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polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties
Accepted Manuscript Original article Synthesis of Fe3O4/polypyrrole/polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties Bingzhen Li, Xiaodi Weng, Guojing Wu, Yang Zhang, Xuliang Lv, Guangxin Gu PII: DOI: Reference:
S1319-6103(16)30109-0 http://dx.doi.org/10.1016/j.jscs.2016.11.005 JSCS 847
To appear in:
Journal of Saudi Chemical Society
Received Date: Accepted Date:
3 October 2016 30 November 2016
Please cite this article as: B. Li, X. Weng, G. Wu, Y. Zhang, X. Lv, G. Gu, Synthesis of Fe3O4/polypyrrole/polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties, Journal of Saudi Chemical Society (2016), doi: http://dx.doi.org/10.1016/j.jscs.2016.11.005
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Synthesis of Fe3O4/polypyrrole/polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties Bingzhen Li a, Xiaodi Weng a, Guojing Wu d, Yang Zhang c, Xuliang Lv *, a, Guangxin Gu *, b a
Key laboratory of Science and Technology on Electromagnetic Effects and Electro-optical Engineering,
PLA University of Science & Technology, Nanjing 210007, PR China. b
Department of Materials Science, Fudan University, Shanghai, 200433, PR China.
c
Nantong Qiurun Nanotechnology Company, Nantong, 226001, PR China.
d
Wuxi joint logistics center, Wuxi, 214000, PR China.
* To whom the correspondence should be addressed. Email: [email protected] , [email protected] Corresponding author: Xuliang Lv at Key laboratory of Science and Technology on Electromagnetic Effects and Electro-optical Engineering, PLA University of Science & Technology, Nanjing 210007, PR China. Email: [email protected] , Phone number: 13851470758. Guangxin Gu at Department of Materials Science, Fudan University, Shanghai, 200433, PR China. Email: [email protected], Phone number: 13003150756 Key terms: nanocomposites; synthesis; electromagnetic property
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Synthesis of Fe3O4/polypyrrole/polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties Abstract Fe3O4/PPy/PANI (Fe3O4/polypyrrole/polyaniline) nanocomposites with excellent microwave absorbing properties have been successfully synthesized and characterized systematically. In detail, Fe3O4 nanoparticles were prepared via an environmental friendly, modified co-precipitation method. Afterward, two conductive polymers, PPy and PANI, were deposited onto the surface of Fe3O4 nanoparticles by in-situ polymerization of pyrrole and aniline. PPy and PANI was “glued” by the strong affinity between the carbonyl groups of PPy and the conjugated chains of PANI. The obtained Fe3O4/PPy/PANI nanocomposites have been found to possess excellent microwave absorbing property with the absorption bandwidth of 10.7 GHz (6.7 -17.4 GHz) and maximum reflection loss at 10.1 GHz (-40.2 dB). It proves that the combination of ultra-small Fe3O4 nanoparticles with two different conductive polymers have a great potential in the application of microwave absorbing materials.
Introduction Microwave absorbing materials have attracted increasing research attention in the past decades, due to their significant role in precise instrument application, promising application in military stealth technology and electromagnetic shielding technology for personal protection [1-4]. The key requirements of a good microwave absorbing material include wide absorption bandwidth, strong attenuation property, light weight, and thin thickness [5-7], which specifically demand remarkable magnetic loss or dielectric loss to attenuate the microwave energy, a good impedance match, adjustment of electromagnetic parameters combining kinds of losing principles and a relatively low density. [8, 9]However, these features are unlikely to occur in one single material: The impedance match is influenced by both the magnetic and electronic
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properties following a complex mechanism which make it extraordinary difficult to adjust; high magnetic loss often involve metal composites, making the density unnecessarily high; a better absorbing performance usually come with extra thickness. [10-12]Thus, composite materials that offer the chances to adjust the complex electromagnetic parameters and physical properties seem to be a rational way to realize these unique properties in the same time. Magnetic nanoparticles such as Fe3O4 has been widely used in microwave absorbing application and proved to provide significant magnetic loss property [13, 14]. However, the application of these particles are restricted by their narrow frequency range and relatively higher density [15]. Recent research progress indicates that the combination of lightweight conductive polymer with magnetic nanoparticles not only lower the density of the composites, but also brings benefits to the
electromagnetic properties
by introducing dielectric loss to the material system[16-21]. As typical conductive polymers, PANI and PPy both have high conductivity, low density, and also are easy to produce and reserve [22, 23]. Therefore, PANI and PPy have been employed in many microwave absorbing composites systems as organic binder, medium, or a coating layer of inorganic particles to improve materials’ dielectric loss and impedance matching property, which in turn enhanced materials’ microwave absorbing performance [24-26]. Sayed Hossein et al. synthesized PANI/MnFe2O4 nanocomposites with core-shell structure, achieving minimum reflection loss at 10.4 GHz of -15.3 dB with a thickness of 1.4 mm. The same group reported the synthesis of PPy/MnFe2O4 with core-shell structure and a minimum reflection loss of -12 dB at 11.3 GHz with the thickness of 1.5 mm[27]. Another core-shell structured Fe3O4@PANI nanoparticles with very thin PANI coating was reported by Sun et al with significantly enhanced microwave absorption property [17]. To our knowledge, there is still no report on the combination of two conductive polymer with magnetic nanoparticles till now, which we believe can potentially increase the complex permittivity and provide
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interfacial polarization that can further improve material systems’ microwave absorbing property. In this article, we have successfully synthesized a ternary nanocomposites Fe3O4/PPy/PANI via co-precipitation method and systematically investigated its application potential as a microwave absorbing material. The detailed synthesis route is demonstrated in Figure 1., Fe3O4 nanoparticles with grain size of approximately 15 nm were synthesized by co-precipitation method [28], which were used as the nucleation sites for the coating process of PPy on the surface of Fe3O4 via in situ polymerization. The abundant carbonyl groups on the surface of PPy have strong affinity to PANI, which ensures the further deposition of PANI on Fe3O4/PPy binary nanocomposite [15].
