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Research Articles

Preparation of Fe3O4-carbon black/poly(vinylidene fluoride) composites with enhanced properties

, , , , &
Pages 805-814 | Received 20 Mar 2023, Accepted 28 Apr 2023, Published online: 15 May 2023

Abstract

In this work, the Fe3O4-carbon black filler was obtained from an in-situ coprecipitation method followed by the modification of the heptadecafluorodecyltrimethoxysilane and the Fe3O4-carbon black/poly(vinylidene fluoride) (PVDF) composites with enhanced properties were prepared by a simple solution blending-water precipitating method. The Fe3O4-carbon black distributed well in the PVDF matrix, which was confirmed by the SEM. According to the results of FTIR and WAXD, a lot of useful polar crystalline phases of PVDF formed in the Fe3O4-carbon black/PVDF composites. The electrically conductive ability, the dielectric permittivity, the dielectric loss factor, and the magnetic saturation value of the Fe3O4-carbon black/PVDF composite increased with the increasing loading amount of Fe3O4-carbon black filler. Especially, when the Fe3O4-carbon black was 5 wt.%, the dielectric permittivity of Fe3O4-carbon black/PVDF composite reached as high as 23.5 at 1000 Hz with a relatively low dielectric loss factor value of 0.38 and a magnetic saturation value of 0.64 emu/g.

1. Introduction

Poly(vinylidene fluoride) (PVDF) is a multi-functional polymer with good piezoelectricity as well as a relatively high dielectric permittivity.[Citation1–9] The piezoelectricity can make the PVDF transfer the mechanical energy into electrical energy owing to its piezoelectric polar β and γ crystal forms. However, the non-polar α crystal form is the most stable crystalline phase for PVDF leading to the difficulty in the formation of the polar β and γ crystal forms of PVDF. Moreover, although the dielectric permittivity of PVDF is quite high among polymers, it is still necessary to be further improved for the purpose of practical application. In the meantime, the incorporation of some fillers with functionality (such as Fe3O4 nanoparticles with magnetism) into PVDF will effectively extend its application.[Citation10–15] Therefore, many researchers have been always seeking an effective way to prepare the multi-functional PVDF-based materials integrating high content polar crystal forms of PVDF, enhanced dielectric permittivity, and other functionalities.

It has been reported that the addition of electrically conductive fillers such as carbon nanotubes, graphene, exfoliated graphite nanosheet, Ag nanoparticle, Ag nanowire into the PVDF matrix can achieve a composite with high content polar crystal form as a result of the interfacial interaction between the PVDF and the electrically conductive filler.[Citation16–21] However, the electrically conductive filler mentioned above are quite expensive. On the other hand, if suitable amount of the electrically conductive fillers are in the parallel state separating with one another in the PVDF matrix, a lot of microcapacitors will form resulting in the enhancement of the dielectric permittivity for the electrically conductive filler/PVDF composite. Nevertheless, it is difficult to control this distribution of the electrically conductive fillers in the PVDF matrix. Recently, Moharana et al. have reported the tri-phase BiFeO3-carbon black/PVDF composite with enhanced dielectric and electrical properties.[Citation10] However, the magnetism and the crystal form of the PVDF matrix in the tri-phase BiFeO3-carbon black/PVDF composite weren’t explored and the special BiFeO3 particles are relatively expensive.

In this work, we fabricated the Fe3O4-carbon black/PVDF composites by a simple solution blending-water precipitating method which could achieve the homogenous distribution of the Fe3O4-carbon black filler in the PVDF matrix. The schematic diagram of the preparation process of the Fe3O4-carbon black/PVDF composites was shown in . The purpose of the utilization of these two functional fillers because the carbon black nanoparticles is a relatively cost-effective electrically conductive filler while the commonly-used Fe3O4 nanoparticles have good magnetism.[Citation11,Citation22,Citation23] Furthermore, the microstructure, the crystallization behavior as well as the magnetic, electrical and dielectric properties of the resultant Fe3O4-carbon black/PVDF composites were investigated.

Figure 1. The schematic diagram of the preparation process of the Fe3O4-carbon black/PVDF composites.

