relaxations at high fre- EM absorption can be expressed by absorption efficiency (AE) and
quency may be caused by the polarization from the charges of BFO/ attenuation constant (a) [47,48]:
wax interfaces.
Fig. 8c,d shows the m0 and m00 of the composites. For different AEð%Þ ¼ A=ð1
RÞ (10)
composites, the m0 just changes slightly. Compared with the other
two composites, the BFO750-PW has a bigger m00 in the frequency
pffiffiffi sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ffi
range. The eddy current coefficients m''(m0 )
2f
1 of the composites 2pf  
change with the increase of frequency. This indicates that the a¼ m00 ε00
m0 ε0 þ m0 2 þ m00 2 ε0 2 þ ε00 2 (11)
c
magnetic loss is not caused by eddy current loss (Fig. S5) [45],
implying that conductance contribution to magnetic loss is negli- Based on the AE curves in Fig. 10a, the AE of BFO750-PW is
gible. Interestingly, the m00 possesses similar multi-relaxation higher than that of BFO700-PW and BFO800-PW, where the
behavior. Three relaxation peaks locate in different frequencies, maximum value is close to 80%. In addition, BFO750-PW has the
which may be caused by domain wall resonance, natural resonance largest a among the composites (Fig. 10b). Fig. 10c shows the
and exchange resonance. Therefore, various electric dipoles and reflection and absorption attenuation situation of electromagnetic
magnetic dipoles coexisting in the composites have multiple wave when it transmits from medium to BFO paraffin wax
 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250 247

Fig. 7. (a) The reflection loss and (b) the frequency dependence of d/lD for the BFO paraffin wax composites at d ¼ 8mm.

composites. When incident wave arrives at the surface of the electromagnetic wave may have multiple reflections behavior,
composites, a part of electromagnetic wave will be reflected off the where electromagnetic wave is reflected multiply among surfaces
surface and enter medium again. The other part of electromagnetic of BFO grains and is absorbed gradually. Based on the discussion, it
wave will be into the composites. In this part, some can be absorbed is demonstrated that absorption attenuation is the dominant
by BFO grains while the others will pass through the composites. mechanism for BFO750-PW.
From the results of the AE and a, it is confirmed that a little amount
of electromagnetic wave is reflected for BFO750-PW, indicating that
reflection has less contribution which absorption is the dominant 4. Conclusion
contribution. This is mainly attributed to the tiny conductance
contribution to the electromagnetic parameters of BFO750-PW, BFO paraffin wax composites show effective EMI shielding and
which leads to most of electromagnetic wave enter the composite. EM absorption. The investigation on the EMI shielding and EM
More crucially, according to the electromagnetic properties, a large absorption properties indicates that absorption attenuation is the
amount of electric dipoles and magnetic dipoles coexist in BFO750- dominant mechanism. It is attributed to both of multiple dielectric
PW. They intensively interact with electromagnetic wave in the and magnetic relaxation based on the electromagnetic properties.
frequency range and thus cause the strong attenuation (Fig. 10d). In Particularly, BFO750-PW exhibits enhanced EMI shielding and EM
addition, in the BFO paraffin wax composites, BFO grains are absorption properties. Its EMI shielding effectiveness surpasses
dispersed in wax matrix uniformity, with the result that part of 10 dB. The reflection loss shows multiple absorptions behavior with
three absorption peaks due to the contribution of quarter-
248 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250

Fig. 8. The complex permittivity and permeability of the BFO paraffin wax composites.

Fig. 9. The dielectric loss and magnetic loss of the BFO paraffin wax composites.
 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250 249

Fig. 10. (a) Absorption efficiency, (b) attenuation constant of BFO paraffin wax composites, (c) Schematic illustration of reflection, absorption for electromagnetic wave through BFO
paraffin wax composites, (d) the comparing of EMI shielding and EM absorption in the composites.