Methods Raw materials Ferric chloride hexahydrate(FeCl3•6H2O, AR), iron dichloride tetrahydrate (FeCl2•4H2O, AR), ammonium hydroxide (NH3•H2O, AR, 25-28%)，Sodium dodecyl benzene sulfonate (C18H29NaSO3, 95%) and pyrrole (C4H5N, CP) were purchased from Aladdin. Hydrochloric acid (HCl, 36-38%), ethanol (C2H5OH, AR), aniline (C6H5NH2, AR) and ammonium persulfate ((NH4)2S2O8, AR) were obtained from Sinopharm Chemical Reagent. All the chemicals were used as received without further purification unless specifically stated. Synthesis of Fe3O4 nanoparticles The Fe3O4 nanoparticles (NPs) were synthesized by chemical co-precipitation method[28]. In a typical experiment, 0.43g of FeCl2•4H2O and 1.18g of FeCl3•6H2O were dissolved in 40ml deionized water in a flask which was degassed with nitrogen for 20 min and heated up to 50 ℃. Thereafter, 4.5ml of NH3•H2O solution was dropwise added into the mixture under vigorous stirring at the speed of 700 rpm until the pH value of the mixture reached 11. The solution became black immediately when Fe3O4 NPs started to generate. The reaction was kept stirring for 1h at 50 ℃, which was cooled down to room temperature
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afterward. The Fe3O4 NPs were separated out by the magnetic decantation (10×10×4cm3, 1.4T), which was washed by deionized water and ethanol successively for five times and then dried in a vacuum oven at 70℃. Synthesis of Fe3O4/PPy nanocomposites The Fe3O4/PPy nanocomposites were synthesized referring to the method described by Zhao et al.[29]. The whole one-pot synthesis process was carried out in a 250 ml three-necked, round-bottomed flask in which 0.5g of Fe3O4 NPs and 9.0g of FeCl3•6H2O were added to 150ml of deionized water. Then the mixture was stirred with mechanical agitation at the speed of 600 rpm at 25℃ for 3 h to accumulate Fe3+ ions on the surface of nanocomposites by the common ion effect[30]. Afterward 20 mL of C18H29NaSO3 solution (5.85 wt%) and 0.3 mL of PPy monomers were rapidly injected into the mixture. Then the mixture was kept stirring for 12 h at room temperature. The products were collected by the magnetic decantation(10×10×4cm3, 1.4T) and washed by deionized water and ethanol for about five times in alternative manner, which were then dried in a vacuum oven at 60℃ for 4 h. Synthesis of Fe3O4/PPy /PANI nanocomposites In a typical experiment, 0.4g of Fe3O4/PPy nanocomposite was dispersed in 100 ml of 0.1 M HCl solution under ultra-sonication and stirring simultaneously for 1 h. Subsequently, 0.3 ml of aniline monomers were then injected into the suspension and stirred for 1h under ice-water bath. Afterward, 0.9 g of ammonium persulfate (APS) was added to initiate oxidative polymerization which was lasted for 24h. The final Fe3O4/PPy /PANI ternary nanocomposites were collected by the magnetic decantation (10×10×4cm3, 1.4T) and washed successively with deionized water and ethanol until the filtrate become colorless, which was then dried in a vacuum oven at 60℃ for 4 h. Characterization
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X-ray diffraction (XRD) patterns were recorded on an X-Ray diffractometer (D8A Advance, BRUKER). Fourier transform infrared (FTIR) spectra were collected on a Nicolet 6700 infrared spectrometer using pressed KBr discs. The scanning electron microscope (SEM) images and composition analysis was performed by field emission scanning electron microscopy (FE-SEM, Ultra55, Carl Zeiss) and energy dispersive spectrometer (EDS, X-MAX 50, Oxford Instrument). The paraffin based composites were prepared via compressing at room temperature. As prepared nanocomposite powders (20 wt%) were mixed with paraffin for the measurements of electromagnetic parameters at 2–18 GHz using a vector network analyzer (Agilent N5242A), which is utilized to investigate the microwave absorption property of the material systems.