Figure 1. The schematic diagram of the preparation process of the Fe3O4-carbon black/PVDF composites.

2. Experimental

2.1. Materials and sample preparation

PVDF (Solef 6008) was purchased from Solvay Shanghai Branch Company, China. FeCl3·6H2O, NaOH, FeCl2·4H2O, absolute alcohol, carbon black nanoparticles, and dimethylformamide (DMF) were purchased from Guangzhou Chemical Company, China. Heptadecafluorodecyltrimethoxysilane (HFTS) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.

The Fe3O4-carbon black filler was prepared as follow: 2.0 g carbon black nanoparticles, 4.66 g FeCl3·6H2O, 1.72 g FeCl2·4H2O, and 2.76 g NaOH were added into a three-neck bottle and then the reaction was carried out under stirring by the protection of the nitrogen at 90 °C for 4 h. Next, the resultant Fe3O4-carbon black filler was magnetically collected and then washed by deionized water for several times followed by being dried at 70 °C for 24 h under vacuum.

The composites consisting PVDF and Fe3O4-carbon black filler were prepared by the solution blending-water precipitating method. For instance, the Fe3O4-carbon black/PVDF composite containing 1 wt.% Fe3O4-carbon black filler was obtained as follow: first, 0.1 g Fe3O4-carbon black filler and 0.1 g HFTS was dispersed in 100 mL DMF in a three-neck bottle by stirring for 1 h, and then 9.9 g PVDF was added into the resultant mixture of the modified Fe3O4-carbon black filler and 100 mL DMF. Next, after stirring at 90 °C for 4 h, the mixture of the modified Fe3O4-carbon black filler, PVDF, and DMF was putted into the cold water, and the resultant Fe3O4-carbon black/PVDF composite was dried at 70 °C for 24 h under vacuum and then pressed at 160 °C with the pressure of about 16 MPa to obtain the sample PFC1. The Fe3O4-carbon black/PVDF composite containing 3 wt.% and 5 wt.% Fe3O4-carbon black filler were prepared by the similar method mentioned above and abbreviated as PFC3 and PFC5, correspondingly.

2.2. Characterization

The scanning electron microscope (SEM, Zeiss Sigma 300) with the two dimensional energy dispersive spectroscope (EDS) was used to observe the microstructures of the Fe3O4, the carbon black nanoparticles, and the Fe3O4-carbon black filler. The microstructure of the Fe3O4-carbon black/PVDF composite was investigated by the FEI QUANTA 400 FEG SEM. The crystalline phases of the Fe3O4-carbon black filler, the pure PVDF, and the Fe3O4-carbon black/PVDF composites are investigated by the Fourier Transform infrared spectroscopy (FTIR, Thermo Scientific Nicolet IS50) and the Wide-Angle X-ray Diffraction (WAXD, Rikagu Ultima IV). The dielectric permittivities and the dielectric loss factors of the pure PVDF and the Fe3O4-carbon black/PVDF composites were measured using the Keysight E4990A impedance analyzer. The electrical resistivity of the pure PVDF and the Fe3O4-carbon black/PVDF composites were measured by the Keithley 2002 high precision ammeter. The magnetisms of the Fe3O4-carbon black filler and the Fe3O4-carbon black/PVDF composites were measured by the Vibrating Sample Magnetometer (VSM, Quantum Design MPMS SQUID). The thermal stabilities of the pure PVDF and the Fe3O4-carbon black/PVDF composites were measured using the thermo-gravimetric analysis (TGA) using a TGA/DSC3+ system (Mettler).

3. Results and discussion

As shown by the SEM images at different magnifications in , the Fe3O4 nanoparticles agglomerated together with the sphere-like morphology and their sizes were in the range from about 20 nm to about 40 nm. Similar to the SEM result of the pure Fe3O4 nanoparticles, the sphere-like carbon black nanoparticles also heavily agglomerated with different size ranging from about 40 nm to about 400 nm. (see ). It could be found that the sizes of the carbon black nanoparticles were much larger than those of the pure Fe3O4 nanoparticles and then the pure Fe3O4 nanoparticles could be supported on the carbon black nanoparticles during the in-situ preparation. As shown in for the SEM images of the Fe3O4-carbon black/PVDF composite obtained from the in-situ preparation method, a lot of Fe3O4 nanoparticles in the small size have been immobilized on the surface of the carbon black nanoparticles in the large size to achieve the bifunctional filler with two functionalities of the electrical conductivity and magnetism.