wavelength attenuation, and all of three absorption peaks Fe2O3@C@alpha-MnO2 nanospindle with broadened microwave absorption
bandwidth by chemically etching, Small 13 (5) (2017) 1602779.
reach
17 dB at d ¼ 8 mm. BFO paraffin wax composites will
[3] K.D. Jiang, Y. Liu, Y.F. Pan, R. Wang, P.B. Hu, R.J. He, L.L. Zhang, G.X. Tong,
expand the applications of BFO as a multifunctional electromag- Monodisperse NixFe3-xO4 nanospheres: metal-ion-steered size/composition
netism materials in communications, imaging, signal and data control mechanism, static magnetic and enhanced microwave absorbing
protection fields. properties, Appl. Surf. Sci. 404 (2017) 40e48.
[4] Y.L. Wang, K. Ren, J. Sun, W. Li, S.L. Zhao, Z.H. Chen, J.G. Guan, Ultralow content
silver densely-coated glass microsphere for high performance conducting
Acknowledgements polymer-matrix composites, Compos. Sci. Technol. 140 (2017) 89e98.
[5] P.B. Liu, Y. Huang, X. Zhang, Cubic NiFe2O4 particles on graphene-polyaniline
and their enhanced microwave absorption properties, Compos. Sci. Technol.
This research was supported by the Innovation Fund of Inner 107 (2015) 54e60.
Mongolia University of Science and Technology (2016QDL-B03, [6] D.L. Zhao, X. Li, Z.M. Shen, Microwave absorbing property and complex
permittivity and permeability of epoxy composites containing Ni-coated and
2016QDL-S01), the Natural Science Foundation of China (51702169,
Ag filled carbon nanotubes, Compos. Sci. Technol. 68 (14) (2008) 2902e2908.
11604237), the Natural Science Foundation of Inner Mongolia [7] W.L. Song, K.L. Zhang, M. Chen, Z.L. Hou, H. Chen, X. Yuan, Y. Ma, D. Fang,
(2015JQ04, 2017BS0503), Natural Science Foundation of Hebei A universal permittivity-attenuation evaluation diagram for accelerating
Province (E2015105079), the Grassland Talent Plan of Inner design of dielectric-based microwave absorption materials: a case of
graphene-based composites, Carbon 118 (2017) 86e97.
Mongolia Autonomous Region. [8] F. Movassagh-Alanagh, A. Bordbar-Khiabani, A. Ahangari-Asl, Three-phase
PANI@nano-Fe3O4@CFs heterostructure: fabrication, characterization and
investigation of microwave absorption and EMI shielding of PANI@nano-
Appendix A. Supplementary data
Fe3O4@CFs/epoxy hybrid composite, Compos. Sci. Technol. 150 (2017) 65e78.
[9] W. Li, M. Chen, Z. Zeng, H. Jin, Y. Pei, Z. Zhang, Broadband composite radar
Supplementary data related to this article can be found at absorbing structures with resistive frequency selective surface: optimal
design, manufacturing and characterization, Compos. Sci. Technol. 145 (2017)
https://doi.org/10.1016/j.compscitech.2018.02.014.
10e14.
[10] W.L. Song, X.T. Guan, L.Z. Fan, Y.B. Zhao, W.Q. Cao, C.Y. Wang, M.S. Cao, Strong
References and thermostable polymeric graphene/silica textile for lightweight practical
microwave absorption composites, Carbon 100 (2016) 109e117.
[11] Y. Li, T. Wu, K. Jiang, G. Tong, K. Jin, N. Qian, L. Zhao, T. Lv, Mn2þ induced
[1] W.Y. Duan, X.W. Yin, Q. Li, L. Schlier, P. Greil, N. Travitzky, A review of ab-
structure evolution and dual-frequency microwave absorption of MnxFe3-xO4
sorption properties in silicon-based polymer derived ceramics, J. Eur. Ceram.
hollow/porous spherical chains made by a one-pot solvothermal approach,
Soc. 36 (15) (2016) 3681e3689.
J. Mater. Chem. C 4 (29) (2016) 7119e7129.
[2] W.B. You, H. Bi, W. She, Y. Zhang, R.C. Che, Dipolar-distribution cavity gamma-
250 Y. Li et al. / Composites Science and Technology 159 (2018) 240e250

