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biomass cotton for lightweight and high-performance electromagnetic wave absorption applications
Journal Pre-proof Fe@NPC@CF nanocomposites derived from Fe-MOFs/biomass cotton for lightweight and high-performance electromagnetic wave absorption applications Xiang Li, Erbiao Cui, Zhen Xiang, Lunzhou Yu, Juan Xiong, Fei Pan, Wei Lu PII:
S0925-8388(19)34198-2
DOI:
https://doi.org/10.1016/j.jallcom.2019.152952
Reference:
JALCOM 152952
To appear in:
Journal of Alloys and Compounds
Received Date: 18 August 2019 Revised Date:
3 November 2019
Accepted Date: 7 November 2019
Please cite this article as: X. Li, E. Cui, Z. Xiang, L. Yu, J. Xiong, F. Pan, W. Lu, Fe@NPC@CF nanocomposites derived from Fe-MOFs/biomass cotton for lightweight and high-performance electromagnetic wave absorption applications, Journal of Alloys and Compounds (2019), doi: https:// doi.org/10.1016/j.jallcom.2019.152952. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier B.V.
Graphical Abstract
Fe@NPC@CF nanocomposites exhibited an excellence electromagnetic absorption performance due to the synergistic effects of the magnetic and dielectric loss among Fe nanoparticles, NPC and CF.
Fe@NPC@CF nanocomposites derived from Fe-MOFs/Biomass Cotton for lightweight and high-performance Electromagnetic Wave Absorption applications Xiang Lia, Erbiao Cuia, Zhen Xiangb, Lunzhou Yua, Juan Xiongb, Fei Panb, and Wei Lub,∗ a
School of Materials Science & Engineering, University of Shanghai for Science and
Technology, Shanghai 200093, China b
Shanghai Key Lab. of D&A for Metal-Functional Materials, School of Materials
Science & Engineering, Tongji University, Shanghai 201804, China. *Corresponding author. E-mail address: [email protected] (Wei Lu). ABSTRACT Electromagnetic (EM) wave absorbing materials have been extensively applied in the electronic devices and wireless communication to solve the increasingly serious problems of electromagnetic pollution and radiation. In this work, Fe-MOFs/biomass cotton derived Fe@nanoporous carbon@carbon fiber (Fe@NPC@CF) composites were successfully obtained by means of in-situ synthesis and thermal decomposition processes. It was found that the Fe@NPC composites were uniformly distributed on the carbon fibers matrix. As a result, EM wave absorbing performances were greatly promoted via the synergic effects among Fe nanoparticles, nanoporous carbon and carbon fibers. A strong reflection loss (RL) of -46.2 dB and a wide absorbing bandwidth of 5.2 GHz (RL<-10 dB) with a matching thickness of 2.5 mm were achieved for the Fe@NPC@CF 1
composites with a low filling ratio of 25%. Therefore, this work not only paved the way for development of biomass as a green, low-cost and renewable high-performance carbon-based absorber, but also provided a good design and fabricating concept for the composite materials of EM wave absorber. Keywords: MOFs, biomass cotton, Fe@NPC, carbon fiber, synergic effect, electromagnetic wave absorption 1. INTRODUCTION With the rapid development of wireless communication and electronic technology, electromagnetic pollution problems such as electromagnetic radiation and electromagnetic interference have attracted much attention [1-5]. Accordingly, an efficient electromagnetic wave absorbing materials to solve above serious issues should satisfy four characteristics: strong adsorption, broad bandwidth, lightweight, and thin thickness [6-10]. It is well-known that the traditional electromagnetic wave absorbing materials such as dielectric materials [11-13] and magnetic materials [14, 15] have been applied to the field of EM wave absorption. However, there is much space for the improvement in the performance of EM wave absorbing materials. For magnetic materials, the high density, large thickness, and narrow absorbing bandwidth limit its practical applications. For dielectric materials, its application was restricted by the poor impedance matching derived from relatively high complex permittivity and low permeability [16]. 2
Therefore, the composites with dielectric material and magnetic material can realize the fantastic performance of EM wave absorption [17-22], such as Fe3O4/MWCNTs [23], Ni/C [24] and Co/C [25]. In addition to material composition, a reasonable material structure is also a key factor for the superior EM absorption performance [26], including core-shell structure, porous structure and so on [27]. Among them, the porous carbon materials are considered to be a novel EM absorbing materials due to the well-matched impedance [28-31]. For instance, porous flower-like NiO@graphene composites prepared by Wang et al exhibited excellent EM absorbing properties with minimum reflection loss (RLmin) of -59.6 dB at 14.2 GHz, and the absorption bandwidths (RL <-10 dB) ranged from 12.5 GHz to 16.7 GHz with a thickness of only 1.7 mm [32]. Feng et al fabricated the porous FeNi3/N-GN composites with a RLmin of -57.2dB with an ultrathin thickness of only 1.45 mm and the corresponding effective bandwidth is larger than 3.4 GHz (14.6–18 GHz) [33]. Nevertheless, there is still a difficulty in simultaneously controlling the material composition and microstructure to achieve excellent EM wave absorbency. Fortunately, Metal-organic frameworks (MOFs) consist of nanopores and open channels have been regarded as the ideal precursor for nanoporous carbon materials with homogeneous atomic distribution [34, 35]. Moreover, the EM absorbing materials with magnetic nanoparticles adhered to porous carbon matrix 3
have been synthesized by the thermal decomposition of MOFs precursor [36]. For example, Zhang et al reported the Ni@C composite derived from MOFs, reached to -55.7 dB corresponding to 6.0 GHz absorption bandwidth (<−10 dB) with a thickness of 1.85 mm [37]. Yuan et al reported MOFs derived carbonaceous Co3O4/Co/RGO composite with a RLmin of -52.8 dB at 13.2 GHz with a thickness of 2 mm [38]. In our previous work, the RL value of porous Fe3O4@NPC composites derived from Fe-MOFs reached to -65.5 dB, with a matching thickness of 3 mm and a wide frequency bandwidth (4.5 GHz) [39]. The carbonized product forms nanoporous carbon with a large porosity and specific surface area. The low density of porous carbon meets the requirements of light absorbers. Its rich pore structure provides abundant active reflection sites inside the material for EM waves. At the same time, a good conductive network is formed, and the EM wave energy is finally dissipated in the form of Joule heat. Taking account of the amorphous characteristics of the MOFs-derived porous carbon, the enhancement of the dielectric loss by increasing conductivity is required [40-44]. Among the dielectric materials, biomass cotton due to its availability, high specific surface areas, functional groups, and low density, has been used to enhance the microwave attenuation performances. For instance, Li et al. successfully prepared Co/C fibers by using low-cost biomass cotton as carbon source with RL values below -10 dB in the frequency range of 11.3-18 GHz, 4