Figure 2. SEM images of Fe3O4 nanoparticles at different magnifications: (a) 5000× and (b) 30000×.

Figure 2. SEM images of Fe3O4 nanoparticles at different magnifications: (a) 5000× and (b) 30000×.

Figure 3. SEM images of carbon black nanoparticles at different magnifications: (a) 10000× and (b) 20000×.

Figure 3. SEM images of carbon black nanoparticles at different magnifications: (a) 10000× and (b) 20000×.

Figure 4. SEM images of Fe3O4-carbon black filler at different magnifications: (a) 2000×, (b) 5000×, (c) 10000×, and (d) 20000×.

Figure 4. SEM images of Fe3O4-carbon black filler at different magnifications: (a) 2000×, (b) 5000×, (c) 10000×, and (d) 20000×.

The WAXD result of the Fe3O4-carbon black filler is shown in . There are six characteristic diffraction peaks at 2 theta = 30.1°, 35.5°, 43.3°, 53.6°, 57.2°, and 62.8° in the WAXD pattern of the Fe3O4-carbon black filler, which could be attributed to the (220), (311), (400), (422), (511), and (440) crystal planes of the Fe3O4 nanoparticles, correspondingly.[Citation8] This result confirmed that the Fe3O4 nanoparticles have been supported on the carbon black nanoparticles during the in-situ preparation process. Moreover, a weak diffraction peak in the WAXD pattern of the Fe3O4-carbon black filler at 2 theta = 25.1° could be attributed to the (002) crystal plane of the carbon black nanoparticles, which was different from that of the perfect structure of the graphite crystalline with a well-known characteristic WAXD diffraction peak at 2 theta = 26.6°.[Citation24,Citation25]

Figure 5. WAXD result of Fe3O4-Carbon black filler.

Figure 5. WAXD result of Fe3O4-Carbon black filler.

The FTIR result of the Fe3O4-carbon black filler is shown in . It could be observed that several characteristic FTIR peaks between 1700 cm−1 to 760 cm−1 was due to the existence of the oxygenated groups from the carbon black nanoparticles.[Citation24,Citation25] In addition, the FTIR characteristic peak of the Fe3O4 nanoparticles at 574 cm−1 could be found in the FTIR pattern of the Fe3O4-carbon black filler, which proved the existence of the Fe3O4 nanoparticles.[Citation26]

Figure 6. FTIR result of Fe3O4-Carbon black filler.

Figure 6. FTIR result of Fe3O4-Carbon black filler.

The two dimensional EDS result (see ) exhibited that the Fe3O4-carbon black filler after the surface modification by the HFTS contained the carbon element from the carbon black nanoparticles and the HFTS, the oxygen element from the carbon black nanoparticles, the Fe3O4 nanoparticles, and the HFTS, the iron element from the Fe3O4 nanoparticles, as well as the silicon element and the fluorine element from the HFTS, which all evenly distributed. This result indicated that (1) the homogeneous immobilization of Fe3O4 nanoparticles on the carbon black has been realized and (2) the surface of the Fe3O4-carbon black filler has been uniformly modified by the HFTS containing the fluorine element, which could increase the compatibility between the Fe3O4-carbon black filler and the PVDF matrix.

Figure 7. EDS result of Fe3O4-Carbon black filler.

Figure 7. EDS result of Fe3O4-Carbon black filler.

The SEM was also utilized to investigate the microstructure of the Fe3O4-carbon black/PVDF composites with various loading amounts of the Fe3O4-carbon black fillers at different magnification, which confirmed the successful preparation of the Fe3O4-carbon black/PVDF composites by the solution blending-water precipitating method. As shown in for the SEM images of the cross section of the Fe3O4-carbon black/PVDF composites: (1) the Fe3O4-carbon black fillers were well distributed in the PVDF matrix, which could be attributed to the water-precipitating manipulation preventing the aggregation of Fe3O4-carbon black fillers to a certain extent in the preparation process of Fe3O4-carbon black/PVDF composites, (2) many Fe3O4-carbon black fillers were separated by thin PVDF layers with one another, resulting in the micro-capacitance structure with a great contribution to the enhancement of the dielectric permittivities for the Fe3O4-carbon black/PVDF composites, and (3) it could be found that the Fe3O4-carbon black content in the Fe3O4-carbon black/PVDF composites increased with PFC1, PFC3, and PFC5 in sequence.