Results and discussion Synthesis of Fe3O4/PPy /PANI nanocomposite Fig 2 shows the XRD patterns of bare Fe3O4 nanoparticles (Fig 2a), Fe3O4/PPy (Fig 2b) and Fe3O4/PPy /PANI (Fig 2c) nanocomposites, in which the marked diffraction peaks can be attributed to the (220), (311), (400), (422), (511), and (440) planes of face-centered cubic Fe3O4 (JCPDS no.89-2355). It can be clearly seen from the XRD pattern that Fe3O4‘s characteristic diffraction peaks have been retained well in both Fe3O4/PPy (Fig 2b) and Fe3O4/PPy /PANI (Fig 2c) nanocomposites if compared with bare Fe3O4 nanoparticles (Fig 2a), which indicates the deposition of conductive polymer layer has no negative influence on the crystalline structure of nano Fe3O4. To confirm the deposition of PPy and PANI on Fe3O4 nanoparticles, FTIR spectra were obtained which was demonstrated in Fig 3. For bare Fe3O4 nanoparticles (Fig 3a), there are only two characteristic absorption peaks located at 585 cm-1and 3424 cm-1, which can be attributed to Fe-O bond and –OH groups on the surface of the Fe3O4 nanoparticles respectively. After the deposition of PPy, the characteristic absorption
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peaks of PPy appeared in the spectrum of Fe3O4/PPy nanocomposites (Fig 3b). In detail, the peak at 1544 cm-1 are attributed to the C-C stretching vibrations in the pyrrole ring. The peaks at 1046 cm-1 and 1446 are derived from C-N ring stretching. The peaks at 1296 cm-1 and 1166 cm-1 can be assigned to the ¼C H in plane vibration. In addition, the ¼C H out of plane vibration is located at 784 cm-1 and 895 cm-1. These results indicate a compact combination between Fe3O4 nanoparticles and polypyrrole. For Fe3O4/PPy /PANI ternary nanocomposite (Fig 3c), the peak at 1298 cm-1 confirms the presence of polyaniline stretching C-N vibration. The absorption band at 798 cm-1 is attributed to C-H outer plan bending vibration for polyaniline. From these results it can be inferred that the products were ternary nanocomposites composed of Fe3O4, PPy and PANI. To further visualize the deposition of conductive polymer on Fe3O4 NPs, The morphology of Fe3O4, Fe3O4/PPy (Fig 4a) and Fe3O4/PPy /PANI (Fig 4b) nanocomposites have been studied with transmission electron microscopy (TEM) which is shown in Fig 4. The dark regions are Fe3O4 nanoparticles while the grey areas indicate the existence of PPy and PANI layers. It can be seen that the size of Fe3O4 nanoparticles in average is approximately 15 nm, which are covered by a thick polymer layer. Microwave absorbing performance of Fe3O4/PPy /PANI nanocomposites The reflection loss (RL) of the samples can be calculated using measured relative complex permeability and permittivity according to the transmission line theory as listed below[23, 31]:
where
is normalized input impedance,
(377Ω) is the characteristic impedance of free space;
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and
are the permittivity and permeability of the free space, respectively; c is the light velocity in
vacuum and d is thickness of the absorber; f is the microwave frequency. When the RL is lower than -10 dB, it can be seen as 90% of microwave energy is absorbed. So the range where RL is smaller than -10 dB is defined as the effective absorption bandwidth[32]. The influence of material thickness (d) on RL is illustrated in Fig 5. It can be seen clearly that the thickness (d) of an absorber is one of the most essential factors that affect the responding frequency of reflection loss and intensity. The maximum reflection losses of absorbers with different thicknesses all exhibit negative shift to lower frequency as the frequency increases. In Fig 5 (c), wide responding bandwidths over -10 dB can be easily achieved when the thickness is in the range of 2.0 to 4.4 mm. Meanwhile, Fe3O4 and Fe3O4/PPy appears much poorer microwave RL performance in the whole thickness range, which further confirms the enhancement of microwave absorbing capability of Fe3O4/PPy /PANI. Moreover, our ternary nanocomposites can achieve excellent absorption properties in both low and high frequency bands, which can be tuned by the thickness of absorber. We have compared the microwave absorbing properties of our Fe3O4/PPy/PANI ternary nanocomposites with Fe3O4 and other conductive polymer based composites in Table 1. It can be seen that our material has the widest effective bandwidth and most negative RL value, which indicates it as a promising microwave absorbing material for further applications.