which covered the whole Ku-band (12 ~ 18 GHz) [45]. Wei et al prepared waste-cotton
derived
porous
carbon,
combined
with well-dispersed
Ni
nanoparticles with excellent microwave absorption properties (RL＜-20 dB) exhibiting in very broad frequency ranges (2.0 to 8.8 GHz and 10.9 to 18 GHz) [46]. Recently, Zhao et al fabricated carbon-cotton/Co@nanoporous carbon composites with the optimal reflection loss of -51.2 dB and a broad bandwidth of 4.4 GHz [47]. Despite some related reports on biomass cotton derived absorbing material, achieving an excellent EM wave absorbency and obtaining the absorber via a simple way is still an urgent problem. Herein, we fabricated Fe-MOFs/biomass cotton derived Fe@nanoporous carbon@carbon fiber (Fe@NPC@CF) composites in a way of microwave assisted in-situ rapid synthesis and thermal decomposition processes. It was found the materials were well combined with the Fe@NPC composites evenly dispersed on the carbon fiber. The composites showed strong EM absorption properties: a strong minimum reflection loss (RLmin) of -46.2 dB, a wide absorbing bandwidth of 5.2 GHz (RL<-10 dB) with a matching thickness of 2.5 mm and a low filling ratio of 25%. The EM absorbing mechanism can be ascribed to the synergy effects among the internal materials and the good impedance matching caused by the dielectric loss and magnetic loss. Thus, this work not only paved the way for development of biomass as a green, low-cost and renewable high-performance 5
carbon-based absorber, but also provided a good design and fabricating concept for the composite materials of EM wave absorber. 2. EXPERIMENTAL DETAILS 2.1 Materials Pristine cottons, hydrogen peroxide(H2O2), sodium silicate (Na2SiO3), sodium hydroxide (NaOH), N,N-dimethylformamide (DMF), ferric chloride hexahydrate (FeCl3· 6H2O), and 1, 4-benzenedicarboxylic acid (H2BDC). All of them were obtained from Shanghai Aladdin Industrial Corporation. 2.2 Fabrication of Fe@NPC@CF composites The schematic fabricating process of Fe@NPC@CF composites is shown in scheme 1. First, pristine cottons were activated. 0.8 g cottons were immersed into the mixture solution (270 ml) which contains H2O2 (2 mol/L), 1.08 g Na2SiO3 and 2.7 g NaOH. The treatment was undergoing at 90 ℃ for 1 h. After that the product obtained was purified and dried in a vacuum at 60 ℃ for 48 h. The fabrication of Fe-MOF/cotton composites is listed as following: FeCl3· 6H2O (1.990 g, 7.36 mmol) and H2BDC (1.224 g, 7.36 mmol) were dissolved in DMF (160 mL, 2.08 mol) , with magnetic stirring for 30 min .Then the activated cottons were immersed into the solution with sonication for 2 h before the microwave heating at 140 ℃, for 6 min. After that, by vacuum 6
filtration, the product was assembled and washed with ethanol, and finally dried at 60 ℃ for 48 h. In order to get Fe@NPC@CF composites, the heating treatments of Fe-MOF/cotton composites were carried out at 500 ℃, 550 ℃, 600 ℃ for 2 h in Ar atmosphere. The final products were named S500, S550 and S600, respectively. 2.3 Characterization X-ray diffraction (XRD) was performed by using Cu-Kα radiation (λ=1.54 Å) to reveal the crystallographic structure of the samples. The morphology and microstructure were investigated using field emission scanning electron microscope (SEM) and transmission electron microscope (TEM). Raman spectra was used to analyse the state of carbon atoms. N2 adsorption–desorption curves were recorded on a Quad-rasorb-SI instrument and the specific surface area was examined by the Brunauer–Emmett–Teller (BET) process. Thermogravimetric analysis (TG) was carried out in N2 using a Netzsch TG thermal gravimetric analyzer, the sample was heated from 50 ℃ to 900 ℃ at 10 ℃ min−1. The magnetic properties were measured by vibrating sample magnetometer (VSM, Lake Shore7307) with a maximum field of 15 kOe. Microwave absorption properties were measured using vector network analyzer Agilent PNA N5224A from 2 to 18 GHz, by the coaxial-line method, in which the samples were pressed
7
into coaxial rings (Φout: 7.0 mm, Φin: 3.04 mm) after uniformly dispersing in paraffin with a weight proportion of 25%.
Scheme 1. The forming process of Fe@NPC@CF composites. 3. RESULTS AND DISCUSSION
8
Fig. 1. (a) XRD patterns (b) TG curves of the Fe-MOF/cotton precursor (c) Hysteresis loop of S500, S550 and S600 measured at room temperature (d) N2 adsorption-desorption isotherms of S500, S550 and S600. In order to prepare the Fe@NPC@CF nanocomposites, the TG curve of Fe-MOF/cotton precursor was investigated (Fig. 1(a)). It was shown that there were three stages during the heating process. In the initial stage, when the temperature range was below 130 ℃, little mass loss was characterized which could be attributed to evaporation of water. Then, in the range of 130~255 ℃, there was some mass loss because of the initial decomposition of cotton. However, the main mass loss occurred in the temperature range of 255~500 ℃. In this stage, the mass lost very 9
sharply and significantly because of the carbon-cotton burning. Most products of the CFs were formed at this stage and the total decomposition of Fe-MOF also happened. The weight loss caused by thermal decomposition in range of 20~130 ℃, 130~255 ℃ and 255~500 ℃ were 10%, 15% and 54%, respectively. Considering the TG behavior of Fe-MOF/Cotton, the thermal treatment was selected between 500 ℃ and 600 ℃. XRD was carried out to investigate the crystallographic structure of the obtained products. Fig. 1(b) revealed the XRD patterns of S500, S550, S600, which originated from the Fe-MOF/cotton composites under different annealing temperatures. S500 contained Fe3O4 as a main magnetic phase, while S550 and S600 consisted of carbon and Fe. For the sample of S500, there were three principal diffraction peaks ((220), (311), (440)) (JCPDS No.: 75-0449) which were indexed to Fe3O4 phase. On the other hand, the diffraction peaks of S550, S600 made it simple to assert the existence of Fe phase ((110), (200), (211)) (JCPDS No.: 87-0722). In addition, the enhanced peak intensity of the amorphous carbon at 26.5° could be ascribed to the increasing temperature of the heating treatment [48]. To further compare their component, TG curves under N2 atmosphere of the above three samples was presented in the Fig. S1 (a-1, b-1, c-1). The remaining content of S500 under the same condition was higher than that of the other two samples, which indicated the existence of the element oxygen in S500.
