Jie Liu,
Yu Luo,
Yao Wang,
Yuan Deng* and
Xitong Xie
Beijing Key Laboratory for Advanced Functional Materials and Thin Film Technology, School of Materials Science & Engineering, Beihang University, Beijing 100191, China. E-mail: dengyuan@buaa.edu.cn; Fax: +86-10-82313482; Tel: +86-10-82313482
First published on 27th October 2015
The main challenge in the field of capacitors is how to reconcile the contradiction of lowering the dielectric loss while maintaining a high dielectric constant of polymer based composites. In this work, a novel two-phase ferroelectric polymer composite, consisting of semiconducting bismuth sulfide (Bi2S3) nanorods and a poly(vinylidene fluoride) (PVDF) matrix, was fabricated by a sequence of casting, hot-stretching and hot-pressing techniques. Orderly polymer composites based on PVDF assembled with parallel aligned Bi2S3 nanorods were realized in the composites after a hot-stretching-pressing process. It’s interesting to note that those orderly polymer composites exhibit excellent dielectric properties. Results show that the composites with oriented structure have high dielectric constant and unusual low dielectric loss. The parallel aligned Bi2S3 nanorods along the tensile-strain direction could be responsible for the improvement of dielectric properties of the composites. This study also provides an extremely useful method to reduce the dielectric loss of similar kinds of composites.
Many studies show that the dielectric constant would be greatly enhanced when metal and/or ceramic fillers were employed in polymer-based composites.11–15 Dang et al. prepared high-K CCTO/PI functional hybrid films; a high dielectric constant (49) is obtained at 102 Hz when the concentration of the CCTO filler reaches 40 vol%.16 Researchers note, however, that the reliability is of great importance for a capacitor. Therefore, it is urgent to seek a kind of material which can achieve a high dielectric constant and a low dielectric loss at low content. One important approach to improve the dielectric properties of composites is to incorporate ceramic nanoparticles into the polymer matrix to enhance their relative permittivity. For instance, L. Zhang et al. have prepared BST–P(VDF–CTFE) 0–3 nanocomposites, for the composites with a 40 vol% of BST, a dielectric constant of 70 with a loss of 0.07 at 1 kHz is obtained at room temperature.17 Sodano et al. reported a BaTiO3 nanowires/PVDF composite with a dielectric constant of about 44.3, when the concentration of the conducting filler is 30 vol%.18 However, the volume fraction of ceramic particles is usually very high, which will do great damage to the mechanical properties of the polymer based composites.19
To overcome the above shortcomings, inorganic conductors are often employed to increase the dielectric constant of the polymer matrix based on the percolation theory.20 However, the corresponding loss and leakage currents of these composites are too high to meet the requirements of realistic applications. The one-dimensional fillers caused wide attention because of their large aspect ratio,21 so that the composites with these fillers can reach the percolation threshold at low content. Zhang et al. found that the fitting constant fc increases with increasing frequency and they believed that this arises from the critical phenomenon, εeff ∝ fγ−1, for composites close to the fc.22 Nan et al. reported the dielectric properties of PVDF/Bi2S3 nanorod (nr-Bi2S3) composites, and the dielectric constant could reach 160.23 However, it is found that the dielectric loss of these percolative composites is usually quite high. This is because the nanoscale fillers with a large aspect ratio are partially connected to each other and form a conductive network with the increase of conducting fillers, which can be blamed for the electric leakage loss. At the low frequency, the electric leakage could be considered to make the major contribution to the dielectric loss.24 As a result, the dielectric loss of these percolative composites is usually high when the percolation threshold is achieved.25 What really impacts the practical use of these percolative composites materials is dielectric loss, which is rarely mentioned and deserves more attention.
Therefore, the main challenge is how to reconcile the contradiction of lowering the dielectric loss while maintaining high dielectric constant. There are many methods to lower the dielectric loss of nanocomposites, such as treating the nanoparticles with coupling agents;26,27 fabricating nanocomposites via in situ olefin polymerization and employing core@shell structured fillers. Xie et al. successfully lower the dielectric loss of polymer nanocomposites by using core–satellite structured ultra-small silver (Ag) decorated barium titanate (BT) nanoassemblies.28 Nowadays, structure design, as a new method to improve the dielectric properties of polymer composites has drawn wide attention. Our previous results showed that the addition of Bi2S3 could enhance the dielectric properties of the PVDF and polyethylene (PE).29,30 We have also fabricated an orderly polymer composite with zinc flakes (ZFs) oriented parallel in the PVDF, which obtained a high dielectric constant of 176 but a low loss of 0.06 at 103 Hz.31 Along this line, we expect to prepare one-dimensional directional composites by structural design, which have a high dielectric constant and a low dielectric loss at low content.