Figure 8. SEM images of Fe3O4-carbon black filler/PVDF composite: (a) PFC1, (b) PFC2, and (c) PFC3.

Figure 8. SEM images of Fe3O4-carbon black filler/PVDF composite: (a) PFC1, (b) PFC2, and (c) PFC3.

The VSM investigation results of the pure Fe3O4 nanoparticles, the Fe3O4-carbon black filler, and the Fe3O4-carbon black/PVDF composites are shown in , and all the magnetic hysteresis loops exhibited the superparamagnetic behaviors from 50000 Oe to −50000 Oe without the obvious existence of the remanence and the coercivity. Owing to the decreased contents of Fe3O4 component for the Fe3O4-carbon black filler and the Fe3O4-carbon black/PVDF composites when compared with the pure Fe3O4 nanoparticles, the magnetic saturation (Ms) values of the Fe3O4-carbon black filler (24.2 emu/g) and the Fe3O4-carbon black/PVDF composites are lower than that of the pure Fe3O4 nanoparticles (58.9 emu/g). PFC1, PFC3 and PFC5 possessed the Ms values of 0.02 emu/g, 0.28 emu/g, and 0.64 emu/g, respectively, indicating their magnetic function.[Citation26]

Figure 9. VSM results of (a) Fe3O4 nanoparticles and Fe3O4-carbon black filler and (b) Fe3O4-carbon black filler/PVDF composites.

Figure 9. VSM results of (a) Fe3O4 nanoparticles and Fe3O4-carbon black filler and (b) Fe3O4-carbon black filler/PVDF composites.

The TGA results of the pure PVDF and the Fe3O4-carbon black/PVDF composites from room temperature to 900 °C in N2 are shown in . It was found that the incorporation of the Fe3O4-carbon black filler into the PVDF could slightly increase the thermal stability. For examples, the 5 wt.% decomposition temperatures of pure PVDF, PFC1, PFC3, and PFC5 were 413.9 °C, 449.9 °C, 475.5 °C, and 473.6 °C, respectively.

Figure 10. TGA results of PVDF and Fe3O4-carbon black filler/PVDF composites.

Figure 10. TGA results of PVDF and Fe3O4-carbon black filler/PVDF composites.

The WAXD results of the pure PVDF and the Fe3O4-carbon black/PVDF composites with the 2 theta from 10 degree to 30 degree are shown in . The pure PVDF only displayed four characteristic WAXD diffraction peaks of the α crystal form at 17.8 degree, 18.5 degree, 20.0 degree, and 26.7 degree corresponding to the (100), (020), (110), and (120)/(021) crystal planes without the obvious appearance of the β and γ crystal form.[Citation27,Citation28] While for all the Fe3O4-carbon black/PVDF composites, The obvious decrement of the characteristic WAXD diffraction peak intensities of the α crystal form and the appearances of the characteristic WAXD diffraction peaks of the β and γ crystal form at about 20.8 degree originating from the (110) crystal plane could be found in their WAXD results. In addition, the characteristic WAXD diffraction peak of carbon black in the Fe3O4-carbon black/PVDF composites at 2 theta = 25.1 degree was weak probably due to (1) the low content of the carbon black and (2) the interference of the α crystal form of PVDF at 2 theta = 26.7 degree.

Figure 11. WAXD results of PVDF and Fe3O4-carbon black filler/PVDF composites.

Figure 11. WAXD results of PVDF and Fe3O4-carbon black filler/PVDF composites.