10
Fig. 1(c) showed magnetic hysteresis loops of the nanocomposites. The value of saturation magnetizations (MS) influenced the magnetic loss by contributing to high complex permeability. First, the magnetic phase in S500 was Fe3O4, which has smaller magnetic moment than Fe particles in S550 and S600. So the Ms of S500 was the smallest of the three samples. Then, the increase in MS with increasing treatment temperatures for the samples S550 and S600 was mainly ascribed to the decreased spin disorder on the particle surface as a result of increasing crystal size [49]. In addition, the coercivity ( are quite low and the
) values of the samples
for S500, S550, S600 were 200 Oe, 370 Oe, 370 Oe
respectively. Brunauer-Emmett-Teller (BET) test was carried out to inspect the porous character of the products [50]. As shown in Fig. 1(d), S550 demonstrated a typical IV isotherm with a distinct hysteresis loop at the P/P0 range of 0.4-1.0, indicating the existence of mesopores [51]. The specific surface areas of the three samples were approximately 156.80 cm2/g, 344.84 cm2/g and 388.19 cm2/g respectively. The specific surface area for final products increased as the carbonization temperature advanced, which could be noticed apparently. In addition, according to Barrett-Joyner-Halenda (BJH), the total pore volume of S550 was around 0.36 cm3/g with an average pore diameter of 3.8 nm (Fig. S2). Thus, the porous structure extended the transmission path of EM wave due to the large specific 11
surface area and total pore volume, which facilitated the EM wave absorption capability [52].
Fig. 2. SEM images of (a) S500 and (b) 550, (c) S600 (d, e) elemental mapping of S550.
12
Fig. 3. TEM images of (a) S550 (b, c, d) nanoparticles in S500, S550 and S600 respectively. The morphology of the three samples was characterized by SEM and TEM. As shown in Fig. 2 (a, b, c), the NPCs which originated from Fe-MOFs were distributed around the CF with some degrees of collapse, because of the long heating time. Some NPCs had an octahedral-like morphology which inherited from Fe-MOF. The EDS mapping of S550 in Fig. 2 (d, e) reflected the even distribution of C and Fe. Further, the element analysis was shown in Fig. S1 (a-2, b-2, c-2). From Fig.3, it can be observed that the nanoparticles were precipitated from Fe-MOF and dispersed in carbon matrix. Therefore, it could be concluded that the ferromagnetic nanoparticles@NPC@CF composites were successfully obtained.
Fig. 4. Raman spectra of S500, S550 and S600. Raman spectra was used to detect the state of carbon atoms and shown in Fig. 4. The two typical peaks in Fig. 4 were referred to the D band（1345 cm−1）and the G 13
band (1587 cm−1) respectively. The D band represented the disordered carbon while the G band represented the graphite layer. Thus, the ratio of D band to G band (ID/IG) was calculated to characterize the degree of graphitization [53]. The ratio of S500, S550, S600 were around 0.90, 0.75, 0.72, respectively. The ID/IG value declined with the increase of the temperature, which suggested that the degree of graphitization was improved. Therefore, the improved graphitization degree would be beneficial for increasing the carbon conductivity and promoting the EM wave absorption [54].
Fig. 5. The electromagnetic wave reflection loss with various thicknesses of 3 D representation for (a-1) S500 (b-1) S550 (c-1) S600. (a-2, b-2, c-2) corresponding 2 D contour map.
14
EM wave absorption properties are the most important factors which decide the application of the absorbing material. Generally, the characteristics of the final product rely on the reflection loss (RL) value, in which the RL value is below -10 dB, indicating that over 90% of the EM waves are absorbed [55]. The RL value could be calculated based on the following formulas [56]: =
(
= 20log ,
/ )
/
tanℎ [ (2
&'( )&*
%
&'( +&*
/ )×(
∙
)
/
]
(1)
%
(2)
, are the free space impedance, input impedance of the absorber,
respectively. f, d and c represent frequency of electromagnetic wave, absorber thickness, and the light speed, respectively. permittivity and
=
-
−
--
=
-
−
--
is the complex
is the complex permeability. Fig. 5 showed the RL
values of the three samples with various thicknesses. The absorbing properties of S500 revealed that this sample was not suitable for absorbing applications. S550 was demonstrated to have the EM absorbing properties with RL value below -10 dB in the range of 5-18 GHz, in which a RLmin of -46.2 dB at 13.6 GHz with a wide absorbing bandwidth of 5.2 GHz (RL<-10 dB) at a matching thickness of 2.5 mm and a low filling ratio of 25% was achieved. In addition, the S600 exhibited a RLmin of -18.7 dB with a matching thickness of 1.5 mm and the absorption
bandwidth (RL<-10 dB) of 4.2 GHz covering from 12.0 to 16.2 GHz range. Hence, the EM wave absorption could be tailored by the heat treatment process. In 15
addition, the EM absorbing properties of other filler loading of 20% and 30% which was named with S1 and S2 respectively, were measured in Fig. S3, in order to obtain the optimal sample. As Fig .S3 revealed, both the samples showed worse properties than S550 which was at a filling ratio of 25%. Compared with other composites in Table 1, the low filling ratio of the material in this work was blazing due to the low density, while the RL value, frequency range and thickness also demonstrated excellently. In addition, the biomass origin made it more qualified to be a green and high-efficient absorber than common composites. Table 1 Comparison of the EM wave absorbing properties with other composites Sample
RLmin (dB)
d (mm)
CoFe2O4/rGO Porous carbon Flower-like NiO CoS2@MoS2 /rGO Co0.8Fe2.2O4/rGO Fe@NPC@CF
-56.8 −42.4 -55.6 -58 -51.2 -46.2
1.96 2 7 2.4 2.1 2.5
Frequency range (RL<-10 dB, GHz) 6.8 1.76 2.7 5.52 7.2 5.2
16
Filling ratio (wt%) 50 70 30 20 50 25
Ref. [57] [58] [59] [60] [61] This work
Fig. 6. The complex permittivity, complex permeability, dielectric loss and magnetic loss tangents of (a-1, a-2, a-3) S500, (b-1, b-2, b-3) S550 and (c-1, c-2, c-3) S600 composites. It is well known that the EM wave absorption properties are tightly connected with the complex permittivity ( ) and complex permeability ( materials, where the real parts (
-
and
EM energy, while imaginary parts (
-
) of the absorbing
) is the symbol of the storage capacity of
--
and
--
) evaluate the EM dissipation
capacity [62]. On the one hand, the dielectric loss influenced by the polarization ability including the interfacial polarization and dipolar polarization. The porous character of the material greatly enhanced the interfacial polarization between the 17
nanoparticles and the pores, and improved the dipolar polarization provided by nanoporous carbon [39, 63]. As shown in Fig. 6, S500 had the lowest values of and
--
-
. In addition, the two curves had no obvious fluctuations. Thus, there was
no doubt that S500 was not suitable for EM wave absorption, because the low complex permittivity indicated great wave-transparent capability but terrible dissipated behavior [47]. The complex permittivity of S550 raised and between 5.1~9.2 while
--
-
was