Conclusions In summary, Fe3O4 nanoparticles have been successfully synthesized by environmentally-friendly co-precipitation method. Fe3O4/PPy binary nanocomposites and Fe3O4/PPy /PANI were successfully synthesized by in situ polymerization of pyrrole and aniline. The strong affinity between PPy and PANI via carbonyl groups have ensured the interaction of PPy and PANI on the surface of Fe3O4 NPs. As-obtained
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Fe3O4/PPy/PANI ternary nanocomposites have shown substantially enhanced microwave absorbing performance if compared to bare Fe3O4 and Fe3O4/PPy binary nanocomposites, which is also much better than many earlier reported similar materials. Investigations on the electromagnetic properties indicate that the conductive network and lower resistance benefiting from the introduction of conductive polymers contribute further to the impedance match and the interfacial polarization between each medium, which enhances the dielectric loss significantly. We believe this work can offer some guidance to the design and development of novel lightweight materials with outstanding microwave absorbing performance.
Acknowledgments This work is supported by the National Key Research and Development Program (2016YFA0202900), the Army Advanced Research fund of China (9140C950205150C95394 AND FD2015008).
Declaration of interest statement The authors report no declarations of interest.
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Table 1 Performance comparison of Fe3O4/PPy /PANI ternary nanocomposite with reported Fe3O4 and similar conductive polymer based composites
Fig 1
sample
wt (%)
Thickness(mm)
Max RL (frequency)
Bandwidth over -10 dB
Effective bandwidth
Ref
Fe3O4/PANI
40
2.0
-13.8dB (16.7 GHz)
16.3-17.2
0.9
[17]
Fe3O4/MWCNT/PANI
20
2.0
−8.0dB (14.7 GHz)
0
0
[33]
graphene@Fe3O4@SiO2@PANI
25
2.0
−19.4dB (16.4 GHz)
10.4−18.0
4.4
[34]
Fe3O4 microspheres/PANI
50
2.0
−37.4 dB (15.4 GHz)
13.0−18.0
5.0
[35]
Fe3O4/CIP/PANI
30
2.0
−25.5 dB (10.1 GHz)
7.1−9.9
2.8
[36]
Fe3O4/polypyrrole/carbon
20
3.0
-25.9 dB (10.2 GHz)
8.0-12.5
4.5
[37]
Fe3O4/PPy /PANI
20
2.0
-47.3 dB (13.45 GHz)
9.0-18.0
9.0
This work
Schematic demonstration of the synthetic protocol for Fe3O4/PPy/PANI ternary nanocomposites
Fig 2
XRD diffraction patterns of the nanocomposites: a: Fe3O4, b: Fe3O4/PPy, c: Fe3O4/PPy /PANI
Fig 3
FT-IR spectra of the nanocomposites: a: Fe3O4, b: Fe3O4/PPy, c: Fe3O4/PPy /PANI
Fig 4
TEM images of the nanocomposites a: Fe3O4/PPy, b: Fe3O4/PPy /PANI
Fig 5
microwave RL of three nanocomposites at different absorber thickness: a: Fe3O4, b: Fe3O4/PPy, c: Fe3O4/PPy /PANI
Table 1 Performance comparison of Fe3O4/PPy /PANI ternary nanocomposite with reported Fe3O4 and similar conductive polymer based composites sample
wt (%)
Thickness(mm)
Max RL (frequency)
Bandwidth over -10 dB
Effective bandwidth
Ref
Fe3O4/PANI
40
2.0
-13.8dB (16.7 GHz)
16.3-17.2
0.9
[17]
Fe3O4/MWCNT/PANI
20
2.0
−8.0dB (14.7 GHz)
0
0
[40]
graphene@Fe3O4@SiO2@PANI
25
2.0
−19.4dB (16.4 GHz)
10.4−18.0
4.4
[41]
Fe3O4 microspheres/PANI
50
2.0
−37.4 dB (15.4 GHz)
13.0−18.0
5.0
[42]
Fe3O4/CIP/PANI
30
2.0
−25.5 dB (10.1 GHz)
7.1−9.9
2.8
[43]
Fe3O4/polypyrrole/carbon
20
3.0
-25.9 dB (10.2 GHz)
8.0-12.5
4.5
[44]
Fe3O4/PPy /PANI
20
2.0
-47.3 dB (13.45 GHz)
9.0-18.0
9.0
This work
Figure1
Figure2
Figure3
Figure4
Figure5
S1319-6103(16)30109-0 http://dx.doi.org/10.1016/j.jscs.2016.11.005 JSCS 847
To appear in:
Journal of Saudi Chemical Society
Received Date: Accepted Date:
3 October 2016 30 November 2016
Please cite this article as: B. Li, X. Weng, G. Wu, Y. Zhang, X. Lv, G. Gu, Synthesis of Fe3O4/polypyrrole/polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties, Journal of Saudi Chemical Society (2016), doi: http://dx.doi.org/10.1016/j.jscs.2016.11.005
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Synthesis of Fe3O4/polypyrrole/polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties Bingzhen Li a, Xiaodi Weng a, Guojing Wu d, Yang Zhang c, Xuliang Lv *, a, Guangxin Gu *, b a
Key laboratory of Science and Technology on Electromagnetic Effects and Electro-optical Engineering,
PLA University of Science & Technology, Nanjing 210007, PR China. b
Department of Materials Science, Fudan University, Shanghai, 200433, PR China.