The FTIR spectra of the pure PVDF and the Fe3O4-carbon black/PVDF composites are shown in . The characteristic peaks of the non-polar α crystal form at 763 cm−1, 794 cm−1, 855 cm−1, 974 cm−1, 1211 cm−1, and 1382 cm−1 could be observed in the FTIR spectrum of the pure PVDF,[Citation27,Citation28] while the intensity of the characteristic peaks of the polar β and γ crystal forms at 839 cm−1 was weak. For all the Fe3O4-carbon black/PVDF composites, the obviously increased intensities of the characteristic peaks of the polar β and γ crystal forms at 839 cm−1 could be found in their FTIR spectra indicating that the addition of Fe3O4-carbon black filler into the PVDF matrix could partly transfer the non-polar α crystal form of PVDF to the polar β and γ crystal forms. The possible reasons of this phenomenon could be attributed to the transition of the α phase crystalline with TGTG' sequence to the β phase crystalline with TTTT sequence or the γ phase crystalline with T3GT3G' sequence by the interfacial interaction between the PVDF and the Fe3O4-carbon black filler modified with the HFTS. The content of the polar β and γ crystal forms of PVDF in various samples were calculated as follow:[Citation5,Citation28Citation30](1) F(α, β)=A839/[(K839/K763)A764+A839]×100%(1) where F(β,γ) is the content of the polar β and γ crystal forms, A763 is the absorbance for the α crystal form of PVDF at 763 cm−1, A839 is the absorbance for the polar β and γ crystal forms at 839 cm−1, the absorption coefficients of K763 for the α crystal form of PVDF at 763 cm−1 and K839 for the polar β and γ crystal forms at 839 cm−1 are 6.1 × 104 cm2/mol and 7.7 × 104 cm2/mol, respectively. According to EquationEquation 1, the F(β,γ) of pure PVDF, PFC1, PFC3 and PFC5 were calculated to be 23.03%, 72.64%, 73.19%, and 80.36%, respectively. This result indicated the good facilitation ability of the Fe3O4-carbon black filler to form the polar β and γ crystal forms. Especially, for the PFC5 containing relatively high Fe3O4-carbon black filler, its polar β and γ crystal forms of PVDF has already become the main crystalline phase owing to the existence of a lot of interfacial interaction between the PVDF and the Fe3O4-carbon black filler. Therefore, the useful polar β and γ crystal forms of PVDF with piezoelectricity, pyroelectricity, and ferroeletricity were achieved in the Fe3O4-carbon black/PVDF composites.

Figure 12. FTIR results of PVDF and Fe3O4-carbon black filler/PVDF composites.

Figure 12. FTIR results of PVDF and Fe3O4-carbon black filler/PVDF composites.

The measurement result of the electrical resistivity (ρ) for the pure PVDF and the Fe3O4-carbon black/PVDF composites are shown in . Caused by the electrical conductivity of the Fe3O4-carbon black filler, the ρ values of all Fe3O4-carbon black/PVDF composites were lower than that of the pure PVDF and decreased with the loading amount of Fe3O4-carbon black filler. The ρ values of pure PVDF, PFC1, PFC3, and PFC5 were 4.2 × 109 Ω·m, 1.2 × 108 Ω·m, 7.0 × 107 Ω·m, and 2.1 × 107 Ω·m, respectively. This indicated that there weren’t a number of the electrically conductive paths of the Fe3O4-carbon black in the Fe3O4-carbon black/PVDF composites because of the existence of the relatively insulative coverage of the Fe3O4 nanoparticles on the carbon black surface so that the electrically conductive ability of the Fe3O4-carbon black/PVDF composite only enhanced slightly even when the loading of Fe3O4-carbon black filler was 5 wt.%. The enhancement of the electrically conductive ability for the Fe3O4-carbon black/PVDF composites could be ascribed to the hopping and tunneling mechanisms.[Citation31]

Figure 13. Measurement results of (a) electrical resistivity, (b) dielectric permittivity, and (c) dielectric loss factor for PVDF and Fe3O4-carbon black filler/PVDF composites.

Figure 13. Measurement results of (a) electrical resistivity, (b) dielectric permittivity, and (c) dielectric loss factor for PVDF and Fe3O4-carbon black filler/PVDF composites.