was in the range of 2.1~4.2. This could be explained
according to the results of the Raman test. With the increasing heating temperature, the graphitization degree of the samples was enhanced, which increased the complex permittivity. Thus, it contributed to the impedance matching behavior and the excellent dielectric attenuated capability [64]. In addition, for S600, its ε′ (10.2~21.5) and ε″ (2.4~8.5) values were higher than that of the S550. The high complex permittivity would result in reflected EM waves from the absorbing surface because of impedance mismatch. Consequently, the absorbing performance of the S600 was inferior to that of the S550. Ordinarily, the complex permeability could be described as [65]: 1
-
= 1 + ( 2 )cos5
(3)
--
= 1 + ( 2 )sin5
(4)
1
where M is the magnetization, H is the intensity of the external magnetic field, 5 is the phase lag angle of the magnetization behind the external magnetic field. 18
High magnetization contributes to high complex permeability which influenced the magnetic loss deeply. It could be observed that the value of
-
and
--
of S600
was higher than S550. The magnetic loss is commonly decided by eddy current, magnetic hysteresis, and magnetic aftereffect loss. In gigahertz frequency, the magnetic aftereffect, especially magnetic resonance, which is mainly divided into natural resonance (2–10 GHz) and exchange resonance (>10 GHz) does main effect [66-68]. Generally, the magnetic loss tangent (789: = dielectric loss tangent (789 =
--
--
/ - ) and the
/ - ) were calculated to further evaluate the
magnetic and dielectric loss property [69, 70]. In Fig. 6, it could be seen that, comparing with that in S500, the dielectric loss played a more important role than the magnetic loss in S550 and S600. Based on this, the enhancement of the EM wave absorption performance of S550 and S600 was mainly ascribed to the dielectric loss [71]. An important mechanism for dielectric loss material to absorb EM wave arises from the Debye dipolar relaxation process. The complex permittivity
is
described as [62]: =
;
+
<= )<>
+? @AB
In this formula,
= C,
-
−
;,
--
(5)
f, D are the static permittivity, relative permittivity at
high-frequency limit, frequency, and polarization relaxation time, respectively. -
and
--
can be associated with the equations [35]: 19
=
--
;
=
+
<=E <>
(6)
+( @A)F B F
@AB(<= )<> )
(7)
+( @A)F B F
According to Equations (1) and (5), the (
-
−
<= )<>
) +(
--
) =(
<= )<>
-
)
and
--
can be written as:
(8)
Fig. 7. The relationship between real part ( - ) and imaginary part (
--
) of (a) S500,
(b) S550 and (c) S600 composites. Thus, the plot of
--
versus
-
would be a single semicircle, which can be
defined as the Cole–Cole semicircle [72]. Fig. 7 showed the curves of the versus
-
--
for the S500, S550 and S600 composites. Cole-Cole curve of S550
sample showed many distorted semicircles which implied Debye dipolar relaxations. Additionally, the conductive loss due to the generation of conductive current was another key point affecting their dielectric loss, which can be decided by the line tail in their Cole-Cole curves. The tail became long as the heating temperature increased, which indicated that the conductive loss was enhanced [73]. It could be inferred, the extent of the graphitization determines the dielectric loss properties, by providing with highly conductive matrix which ensures a high ε″ 20
value and strong conduction loss. Especially, it should be noted that the porous structure of the composites not only facilitates the scattering of incident EM waves but also increases dipole amount which further strengthens the interfacial polarization. In addition, there are two crucial parameters affecting EM wave absorbing performance, including impedance matching and attenuation constant [74]. In detail, a delta-function method is further proposed to evaluate the impedance matching degree by the following equations [25]. ∣ ∆∣=∣ sinℎ (I
)−J∣
(9)
where K and M can be calculated by relative complex permittivity and complex permeability respectively, as shown below. I =
R TR K@LMN
J =
F
×VWOXS ×VWOXU
(10)
KMN VWOXS ×
R ER (MN VWOXS )
(11)
Fig. 8. Calculated delta value maps of (a) S500, (b) S550 and (c) S600 composites.
21
A small delta value with a large area (close to zero) (|∆| <0.5) indicates an excellent impedance matching degree. As shown in Fig. 8, S550 and S600 composites possessed larger area of close to zero than S500, which revealed that a better impedance matching was achieved in S550 and S600 composites. On the other hand, the EM wave is supposed to be attenuated inside the absorbing material as much as possible. Therefore, the attenuation constant α can be calculated [75]: α=
√
](
-- --
−
- -)
+ L(
-- --
−
- -)
+(
-- -
+
- -- )
(12)
where f is the frequency and c is the velocity of light. As shown in Fig. 9, the attenuation of S500 was very low in the frequency range of 2-18 GHz. In addition, the S550 and S600 composites was proved to have a higher α than that of the S500, suggesting the better attenuation was achieved for S550 and S600 composites. Therefore, according to the EM wave absorption mechanism revealed in Fig. 10, the combination of the optimized impedance matching and enhanced attenuation capability contributed to the improvement of the EM wave absorbing performance.
22
Fig. 9. Attenuation constant (α) of S500, S550 and S600 composites.
Fig. 10. Schematic illustration of the EM wave absorption mechanism. 4. CONCLUSIONS In summary, using the precursor materials of biomass cotton, we demonstrated a quick and facile strategy to fabricate the Fe@nanoporous carbon@carbon fiber (Fe@NPC@CF) nanocomposites by the microwave assisted in-situ rapid synthesis and thermal 23
decomposition processes. A strong minimum reflection loss (RLmin) of -46.2 dB and a wide absorbing bandwidth of 5.2 GHz (RL<-10 dB) with a matching thickness of 2.5 mm were achieved for the Fe@NPC@CF composites with a low filling ratio of 25%. The excellent EM absorption performances of the composites were ascribed to the designed constitution and structure, which contributed to the impedance matching and attenuation based on the cooperation of dialectic loss and magnetic loss. Also, the porous characteristic of the material extended the transmission path of EM wave and facilitated the absorption. Therefore, the current investigation demonstrated that sustainable biomass derived material has a huge potential for the application in EM wave absorbing field. ACKNOWLEDGMENTS This project was supported by the National Natural Science Foundation of China (No 51671146,), the Program of Shanghai Technology Research Leader (18XD1423800 and the Fundamental Research Funds for the Central Universities (22120180096) REFERENCES [1] S. Ni, X. Wang, G. Zhou, F. Yang, J. Wang, D. He, Designed synthesis of wide range microwave absorption Fe3O4–carbon sphere composite, Journal of Alloys and Compounds 489(1) (2010) 252-256. [2] Z. Yang, Y. Wan, G. Xiong, D. Li, Q. Li, C. Ma, R. Guo, H. Luo, Facile synthesis of ZnFe2O4/reduced graphene oxide nanohybrids for enhanced microwave absorption properties, Materials Research Bulletin 61 (2015) 292-297.