c
Nantong Qiurun Nanotechnology Company, Nantong, 226001, PR China.
d
Wuxi joint logistics center, Wuxi, 214000, PR China.
* To whom the correspondence should be addressed. Email: [email protected] , [email protected] Corresponding author: Xuliang Lv at Key laboratory of Science and Technology on Electromagnetic Effects and Electro-optical Engineering, PLA University of Science & Technology, Nanjing 210007, PR China. Email: [email protected] , Phone number: 13851470758. Guangxin Gu at Department of Materials Science, Fudan University, Shanghai, 200433, PR China. Email: [email protected], Phone number: 13003150756 Key terms: nanocomposites; synthesis; electromagnetic property
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Synthesis of Fe3O4/polypyrrole/polyaniline nanocomposites by in-situ method and their electromagnetic absorbing properties Abstract Fe3O4/PPy/PANI (Fe3O4/polypyrrole/polyaniline) nanocomposites with excellent microwave absorbing properties have been successfully synthesized and characterized systematically. In detail, Fe3O4 nanoparticles were prepared via an environmental friendly, modified co-precipitation method. Afterward, two conductive polymers, PPy and PANI, were deposited onto the surface of Fe3O4 nanoparticles by in-situ polymerization of pyrrole and aniline. PPy and PANI was “glued” by the strong affinity between the carbonyl groups of PPy and the conjugated chains of PANI. The obtained Fe3O4/PPy/PANI nanocomposites have been found to possess excellent microwave absorbing property with the absorption bandwidth of 10.7 GHz (6.7 -17.4 GHz) and maximum reflection loss at 10.1 GHz (-40.2 dB). It proves that the combination of ultra-small Fe3O4 nanoparticles with two different conductive polymers have a great potential in the application of microwave absorbing materials.
Introduction Microwave absorbing materials have attracted increasing research attention in the past decades, due to their significant role in precise instrument application, promising application in military stealth technology and electromagnetic shielding technology for personal protection [1-4]. The key requirements of a good microwave absorbing material include wide absorption bandwidth, strong attenuation property, light weight, and thin thickness [5-7], which specifically demand remarkable magnetic loss or dielectric loss to attenuate the microwave energy, a good impedance match, adjustment of electromagnetic parameters combining kinds of losing principles and a relatively low density. [8, 9]However, these features are unlikely to occur in one single material: The impedance match is influenced by both the magnetic and electronic
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properties following a complex mechanism which make it extraordinary difficult to adjust; high magnetic loss often involve metal composites, making the density unnecessarily high; a better absorbing performance usually come with extra thickness. [10-12]Thus, composite materials that offer the chances to adjust the complex electromagnetic parameters and physical properties seem to be a rational way to realize these unique properties in the same time. Magnetic nanoparticles such as Fe3O4 has been widely used in microwave absorbing application and proved to provide significant magnetic loss property [13, 14]. However, the application of these particles are restricted by their narrow frequency range and relatively higher density [15]. Recent research progress indicates that the combination of lightweight conductive polymer with magnetic nanoparticles not only lower the density of the composites, but also brings benefits to the
electromagnetic properties
by introducing dielectric loss to the material system[16-21]. As typical conductive polymers, PANI and PPy both have high conductivity, low density, and also are easy to produce and reserve [22, 23]. Therefore, PANI and PPy have been employed in many microwave absorbing composites systems as organic binder, medium, or a coating layer of inorganic particles to improve materials’ dielectric loss and impedance matching property, which in turn enhanced materials’ microwave absorbing performance [24-26]. Sayed Hossein et al. synthesized PANI/MnFe2O4 nanocomposites with core-shell structure, achieving minimum reflection loss at 10.4 GHz of -15.3 dB with a thickness of 1.4 mm. The same group reported the synthesis of PPy/MnFe2O4 with core-shell structure and a minimum reflection loss of -12 dB at 11.3 GHz with the thickness of 1.5 mm[27]. Another core-shell structured Fe3O4@PANI nanoparticles with very thin PANI coating was reported by Sun et al with significantly enhanced microwave absorption property [17]. To our knowledge, there is still no report on the combination of two conductive polymer with magnetic nanoparticles till now, which we believe can potentially increase the complex permittivity and provide
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interfacial polarization that can further improve material systems’ microwave absorbing property. In this article, we have successfully synthesized a ternary nanocomposites Fe3O4/PPy/PANI via co-precipitation method and systematically investigated its application potential as a microwave absorbing material. The detailed synthesis route is demonstrated in Figure 1., Fe3O4 nanoparticles with grain size of approximately 15 nm were synthesized by co-precipitation method [28], which were used as the nucleation sites for the coating process of PPy on the surface of Fe3O4 via in situ polymerization. The abundant carbonyl groups on the surface of PPy have strong affinity to PANI, which ensures the further deposition of PANI on Fe3O4/PPy binary nanocomposite [15].