The measurement result of the dielectric permittivities (ε) for the pure PVDF and the Fe3O4-carbon black/PVDF composites at 1000 Hz are shown in . Similar to the measurement result of the ρ values, PFC1, PFC3 and PFC5 possessed the ε values of 12.6, 14.4, and 23.5 at 1000 Hz, respectively, which increased with the loading amount of the Fe3O4-carbon black filler and were much higher than that of the pure PVDF of 8.3. The enhancement extents of the ε for PFC1, PFC3 and PFC5 in comparison with that of the pure PVDF were 51.8%, 73.5%, and 183.1%, respectively. These obvious improvements of the ε value for Fe3O4-carbon black/PVDF composites could be ascribed to two main factors originating from the Fe3O4-carbon black filler: (1) the existence of a lots of the electrically conductive Fe3O4-carbon black/electrically insulative PVDF/electrically conductive Fe3O4-carbon black microcapacitors and (2) the Maxwell-Wagner-Sillars polarization effect due to the accumulated charges at the interface between the PVDF matrix and the Fe3O4-carbon black filler as well as between the Fe3O4 nanoparticles and carbon black nanoparticles.[Citation4,Citation32–34] In addition to the incorporation of the conductive filler into the polymer matrix, the utilization of the stiff brittle ceramic or semiconductor metal with a high ε value is another commonly-used method to achieve a high dielectric-permittivity polymeric composite. However, it is necessary to add a large amount of these fillers into the polymer resulting in the poor mechanical properties of the ceramic/polymer composite. For example, Xu et al. have prepared the TiO2@SrTiO3@polydamine nanowires (15 wt.%)/PVDF composite with a ε value of only about 10.0 at 1000 Hz.[Citation35] Zhou et al. prepared the BaTiO3 (25 wt.%)/poly(methyl methacrylate) (PMMA) composite with a ε value of only 4.2 at 1000 Hz and the corresponding value of the pure PMMA was 3.5.[Citation36] While for the PFC5 sample in this work, its loading amount of the Fe3O4-carbon black filler was only 5 wt.% and the resultant dielectric permittivity reached as high as 23.5 at 1000 Hz.

The measurement result of the dielectric loss factors (tanδ) for the pure PVDF and the Fe3O4-carbon black/PVDF composites at 1000 Hz are shown in . Similar to the measurement results of the ρ values and the ε values, the tanδ values of the Fe3O4-carbon black/PVDF composites increased with the loading amount of the Fe3O4-carbon black filler, which were all higher than that of the pure PVDF. The tanδ value of the pure PVDF was 0.024 at 1000 Hz, while the corresponding values of PFC1, PFC3 and PFC5 were 0.17, 0.24, and 0.38, respectively. These improvements of the tanδ values of the Fe3O4-carbon black/PVDF composites in comparison with that of the pure PVDF could be ascribed to the high current leakage resulting from the relatively high electrical conductivity as mentioned above. It is important to avoid the high tanδ value which will lead to the electrical energy loss and the large heat generation. Although the tanδ value of PFC5 was relatively high, it was still acceptable for the practical application as an dielectric material.[Citation37]

4. Conclusions

The Fe3O4-carbon black/(PVDF) composites with multiple functions including the enhanced electrical, dielectric, and magnetic properties as well as the high-content useful polar β and γ crystal forms of PVDF were prepared by a simple solution blending-water precipitating method. Especially, when the loading amount of the Fe3O4-carbon black was 5 wt.%, the content of the polar β and γ crystal forms of PVDF and the dielectric permittivity at 1000 Hz for Fe3O4-carbon black/(PVDF) composite were 80.4% and 23.5, respectively, which were much higher than those of the pure PVDF with the corresponding values of 23.1% and 8.3, respectively. These results could be attributed to the homogeneous distribution of the Fe3O4-carbon black filler and the interfacial interaction in the PVDF matrix. We hope that our study might provide an effective way for the preparation of other multifunctional PVDF-based composites.

Disclosure statement

No potential conflict of interest was reported by the authors.

Additional information

Funding

The authors would like to acknowledge the support of the Guangdong province natural science foundation, China (2022A1515010475), the professorial and doctoral scientific research foundation of Huizhou University, China (2018JB001), and the Dr. Jing-Shui Xu and Mr. Zi-Yun Xu for their help in revising the paper.

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