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·Strong reflection loss of -46.2 dB and wide absorbing bandwidth of 5.2 GHz with matching thickness of 2.5 mm
·Biomass material using cotton as precursor : green, low-cost and renewable ·Microwave assisted in-situ rapid synthesis ·Light weight with low filling ratio of only 25%
Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
S0925-8388(19)34198-2
DOI:
https://doi.org/10.1016/j.jallcom.2019.152952
Reference:
JALCOM 152952
To appear in:
Journal of Alloys and Compounds
Received Date: 18 August 2019 Revised Date:
3 November 2019
Accepted Date: 7 November 2019
Please cite this article as: X. Li, E. Cui, Z. Xiang, L. Yu, J. Xiong, F. Pan, W. Lu, Fe@NPC@CF nanocomposites derived from Fe-MOFs/biomass cotton for lightweight and high-performance electromagnetic wave absorption applications, Journal of Alloys and Compounds (2019), doi: https:// doi.org/10.1016/j.jallcom.2019.152952. This is a PDF file of an article that has undergone enhancements after acceptance, such as the addition of a cover page and metadata, and formatting for readability, but it is not yet the definitive version of record. This version will undergo additional copyediting, typesetting and review before it is published in its final form, but we are providing this version to give early visibility of the article. Please note that, during the production process, errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain. © 2019 Published by Elsevier B.V.
Graphical Abstract
Fe@NPC@CF nanocomposites exhibited an excellence electromagnetic absorption performance due to the synergistic effects of the magnetic and dielectric loss among Fe nanoparticles, NPC and CF.
Fe@NPC@CF nanocomposites derived from Fe-MOFs/Biomass Cotton for lightweight and high-performance Electromagnetic Wave Absorption applications Xiang Lia, Erbiao Cuia, Zhen Xiangb, Lunzhou Yua, Juan Xiongb, Fei Panb, and Wei Lub,∗ a
School of Materials Science & Engineering, University of Shanghai for Science and
Technology, Shanghai 200093, China b
Shanghai Key Lab. of D&A for Metal-Functional Materials, School of Materials
Science & Engineering, Tongji University, Shanghai 201804, China. *Corresponding author. E-mail address: [email protected] (Wei Lu). ABSTRACT Electromagnetic (EM) wave absorbing materials have been extensively applied in the electronic devices and wireless communication to solve the increasingly serious problems of electromagnetic pollution and radiation. In this work, Fe-MOFs/biomass cotton derived Fe@nanoporous carbon@carbon fiber (Fe@NPC@CF) composites were successfully obtained by means of in-situ synthesis and thermal decomposition processes. It was found that the Fe@NPC composites were uniformly distributed on the carbon fibers matrix. As a result, EM wave absorbing performances were greatly promoted via the synergic effects among Fe nanoparticles, nanoporous carbon and carbon fibers. A strong reflection loss (RL) of -46.2 dB and a wide absorbing bandwidth of 5.2 GHz (RL<-10 dB) with a matching thickness of 2.5 mm were achieved for the Fe@NPC@CF 1
composites with a low filling ratio of 25%. Therefore, this work not only paved the way for development of biomass as a green, low-cost and renewable high-performance carbon-based absorber, but also provided a good design and fabricating concept for the composite materials of EM wave absorber. Keywords: MOFs, biomass cotton, Fe@NPC, carbon fiber, synergic effect, electromagnetic wave absorption 1. INTRODUCTION With the rapid development of wireless communication and electronic technology, electromagnetic pollution problems such as electromagnetic radiation and electromagnetic interference have attracted much attention [1-5]. Accordingly, an efficient electromagnetic wave absorbing materials to solve above serious issues should satisfy four characteristics: strong adsorption, broad bandwidth, lightweight, and thin thickness [6-10]. It is well-known that the traditional electromagnetic wave absorbing materials such as dielectric materials [11-13] and magnetic materials [14, 15] have been applied to the field of EM wave absorption. However, there is much space for the improvement in the performance of EM wave absorbing materials. For magnetic materials, the high density, large thickness, and narrow absorbing bandwidth limit its practical applications. For dielectric materials, its application was restricted by the poor impedance matching derived from relatively high complex permittivity and low permeability [16]. 2
Therefore, the composites with dielectric material and magnetic material can realize the fantastic performance of EM wave absorption [17-22], such as Fe3O4/MWCNTs [23], Ni/C [24] and Co/C [25]. In addition to material composition, a reasonable material structure is also a key factor for the superior EM absorption performance [26], including core-shell structure, porous structure and so on [27]. Among them, the porous carbon materials are considered to be a novel EM absorbing materials due to the well-matched impedance [28-31]. For instance, porous flower-like NiO@graphene composites prepared by Wang et al exhibited excellent EM absorbing properties with minimum reflection loss (RLmin) of -59.6 dB at 14.2 GHz, and the absorption bandwidths (RL <-10 dB) ranged from 12.5 GHz to 16.7 GHz with a thickness of only 1.7 mm [32]. Feng et al fabricated the porous FeNi3/N-GN composites with a RLmin of -57.2dB with an ultrathin thickness of only 1.45 mm and the corresponding effective bandwidth is larger than 3.4 GHz (14.6–18 GHz) [33]. Nevertheless, there is still a difficulty in simultaneously controlling the material composition and microstructure to achieve excellent EM wave absorbency. Fortunately, Metal-organic frameworks (MOFs) consist of nanopores and open channels have been regarded as the ideal precursor for nanoporous carbon materials with homogeneous atomic distribution [34, 35]. Moreover, the EM absorbing materials with magnetic nanoparticles adhered to porous carbon matrix 3
have been synthesized by the thermal decomposition of MOFs precursor [36]. For example, Zhang et al reported the Ni@C composite derived from MOFs, reached to -55.7 dB corresponding to 6.0 GHz absorption bandwidth (<−10 dB) with a thickness of 1.85 mm [37]. Yuan et al reported MOFs derived carbonaceous Co3O4/Co/RGO composite with a RLmin of -52.8 dB at 13.2 GHz with a thickness of 2 mm [38]. In our previous work, the RL value of porous Fe3O4@NPC composites derived from Fe-MOFs reached to -65.5 dB, with a matching thickness of 3 mm and a wide frequency bandwidth (4.5 GHz) [39]. The carbonized product forms nanoporous carbon with a large porosity and specific surface area. The low density of porous carbon meets the requirements of light absorbers. Its rich pore structure provides abundant active reflection sites inside the material for EM waves. At the same time, a good conductive network is formed, and the EM wave energy is finally dissipated in the form of Joule heat. Taking account of the amorphous characteristics of the MOFs-derived porous carbon, the enhancement of the dielectric loss by increasing conductivity is required [40-44]. Among the dielectric materials, biomass cotton due to its availability, high specific surface areas, functional groups, and low density, has been used to enhance the microwave attenuation performances. For instance, Li et al. successfully prepared Co/C fibers by using low-cost biomass cotton as carbon source with RL values below -10 dB in the frequency range of 11.3-18 GHz, 4