[12] Y. Liu, T. Cui, T. Wu, Y. Li, G. Tong, Excellent microwave-absorbing properties pinned defect-dipoles for high-performance colossal permittivity materials,
of elliptical Fe3O4 nanorings made by a rapid microwave-assisted hydro- Nat. Mater. 12 (9) (2013) 821e826.
thermal approach, Nanotechnology 27 (16) (2016). [32] A. Tamilselvan, S. Balakumar, M. Sakar, C. Nayek, P. Murugavel, K.S. Kumar,
[13] B. Wen, M.S. Cao, M.M. Lu, W.Q. Cao, H.L. Shi, J. Liu, X.X. Wang, H.B. Jin, Role of oxygen vacancy and Fe-O-Fe bond angle in compositional, magnetic,
X.Y. Fang, W.Z. Wang, J. Yuan, Reduced graphene oxides: light-weight and and dielectric relaxation on Eu-substituted BiFeO3 nanoparticles, Dalton
high-efficiency electromagnetic interference shielding at elevated tempera- Trans. 43 (15) (2014) 5731e5738.
tures, Adv. Mater. 26 (21) (2014) 3484e3489. [33] P. Saini, V. Choudhary, N. Vijayan, R.K. Kotnala, Improved electromagnetic
[14] M.H. Al-Saleh, U. Sundararaj, Electromagnetic interference shielding mecha- interference shielding response of poly(aniline)-coated fabrics containing
nisms of CNT/polymer composites, Carbon 47 (7) (2009) 1738e1746. dielectric and magnetic nanoparticles, J. Phys. Chem. C 116 (24) (2012)
[15] W.L. Song, M.S. Cao, M.M. Lu, S. Bi, C.Y. Wang, J. Liu, J. Yuan, L.Z. Fan, Flexible 13403e13412.
graphene/polymer composite films in sandwich structures for effective elec- [34] W.Y. Duan, X.W. Yin, Q. Li, X.M. Liu, L.F. Cheng, L.T. Zhang, Synthesis and
tromagnetic interference shielding, Carbon 66 (2014) 67e76. microwave absorption properties of SiC nanowires reinforced SiOC ceramic,
[16] W.L. Song, C. Gong, H. Li, X.D. Chen, M. Chen, X. Yuan, H. Chen, Y. Yang, J. Eur. Ceram. Soc. 34 (2) (2014) 257e266.
D. Fang, Graphene-based sandwich structures for frequency selectable elec- [35] Z. Chen, C. Xu, C. Ma, W. Ren, H.-M. Cheng, Lightweight and flexible graphene
tromagnetic shielding, ACS Appl. Mater. Interfaces 9 (41) (2017) foam composites for high-performance electromagnetic interference shield-
36119e36129. ing, Adv. Mater. 25 (9) (2013) 1296e1300.
[17] J. Liu, H.B. Zhang, Y. Liu, Q. Wang, Z. Liu, Y.W. Mai, Z.Z. Yu, Magnetic, elec- [36] D. Micheli, R. Pastore, C. Apollo, M. Marchetti, G. Gradoni, V.M. Primiani,
trically conductive and lightweight graphene/iron pentacarbonyl porous films F. Moglie, Broadband electromagnetic absorbers using carbon nanostructure-
enhanced with chitosan for highly efficient broadband electromagnetic based composites, IEEE Trans. Microw. Theor. Tech. 59 (10) (2011)
interference shielding, Compos. Sci. Technol. 151 (2017) 71e78. 2633e2646.
[18] D.D.L. Chung, Electromagnetic interference shielding effectiveness of carbon [37] Y.C. Qing, Y. Mu, Y.Y. Zhou, F. Luo, D.M. Zhu, W.C. Zhou, Multiwalled carbon
materials, Carbon 39 (2001) 279e285. nanotubes BaTiO3/silica composites with high complex permittivity and
[19] C.S. Zhang, Q.-Q. Ni, S.Y. Fu, K. Kurashiki, Electromagnetic interference improved electromagnetic interference shielding at elevated temperature,
shielding effect of nanocomposites with carbon nanotube and shape memory J. Eur. Ceram. Soc. 34 (10) (2014) 2229e2237.
polymer, Compos. Sci. Technol. 67 (14) (2007) 2973e2980. [38] Y. Liu, Y. Li, K. Jiang, G. Tong, T. Lv, W. Wu, Controllable synthesis of elliptical
[20] S.H. Lee, S. Yu, F. Shahzad, J.P. Hong, W.N. Kim, C. Park, S.M. Hong, C.M. Koo, Fe3O4@C and Fe3O4/Fe@C nanorings for plasmon resonance-enhanced mi-
Highly anisotropic Cu oblate ellipsoids incorporated polymer composites with crowave absorption, J. Mater. Chem. C 4 (30) (2016) 7316e7323.
excellent performance for broadband electromagnetic interference shielding, [39] B. Wen, M.S. Cao, Z.L. Hou, W.L. Song, L. Zhang, M.M. Lu, H.B. Jin, X.Y. Fang,
Compos. Sci. Technol. 144 (2017) 57e62. W.Z. Wang, J. Yuan, Temperature dependent microwave attenuation behavior