Methods Raw materials Ferric chloride hexahydrate(FeCl3•6H2O, AR), iron dichloride tetrahydrate (FeCl2•4H2O, AR), ammonium hydroxide (NH3•H2O, AR, 25-28%)，Sodium dodecyl benzene sulfonate (C18H29NaSO3, 95%) and pyrrole (C4H5N, CP) were purchased from Aladdin. Hydrochloric acid (HCl, 36-38%), ethanol (C2H5OH, AR), aniline (C6H5NH2, AR) and ammonium persulfate ((NH4)2S2O8, AR) were obtained from Sinopharm Chemical Reagent. All the chemicals were used as received without further purification unless specifically stated. Synthesis of Fe3O4 nanoparticles The Fe3O4 nanoparticles (NPs) were synthesized by chemical co-precipitation method[28]. In a typical experiment, 0.43g of FeCl2•4H2O and 1.18g of FeCl3•6H2O were dissolved in 40ml deionized water in a flask which was degassed with nitrogen for 20 min and heated up to 50 ℃. Thereafter, 4.5ml of NH3•H2O solution was dropwise added into the mixture under vigorous stirring at the speed of 700 rpm until the pH value of the mixture reached 11. The solution became black immediately when Fe3O4 NPs started to generate. The reaction was kept stirring for 1h at 50 ℃, which was cooled down to room temperature
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afterward. The Fe3O4 NPs were separated out by the magnetic decantation (10×10×4cm3, 1.4T), which was washed by deionized water and ethanol successively for five times and then dried in a vacuum oven at 70℃. Synthesis of Fe3O4/PPy nanocomposites The Fe3O4/PPy nanocomposites were synthesized referring to the method described by Zhao et al.[29]. The whole one-pot synthesis process was carried out in a 250 ml three-necked, round-bottomed flask in which 0.5g of Fe3O4 NPs and 9.0g of FeCl3•6H2O were added to 150ml of deionized water. Then the mixture was stirred with mechanical agitation at the speed of 600 rpm at 25℃ for 3 h to accumulate Fe3+ ions on the surface of nanocomposites by the common ion effect[30]. Afterward 20 mL of C18H29NaSO3 solution (5.85 wt%) and 0.3 mL of PPy monomers were rapidly injected into the mixture. Then the mixture was kept stirring for 12 h at room temperature. The products were collected by the magnetic decantation(10×10×4cm3, 1.4T) and washed by deionized water and ethanol for about five times in alternative manner, which were then dried in a vacuum oven at 60℃ for 4 h. Synthesis of Fe3O4/PPy /PANI nanocomposites In a typical experiment, 0.4g of Fe3O4/PPy nanocomposite was dispersed in 100 ml of 0.1 M HCl solution under ultra-sonication and stirring simultaneously for 1 h. Subsequently, 0.3 ml of aniline monomers were then injected into the suspension and stirred for 1h under ice-water bath. Afterward, 0.9 g of ammonium persulfate (APS) was added to initiate oxidative polymerization which was lasted for 24h. The final Fe3O4/PPy /PANI ternary nanocomposites were collected by the magnetic decantation (10×10×4cm3, 1.4T) and washed successively with deionized water and ethanol until the filtrate become colorless, which was then dried in a vacuum oven at 60℃ for 4 h. Characterization
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X-ray diffraction (XRD) patterns were recorded on an X-Ray diffractometer (D8A Advance, BRUKER). Fourier transform infrared (FTIR) spectra were collected on a Nicolet 6700 infrared spectrometer using pressed KBr discs. The scanning electron microscope (SEM) images and composition analysis was performed by field emission scanning electron microscopy (FE-SEM, Ultra55, Carl Zeiss) and energy dispersive spectrometer (EDS, X-MAX 50, Oxford Instrument). The paraffin based composites were prepared via compressing at room temperature. As prepared nanocomposite powders (20 wt%) were mixed with paraffin for the measurements of electromagnetic parameters at 2–18 GHz using a vector network analyzer (Agilent N5242A), which is utilized to investigate the microwave absorption property of the material systems.