which covered the whole Ku-band (12 ~ 18 GHz) [45]. Wei et al prepared waste-cotton
derived
porous
carbon,
combined
with well-dispersed
Ni
nanoparticles with excellent microwave absorption properties (RL＜-20 dB) exhibiting in very broad frequency ranges (2.0 to 8.8 GHz and 10.9 to 18 GHz) [46]. Recently, Zhao et al fabricated carbon-cotton/Co@nanoporous carbon composites with the optimal reflection loss of -51.2 dB and a broad bandwidth of 4.4 GHz [47]. Despite some related reports on biomass cotton derived absorbing material, achieving an excellent EM wave absorbency and obtaining the absorber via a simple way is still an urgent problem. Herein, we fabricated Fe-MOFs/biomass cotton derived Fe@nanoporous carbon@carbon fiber (Fe@NPC@CF) composites in a way of microwave assisted in-situ rapid synthesis and thermal decomposition processes. It was found the materials were well combined with the Fe@NPC composites evenly dispersed on the carbon fiber. The composites showed strong EM absorption properties: a strong minimum reflection loss (RLmin) of -46.2 dB, a wide absorbing bandwidth of 5.2 GHz (RL<-10 dB) with a matching thickness of 2.5 mm and a low filling ratio of 25%. The EM absorbing mechanism can be ascribed to the synergy effects among the internal materials and the good impedance matching caused by the dielectric loss and magnetic loss. Thus, this work not only paved the way for development of biomass as a green, low-cost and renewable high-performance 5
carbon-based absorber, but also provided a good design and fabricating concept for the composite materials of EM wave absorber. 2. EXPERIMENTAL DETAILS 2.1 Materials Pristine cottons, hydrogen peroxide(H2O2), sodium silicate (Na2SiO3), sodium hydroxide (NaOH), N,N-dimethylformamide (DMF), ferric chloride hexahydrate (FeCl3· 6H2O), and 1, 4-benzenedicarboxylic acid (H2BDC). All of them were obtained from Shanghai Aladdin Industrial Corporation. 2.2 Fabrication of Fe@NPC@CF composites The schematic fabricating process of Fe@NPC@CF composites is shown in scheme 1. First, pristine cottons were activated. 0.8 g cottons were immersed into the mixture solution (270 ml) which contains H2O2 (2 mol/L), 1.08 g Na2SiO3 and 2.7 g NaOH. The treatment was undergoing at 90 ℃ for 1 h. After that the product obtained was purified and dried in a vacuum at 60 ℃ for 48 h. The fabrication of Fe-MOF/cotton composites is listed as following: FeCl3· 6H2O (1.990 g, 7.36 mmol) and H2BDC (1.224 g, 7.36 mmol) were dissolved in DMF (160 mL, 2.08 mol) , with magnetic stirring for 30 min .Then the activated cottons were immersed into the solution with sonication for 2 h before the microwave heating at 140 ℃, for 6 min. After that, by vacuum 6
filtration, the product was assembled and washed with ethanol, and finally dried at 60 ℃ for 48 h. In order to get Fe@NPC@CF composites, the heating treatments of Fe-MOF/cotton composites were carried out at 500 ℃, 550 ℃, 600 ℃ for 2 h in Ar atmosphere. The final products were named S500, S550 and S600, respectively. 2.3 Characterization X-ray diffraction (XRD) was performed by using Cu-Kα radiation (λ=1.54 Å) to reveal the crystallographic structure of the samples. The morphology and microstructure were investigated using field emission scanning electron microscope (SEM) and transmission electron microscope (TEM). Raman spectra was used to analyse the state of carbon atoms. N2 adsorption–desorption curves were recorded on a Quad-rasorb-SI instrument and the specific surface area was examined by the Brunauer–Emmett–Teller (BET) process. Thermogravimetric analysis (TG) was carried out in N2 using a Netzsch TG thermal gravimetric analyzer, the sample was heated from 50 ℃ to 900 ℃ at 10 ℃ min−1. The magnetic properties were measured by vibrating sample magnetometer (VSM, Lake Shore7307) with a maximum field of 15 kOe. Microwave absorption properties were measured using vector network analyzer Agilent PNA N5224A from 2 to 18 GHz, by the coaxial-line method, in which the samples were pressed
7
into coaxial rings (Φout: 7.0 mm, Φin: 3.04 mm) after uniformly dispersing in paraffin with a weight proportion of 25%.
Scheme 1. The forming process of Fe@NPC@CF composites. 3. RESULTS AND DISCUSSION
8
Fig. 1. (a) XRD patterns (b) TG curves of the Fe-MOF/cotton precursor (c) Hysteresis loop of S500, S550 and S600 measured at room temperature (d) N2 adsorption-desorption isotherms of S500, S550 and S600. In order to prepare the Fe@NPC@CF nanocomposites, the TG curve of Fe-MOF/cotton precursor was investigated (Fig. 1(a)). It was shown that there were three stages during the heating process. In the initial stage, when the temperature range was below 130 ℃, little mass loss was characterized which could be attributed to evaporation of water. Then, in the range of 130~255 ℃, there was some mass loss because of the initial decomposition of cotton. However, the main mass loss occurred in the temperature range of 255~500 ℃. In this stage, the mass lost very 9
sharply and significantly because of the carbon-cotton burning. Most products of the CFs were formed at this stage and the total decomposition of Fe-MOF also happened. The weight loss caused by thermal decomposition in range of 20~130 ℃, 130~255 ℃ and 255~500 ℃ were 10%, 15% and 54%, respectively. Considering the TG behavior of Fe-MOF/Cotton, the thermal treatment was selected between 500 ℃ and 600 ℃. XRD was carried out to investigate the crystallographic structure of the obtained products. Fig. 1(b) revealed the XRD patterns of S500, S550, S600, which originated from the Fe-MOF/cotton composites under different annealing temperatures. S500 contained Fe3O4 as a main magnetic phase, while S550 and S600 consisted of carbon and Fe. For the sample of S500, there were three principal diffraction peaks ((220), (311), (440)) (JCPDS No.: 75-0449) which were indexed to Fe3O4 phase. On the other hand, the diffraction peaks of S550, S600 made it simple to assert the existence of Fe phase ((110), (200), (211)) (JCPDS No.: 87-0722). In addition, the enhanced peak intensity of the amorphous carbon at 26.5° could be ascribed to the increasing temperature of the heating treatment [48]. To further compare their component, TG curves under N2 atmosphere of the above three samples was presented in the Fig. S1 (a-1, b-1, c-1). The remaining content of S500 under the same condition was higher than that of the other two samples, which indicated the existence of the element oxygen in S500.