[21] W.L. Song, P. Wang, L. Cao, A. Anderson, M.J. Meziani, A.J. Farr, Y.P. Sun, for carbon-nanotube/silica composites, Carbon 65 (2013) 124e139.
Polymer/boron nitride nanocomposite materials for superior thermal trans- [40] T. Wu, Y. Liu, X. Zeng, T. Cui, Y. Zhao, Y. Li, G. Tong, Facile hydrothermal
port performance, Angew. Chem. Int. Ed. 51 (26) (2012) 6498e6501. synthesis of Fe3O4/C vore-shell nanorings for efficient low-frequency micro-
[22] M.J. Meziani, W.L. Song, P. Wang, F. Lu, Z. Hou, A. Anderson, H. Maimaiti, Y.- wave absorption, ACS Appl. Mater. Interfaces 8 (11) (2016) 7370e7380.
P. Sun, Boron nitride nanomaterials for thermal management applications, [41] G. Tong, Y. Liu, T. Cui, Y. Li, Y. Zhao, J. Guan, Tunable dielectric properties and
ChemPhysChem 16 (7) (2015) 1339e1346. excellent microwave absorbing properties of elliptical Fe3O4 nanorings, Appl.
[23] S. Biswas, I. Arief, S.S. Panja, S. Bose, Absorption-dominated electromagnetic Phys. Lett. 108 (7) (2016).
wave suppressor derived from ferrite-doped cross-linked graphene frame- [42] Z.L. Hou, H.F. Zhou, L.B. Kong, H.B. Jin, X. Qi, M.S. Cao, Enhanced ferromag-
work and conducting carbon, ACS Appl. Mater. Interfaces 9 (3) (2017) netism and microwave absorption properties of BiFeO3 nanocrystals with Ho
3030e3039. substitution, Mater. Lett. 84 (2012) 110e113.
[24] M.M. Kumar, V.R. Palkar, K. Srinivas, S.V. Suryanarayana, Ferroelectricity in a [43] F.S. Wen, N. Wang, F. Zhang, Enhanced microwave absorption properties in
pure BiFeO3 ceramic, Appl. Phys. Lett. 76 (19) (2000) 2764e2766. BiFeO3 ceramics prepared by high-pressure synthesis, Solid State Commun.
[25] G. Catalan, J.F. Scott, Physics and applications of bismuth ferrite, Adv. Mater. 150 (39e40) (2010) 1888e1891.
21 (24) (2009) 2463e2485. [44] K. Lakshmi, H. John, K.T. Mathew, R. Joseph, K.E. George, Microwave absorp-
[26] Y. Li, W.Q. Cao, J. Yuan, D.W. Wang, M.S. Cao, Nd doping of bismuth ferrite to tion, reflection and EMI shielding of PUePANI composite, Acta Mater. 57
tune electromagnetic properties and increase microwave absorption by (9e10) (2009) 371e375.
magnetic-dielectric synergy, J. Mater. Chem. C 3 (36) (2015) 9276e9282. [45] Y. Li, M.S. Cao, D.W. Wang, J. Yuan, High-efficiency and dynamic stable elec-
[27] Y. Li, X.Y. Fang, M.S. Cao, Thermal frequency shift and tunable microwave tromagnetic wave attenuation for La doped bismuth ferrite at elevated tem-
absorption in BiFeO3 family, Sci. Rep. 6 (2016). perature and gigahertz frequency, RSC Adv. 5 (94) (2015) 77184e77191.
[28] H.A. Reshi, A.P. Singh, S. Pillai, T.A. Para, S.K. Dhawan, V. Shelke, X-band fre- [46] M.S. Cao, J. Zhu, J. Yuan, T.F. Zhang, Z.H. Peng, Z.J. Gao, G. Xiao, S.M. Qin,
quency response and electromagnetic interference shielding in multiferroic Computation design and performance prediction towards a multi-layer mi-
BiFeO3 nanomaterials, Appl. Phys. Lett. 109 (14) (2016). crowave absorber, Mater. Des. 23 (6) (2002) 557e564.
[29] Y. Li, M.S. Cao, Enhanced electromagnetic properties and microwave attenu- [47] A. Gupta, V. Choudhary, Electromagnetic interference shielding behavior of
ation of BiFeO3-BaFe7(MnTi)(2.5)O19 driven by multi-relaxation and strong poly(trimethylene terephthalate)/multi-walled carbon nanotube composites,
ferromagnetic resonance, Mater. Des. 110 (2016) 99e104. Compos. Sci. Technol. 71 (13) (2011) 1563e1568.
[30] T. Yamashita, P. Hayes, Analysis of XPS spectra of Fe2þ and Fe3þ ions in oxide [48] F. Qin, C. Brosseau, A review and analysis of microwave absorption in polymer
materials, Appl. Surf. Sci. 254 (8) (2008) 2441e2449. composites filled with carbonaceous particles, J. Appl. Phys. 111 (6) (2012)
[31] W. Hu, Y. Liu, R.L. Withers, T.J. Frankcombe, L. Noren, A. Snashall, M. Kitchin, 061301.
P. Smith, B. Gong, H. Chen, J. Schiemer, F. Brink, J. Wong-Leung, Electron-