Results and discussion Synthesis of Fe3O4/PPy /PANI nanocomposite Fig 2 shows the XRD patterns of bare Fe3O4 nanoparticles (Fig 2a), Fe3O4/PPy (Fig 2b) and Fe3O4/PPy /PANI (Fig 2c) nanocomposites, in which the marked diffraction peaks can be attributed to the (220), (311), (400), (422), (511), and (440) planes of face-centered cubic Fe3O4 (JCPDS no.89-2355). It can be clearly seen from the XRD pattern that Fe3O4‘s characteristic diffraction peaks have been retained well in both Fe3O4/PPy (Fig 2b) and Fe3O4/PPy /PANI (Fig 2c) nanocomposites if compared with bare Fe3O4 nanoparticles (Fig 2a), which indicates the deposition of conductive polymer layer has no negative influence on the crystalline structure of nano Fe3O4. To confirm the deposition of PPy and PANI on Fe3O4 nanoparticles, FTIR spectra were obtained which was demonstrated in Fig 3. For bare Fe3O4 nanoparticles (Fig 3a), there are only two characteristic absorption peaks located at 585 cm-1and 3424 cm-1, which can be attributed to Fe-O bond and –OH groups on the surface of the Fe3O4 nanoparticles respectively. After the deposition of PPy, the characteristic absorption
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peaks of PPy appeared in the spectrum of Fe3O4/PPy nanocomposites (Fig 3b). In detail, the peak at 1544 cm-1 are attributed to the C-C stretching vibrations in the pyrrole ring. The peaks at 1046 cm-1 and 1446 are derived from C-N ring stretching. The peaks at 1296 cm-1 and 1166 cm-1 can be assigned to the ¼C H in plane vibration. In addition, the ¼C H out of plane vibration is located at 784 cm-1 and 895 cm-1. These results indicate a compact combination between Fe3O4 nanoparticles and polypyrrole. For Fe3O4/PPy /PANI ternary nanocomposite (Fig 3c), the peak at 1298 cm-1 confirms the presence of polyaniline stretching C-N vibration. The absorption band at 798 cm-1 is attributed to C-H outer plan bending vibration for polyaniline. From these results it can be inferred that the products were ternary nanocomposites composed of Fe3O4, PPy and PANI. To further visualize the deposition of conductive polymer on Fe3O4 NPs, The morphology of Fe3O4, Fe3O4/PPy (Fig 4a) and Fe3O4/PPy /PANI (Fig 4b) nanocomposites have been studied with transmission electron microscopy (TEM) which is shown in Fig 4. The dark regions are Fe3O4 nanoparticles while the grey areas indicate the existence of PPy and PANI layers. It can be seen that the size of Fe3O4 nanoparticles in average is approximately 15 nm, which are covered by a thick polymer layer. Microwave absorbing performance of Fe3O4/PPy /PANI nanocomposites The reflection loss (RL) of the samples can be calculated using measured relative complex permeability and permittivity according to the transmission line theory as listed below[23, 31]:
where
is normalized input impedance,
(377Ω) is the characteristic impedance of free space;
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and
are the permittivity and permeability of the free space, respectively; c is the light velocity in
vacuum and d is thickness of the absorber; f is the microwave frequency. When the RL is lower than -10 dB, it can be seen as 90% of microwave energy is absorbed. So the range where RL is smaller than -10 dB is defined as the effective absorption bandwidth[32]. The influence of material thickness (d) on RL is illustrated in Fig 5. It can be seen clearly that the thickness (d) of an absorber is one of the most essential factors that affect the responding frequency of reflection loss and intensity. The maximum reflection losses of absorbers with different thicknesses all exhibit negative shift to lower frequency as the frequency increases. In Fig 5 (c), wide responding bandwidths over -10 dB can be easily achieved when the thickness is in the range of 2.0 to 4.4 mm. Meanwhile, Fe3O4 and Fe3O4/PPy appears much poorer microwave RL performance in the whole thickness range, which further confirms the enhancement of microwave absorbing capability of Fe3O4/PPy /PANI. Moreover, our ternary nanocomposites can achieve excellent absorption properties in both low and high frequency bands, which can be tuned by the thickness of absorber. We have compared the microwave absorbing properties of our Fe3O4/PPy/PANI ternary nanocomposites with Fe3O4 and other conductive polymer based composites in Table 1. It can be seen that our material has the widest effective bandwidth and most negative RL value, which indicates it as a promising microwave absorbing material for further applications.