10
Fig. 1(c) showed magnetic hysteresis loops of the nanocomposites. The value of saturation magnetizations (MS) influenced the magnetic loss by contributing to high complex permeability. First, the magnetic phase in S500 was Fe3O4, which has smaller magnetic moment than Fe particles in S550 and S600. So the Ms of S500 was the smallest of the three samples. Then, the increase in MS with increasing treatment temperatures for the samples S550 and S600 was mainly ascribed to the decreased spin disorder on the particle surface as a result of increasing crystal size [49]. In addition, the coercivity ( are quite low and the
) values of the samples
for S500, S550, S600 were 200 Oe, 370 Oe, 370 Oe
respectively. Brunauer-Emmett-Teller (BET) test was carried out to inspect the porous character of the products [50]. As shown in Fig. 1(d), S550 demonstrated a typical IV isotherm with a distinct hysteresis loop at the P/P0 range of 0.4-1.0, indicating the existence of mesopores [51]. The specific surface areas of the three samples were approximately 156.80 cm2/g, 344.84 cm2/g and 388.19 cm2/g respectively. The specific surface area for final products increased as the carbonization temperature advanced, which could be noticed apparently. In addition, according to Barrett-Joyner-Halenda (BJH), the total pore volume of S550 was around 0.36 cm3/g with an average pore diameter of 3.8 nm (Fig. S2). Thus, the porous structure extended the transmission path of EM wave due to the large specific 11
surface area and total pore volume, which facilitated the EM wave absorption capability [52].
Fig. 2. SEM images of (a) S500 and (b) 550, (c) S600 (d, e) elemental mapping of S550.
12
Fig. 3. TEM images of (a) S550 (b, c, d) nanoparticles in S500, S550 and S600 respectively. The morphology of the three samples was characterized by SEM and TEM. As shown in Fig. 2 (a, b, c), the NPCs which originated from Fe-MOFs were distributed around the CF with some degrees of collapse, because of the long heating time. Some NPCs had an octahedral-like morphology which inherited from Fe-MOF. The EDS mapping of S550 in Fig. 2 (d, e) reflected the even distribution of C and Fe. Further, the element analysis was shown in Fig. S1 (a-2, b-2, c-2). From Fig.3, it can be observed that the nanoparticles were precipitated from Fe-MOF and dispersed in carbon matrix. Therefore, it could be concluded that the ferromagnetic nanoparticles@NPC@CF composites were successfully obtained.
Fig. 4. Raman spectra of S500, S550 and S600. Raman spectra was used to detect the state of carbon atoms and shown in Fig. 4. The two typical peaks in Fig. 4 were referred to the D band（1345 cm−1）and the G 13
band (1587 cm−1) respectively. The D band represented the disordered carbon while the G band represented the graphite layer. Thus, the ratio of D band to G band (ID/IG) was calculated to characterize the degree of graphitization [53]. The ratio of S500, S550, S600 were around 0.90, 0.75, 0.72, respectively. The ID/IG value declined with the increase of the temperature, which suggested that the degree of graphitization was improved. Therefore, the improved graphitization degree would be beneficial for increasing the carbon conductivity and promoting the EM wave absorption [54].
Fig. 5. The electromagnetic wave reflection loss with various thicknesses of 3 D representation for (a-1) S500 (b-1) S550 (c-1) S600. (a-2, b-2, c-2) corresponding 2 D contour map.
14
EM wave absorption properties are the most important factors which decide the application of the absorbing material. Generally, the characteristics of the final product rely on the reflection loss (RL) value, in which the RL value is below -10 dB, indicating that over 90% of the EM waves are absorbed [55]. The RL value could be calculated based on the following formulas [56]: =
(
= 20log ,
/ )
/
tanℎ [ (2
&'( )&*
%
&'( +&*
/ )×(
∙
)
/
]
(1)
%
(2)
, are the free space impedance, input impedance of the absorber,
respectively. f, d and c represent frequency of electromagnetic wave, absorber thickness, and the light speed, respectively. permittivity and
=
-
−
--
=
-
−
--
is the complex
is the complex permeability. Fig. 5 showed the RL
values of the three samples with various thicknesses. The absorbing properties of S500 revealed that this sample was not suitable for absorbing applications. S550 was demonstrated to have the EM absorbing properties with RL value below -10 dB in the range of 5-18 GHz, in which a RLmin of -46.2 dB at 13.6 GHz with a wide absorbing bandwidth of 5.2 GHz (RL<-10 dB) at a matching thickness of 2.5 mm and a low filling ratio of 25% was achieved. In addition, the S600 exhibited a RLmin of -18.7 dB with a matching thickness of 1.5 mm and the absorption
bandwidth (RL<-10 dB) of 4.2 GHz covering from 12.0 to 16.2 GHz range. Hence, the EM wave absorption could be tailored by the heat treatment process. In 15
addition, the EM absorbing properties of other filler loading of 20% and 30% which was named with S1 and S2 respectively, were measured in Fig. S3, in order to obtain the optimal sample. As Fig .S3 revealed, both the samples showed worse properties than S550 which was at a filling ratio of 25%. Compared with other composites in Table 1, the low filling ratio of the material in this work was blazing due to the low density, while the RL value, frequency range and thickness also demonstrated excellently. In addition, the biomass origin made it more qualified to be a green and high-efficient absorber than common composites. Table 1 Comparison of the EM wave absorbing properties with other composites Sample
RLmin (dB)
d (mm)
CoFe2O4/rGO Porous carbon Flower-like NiO CoS2@MoS2 /rGO Co0.8Fe2.2O4/rGO Fe@NPC@CF
-56.8 −42.4 -55.6 -58 -51.2 -46.2
1.96 2 7 2.4 2.1 2.5
Frequency range (RL<-10 dB, GHz) 6.8 1.76 2.7 5.52 7.2 5.2
16
Filling ratio (wt%) 50 70 30 20 50 25
Ref. [57] [58] [59] [60] [61] This work
Fig. 6. The complex permittivity, complex permeability, dielectric loss and magnetic loss tangents of (a-1, a-2, a-3) S500, (b-1, b-2, b-3) S550 and (c-1, c-2, c-3) S600 composites. It is well known that the EM wave absorption properties are tightly connected with the complex permittivity ( ) and complex permeability ( materials, where the real parts (
-
and
EM energy, while imaginary parts (
-
) of the absorbing
) is the symbol of the storage capacity of
--
and
--
) evaluate the EM dissipation
capacity [62]. On the one hand, the dielectric loss influenced by the polarization ability including the interfacial polarization and dipolar polarization. The porous character of the material greatly enhanced the interfacial polarization between the 17
nanoparticles and the pores, and improved the dipolar polarization provided by nanoporous carbon [39, 63]. As shown in Fig. 6, S500 had the lowest values of and
--
-
. In addition, the two curves had no obvious fluctuations. Thus, there was
no doubt that S500 was not suitable for EM wave absorption, because the low complex permittivity indicated great wave-transparent capability but terrible dissipated behavior [47]. The complex permittivity of S550 raised and between 5.1~9.2 while
--
-
was
was in the range of 2.1~4.2. This could be explained
according to the results of the Raman test. With the increasing heating temperature, the graphitization degree of the samples was enhanced, which increased the complex permittivity. Thus, it contributed to the impedance matching behavior and the excellent dielectric attenuated capability [64]. In addition, for S600, its ε′ (10.2~21.5) and ε″ (2.4~8.5) values were higher than that of the S550. The high complex permittivity would result in reflected EM waves from the absorbing surface because of impedance mismatch. Consequently, the absorbing performance of the S600 was inferior to that of the S550. Ordinarily, the complex permeability could be described as [65]: 1
-
= 1 + ( 2 )cos5
(3)
--
= 1 + ( 2 )sin5
(4)
1
where M is the magnetization, H is the intensity of the external magnetic field, 5 is the phase lag angle of the magnetization behind the external magnetic field. 18
High magnetization contributes to high complex permeability which influenced the magnetic loss deeply. It could be observed that the value of
-
and
--
of S600
was higher than S550. The magnetic loss is commonly decided by eddy current, magnetic hysteresis, and magnetic aftereffect loss. In gigahertz frequency, the magnetic aftereffect, especially magnetic resonance, which is mainly divided into natural resonance (2–10 GHz) and exchange resonance (>10 GHz) does main effect [66-68]. Generally, the magnetic loss tangent (789: = dielectric loss tangent (789 =
--
--
/ - ) and the
/ - ) were calculated to further evaluate the
magnetic and dielectric loss property [69, 70]. In Fig. 6, it could be seen that, comparing with that in S500, the dielectric loss played a more important role than the magnetic loss in S550 and S600. Based on this, the enhancement of the EM wave absorption performance of S550 and S600 was mainly ascribed to the dielectric loss [71]. An important mechanism for dielectric loss material to absorb EM wave arises from the Debye dipolar relaxation process. The complex permittivity
is
described as [62]: =
;
+
<= )<>
+? @AB
In this formula,
= C,
-
−
;,
--
(5)
f, D are the static permittivity, relative permittivity at
high-frequency limit, frequency, and polarization relaxation time, respectively. -
and
--
can be associated with the equations [35]: 19
=
--
;
=
+
<=E <>
(6)
+( @A)F B F
@AB(<= )<> )
(7)
+( @A)F B F
According to Equations (1) and (5), the (
-
−
<= )<>
) +(
--
) =(
<= )<>
-
)
and
--
can be written as:
(8)
Fig. 7. The relationship between real part ( - ) and imaginary part (
--
) of (a) S500,
(b) S550 and (c) S600 composites. Thus, the plot of
--
versus
-
would be a single semicircle, which can be
defined as the Cole–Cole semicircle [72]. Fig. 7 showed the curves of the versus
-
--
for the S500, S550 and S600 composites. Cole-Cole curve of S550
sample showed many distorted semicircles which implied Debye dipolar relaxations. Additionally, the conductive loss due to the generation of conductive current was another key point affecting their dielectric loss, which can be decided by the line tail in their Cole-Cole curves. The tail became long as the heating temperature increased, which indicated that the conductive loss was enhanced [73]. It could be inferred, the extent of the graphitization determines the dielectric loss properties, by providing with highly conductive matrix which ensures a high ε″ 20
value and strong conduction loss. Especially, it should be noted that the porous structure of the composites not only facilitates the scattering of incident EM waves but also increases dipole amount which further strengthens the interfacial polarization. In addition, there are two crucial parameters affecting EM wave absorbing performance, including impedance matching and attenuation constant [74]. In detail, a delta-function method is further proposed to evaluate the impedance matching degree by the following equations [25]. ∣ ∆∣=∣ sinℎ (I
)−J∣
(9)
where K and M can be calculated by relative complex permittivity and complex permeability respectively, as shown below. I =
R TR K@LMN
J =
F
×VWOXS ×VWOXU
(10)
KMN VWOXS ×
R ER (MN VWOXS )
(11)
Fig. 8. Calculated delta value maps of (a) S500, (b) S550 and (c) S600 composites.
21
A small delta value with a large area (close to zero) (|∆| <0.5) indicates an excellent impedance matching degree. As shown in Fig. 8, S550 and S600 composites possessed larger area of close to zero than S500, which revealed that a better impedance matching was achieved in S550 and S600 composites. On the other hand, the EM wave is supposed to be attenuated inside the absorbing material as much as possible. Therefore, the attenuation constant α can be calculated [75]: α=
√
](
-- --
−
- -)
+ L(
-- --
−
- -)
+(
-- -
+
- -- )
(12)
where f is the frequency and c is the velocity of light. As shown in Fig. 9, the attenuation of S500 was very low in the frequency range of 2-18 GHz. In addition, the S550 and S600 composites was proved to have a higher α than that of the S500, suggesting the better attenuation was achieved for S550 and S600 composites. Therefore, according to the EM wave absorption mechanism revealed in Fig. 10, the combination of the optimized impedance matching and enhanced attenuation capability contributed to the improvement of the EM wave absorbing performance.
22
Fig. 9. Attenuation constant (α) of S500, S550 and S600 composites.
Fig. 10. Schematic illustration of the EM wave absorption mechanism. 4. CONCLUSIONS In summary, using the precursor materials of biomass cotton, we demonstrated a quick and facile strategy to fabricate the Fe@nanoporous carbon@carbon fiber (Fe@NPC@CF) nanocomposites by the microwave assisted in-situ rapid synthesis and thermal 23
decomposition processes. A strong minimum reflection loss (RLmin) of -46.2 dB and a wide absorbing bandwidth of 5.2 GHz (RL<-10 dB) with a matching thickness of 2.5 mm were achieved for the Fe@NPC@CF composites with a low filling ratio of 25%. The excellent EM absorption performances of the composites were ascribed to the designed constitution and structure, which contributed to the impedance matching and attenuation based on the cooperation of dialectic loss and magnetic loss. Also, the porous characteristic of the material extended the transmission path of EM wave and facilitated the absorption. Therefore, the current investigation demonstrated that sustainable biomass derived material has a huge potential for the application in EM wave absorbing field. ACKNOWLEDGMENTS This project was supported by the National Natural Science Foundation of China (No 51671146,), the Program of Shanghai Technology Research Leader (18XD1423800 and the Fundamental Research Funds for the Central Universities (22120180096) REFERENCES [1] S. Ni, X. Wang, G. Zhou, F. Yang, J. Wang, D. He, Designed synthesis of wide range microwave absorption Fe3O4–carbon sphere composite, Journal of Alloys and Compounds 489(1) (2010) 252-256. [2] Z. Yang, Y. Wan, G. Xiong, D. Li, Q. Li, C. Ma, R. Guo, H. Luo, Facile synthesis of ZnFe2O4/reduced graphene oxide nanohybrids for enhanced microwave absorption properties, Materials Research Bulletin 61 (2015) 292-297.
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·Strong reflection loss of -46.2 dB and wide absorbing bandwidth of 5.2 GHz with matching thickness of 2.5 mm
·Biomass material using cotton as precursor : green, low-cost and renewable ·Microwave assisted in-situ rapid synthesis ·Light weight with low filling ratio of only 25%
Declaration of interests The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.