Conclusions In summary, Fe3O4 nanoparticles have been successfully synthesized by environmentally-friendly co-precipitation method. Fe3O4/PPy binary nanocomposites and Fe3O4/PPy /PANI were successfully synthesized by in situ polymerization of pyrrole and aniline. The strong affinity between PPy and PANI via carbonyl groups have ensured the interaction of PPy and PANI on the surface of Fe3O4 NPs. As-obtained
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Fe3O4/PPy/PANI ternary nanocomposites have shown substantially enhanced microwave absorbing performance if compared to bare Fe3O4 and Fe3O4/PPy binary nanocomposites, which is also much better than many earlier reported similar materials. Investigations on the electromagnetic properties indicate that the conductive network and lower resistance benefiting from the introduction of conductive polymers contribute further to the impedance match and the interfacial polarization between each medium, which enhances the dielectric loss significantly. We believe this work can offer some guidance to the design and development of novel lightweight materials with outstanding microwave absorbing performance.
Acknowledgments This work is supported by the National Key Research and Development Program (2016YFA0202900), the Army Advanced Research fund of China (9140C950205150C95394 AND FD2015008).
Declaration of interest statement The authors report no declarations of interest.
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Table 1 Performance comparison of Fe3O4/PPy /PANI ternary nanocomposite with reported Fe3O4 and similar conductive polymer based composites
Fig 1
sample
wt (%)
Thickness(mm)
Max RL (frequency)
Bandwidth over -10 dB
Effective bandwidth
Ref
Fe3O4/PANI
40
2.0
-13.8dB (16.7 GHz)
16.3-17.2
0.9
[17]
Fe3O4/MWCNT/PANI
20
2.0
−8.0dB (14.7 GHz)
0
0
[33]
graphene@Fe3O4@SiO2@PANI
25
2.0
−19.4dB (16.4 GHz)
10.4−18.0
4.4
[34]
Fe3O4 microspheres/PANI
50
2.0
−37.4 dB (15.4 GHz)
13.0−18.0
5.0
[35]
Fe3O4/CIP/PANI
30
2.0
−25.5 dB (10.1 GHz)
7.1−9.9
2.8
[36]
Fe3O4/polypyrrole/carbon
20
3.0
-25.9 dB (10.2 GHz)
8.0-12.5
4.5
[37]
Fe3O4/PPy /PANI
20
2.0
-47.3 dB (13.45 GHz)
9.0-18.0
9.0
This work
Schematic demonstration of the synthetic protocol for Fe3O4/PPy/PANI ternary nanocomposites
Fig 2
XRD diffraction patterns of the nanocomposites: a: Fe3O4, b: Fe3O4/PPy, c: Fe3O4/PPy /PANI
Fig 3
FT-IR spectra of the nanocomposites: a: Fe3O4, b: Fe3O4/PPy, c: Fe3O4/PPy /PANI
Fig 4
TEM images of the nanocomposites a: Fe3O4/PPy, b: Fe3O4/PPy /PANI
Fig 5
microwave RL of three nanocomposites at different absorber thickness: a: Fe3O4, b: Fe3O4/PPy, c: Fe3O4/PPy /PANI
Table 1 Performance comparison of Fe3O4/PPy /PANI ternary nanocomposite with reported Fe3O4 and similar conductive polymer based composites sample
wt (%)
Thickness(mm)
Max RL (frequency)
Bandwidth over -10 dB
Effective bandwidth
Ref
Fe3O4/PANI
40
2.0
-13.8dB (16.7 GHz)
16.3-17.2
0.9
[17]
Fe3O4/MWCNT/PANI
20
2.0
−8.0dB (14.7 GHz)
0
0
[40]
graphene@Fe3O4@SiO2@PANI
25
2.0
−19.4dB (16.4 GHz)
10.4−18.0
4.4
[41]
Fe3O4 microspheres/PANI
50
2.0
−37.4 dB (15.4 GHz)
13.0−18.0
5.0
[42]
Fe3O4/CIP/PANI
30
2.0
−25.5 dB (10.1 GHz)
7.1−9.9
2.8
[43]
Fe3O4/polypyrrole/carbon
20
3.0
-25.9 dB (10.2 GHz)
8.0-12.5
4.5
[44]
Fe3O4/PPy /PANI
20
2.0
-47.3 dB (13.45 GHz)
9.0-18.0
9.0
This work
Figure1
Figure2
Figure3
Figure4
Figure5