Tensile strain is usually employed to enhance the tensile strength and modulus of polymer composites.32 Very few studies have focused on the effect of tensile strain on dielectric properties. Yao et al. studied the effect of tensile strain on the dielectric properties of multiwall carbon nanotube (MWNT)/poly(vinylidenefluoride) (PVDF) nanocomposites, the maximum increment in the dielectric constant of the composite can reach 30% at 102 Hz relative to that before stretching.33 Dang et al. have studied the effect of tensile strain on the morphology and dielectric properties in nanotube/polymer nanocomposites;34 the dielectric constant and conductivity always decreased after the composites were stretched. So in this work, a novel but simple method (hot-stretching and hot-pressing) is developed to lower the dielectric loss of the two-phase Bi2S3/PVDF composites while maintaining a high dielectric constant. By designing such a one-dimensional well-aligned parallel structure, a significant reduction in dielectric loss of the novel two-phase Bi2S3/PVDF composite is observed, while the dielectric constant remains at a high level at a lower content.
The fractured surface morphology of the samples was examined by scanning electron microscopy (FEI Siron 200). The dielectric properties were measured by employing an Agilent 4294A Impedance analyzer in the frequency range of 100 Hz to 10 MHz at room temperature. The out-of-plane dielectric properties of the nanocomposites were studied in this work.
The composite films were fabricated by a casting procedure at 80 °C. The cross-section micrograph Fig. 1b and c of the composite samples demonstrate that the Bi2S3 nanorods are homogeneously dispersed into the PVDF matrix without serious aggregation at low Bi2S3 nanorod content, i.e., fBi2S3 = 2 vol%. However, as fBi2S3 increases, some Bi2S3 aggregates emerge, as shown in Fig. 1d (fBi2S3 = 4 vol%) and Fig. 1f (fBi2S3 = 10 vol%). The films were stretched along the casting direction at 160 °C. After stretching, the nanorods had preferential orientation in the direction parallel to the tensile strain, which could be clearly seen in the cross-section micrograph Fig. 1b, d, and f.
As shown in Fig. 1e, numerous cross surface Bi2S3 nanorods could be observed, and whole nanorods can barely be seen in the picture because this cross-section is perpendicular to the tensile-strain direction. The holes in this picture should be attributed to the extraction of Bi2S3 nanorods, because the size of the hole is basically consistent with the diameter of the Bi2S3 nanorods and there are no clear holes in Fig. 1b. By contrast, no preferential orientation of Bi2S3 nanorods could be observed in the disoriented samples (D-S) (see Fig. 1c). Due to the big difference in the tensile strength and modulus of the PVDF matrix and Bi2S3 nanorods fillers, the stretching process will do great damage to the interface between the matrix and the fillers of the nanocomposite and decreased the dielectric properties. But there are no clear defects to be seen in Fig. 1b at low Bi2S3 nanorods content, which shows that the hot-stretching process can fix the defects at high temperature above PVDF viscoelastic temperature. In the hot-stretching process, we call this phenomenon the effect of “self-repairing” when the matrix material (PVDF) is at its viscoelastic temperature.
From Fig. 1 we can draw a conclusion that the tensile strain played a crucial role in deciding the morphology of Bi2S3/PVDF nanocomposites. After that, a pressure at 200 °C was added along the direction perpendicular to the film plane when the film was cut into pieces, and then were stacked up along the tensile strain direction (the disoriented samples with no direction) into the hot-press mould. The hot-pressing progress could effectively reduce the bubble defect in the composite.
Fig. 2 shows the dependences of dielectric constant, dielectric loss and conductivity of the Bi2S3/PVDF composites with different concentrations of Bi2S3 nanorods with oriented structure and disoriented structure on frequency at room temperature. A conclusion can be drawn that the dielectric constant, dielectric loss and conductivity of the composites always increased with the increasing Bi2S3 nanorods, whether the Bi2S3 nanorods are oriented or not. The dielectric constant of the composites always decreased with the increasing frequency, while the conductivity is increased. At a low frequency range, according to the interfacial polarization or Maxwell–Wagner–Sillars effect,36 because of the different relaxation time of the PVDF and Bi2S3 nanorods lots of free charge carriers generated by surface polarization are blocked at the interfaces between Bi2S3 nanorods and the PVDF matrix, and lots of dipoles form on the Bi2S3 nanorods. The inertia of the formed dipoles causes the polarization spend to take much more time than other dielectric processes, thus the interfacial polarization occurs at low frequency and dielectric constant and loss decrease rapidly when the frequency increases. At a high frequency range, the electrical properties of the composites are dominated by the PVDF. Therefore, the dielectric constant is comparatively independent of frequency and is generally lower than that at low frequency, and the dielectric properties of the Bi2S3/PVDF nanocomposites change little with tensile strain at high frequency.
Fig. 2 Frequency-dependence of: (a) dielectric constant, (b) dielectric loss and (c) conductivity of the oriented and disoriented Bi2S3/PVDF composites with different fBi2S3 at room temperature. |
Fig. 3 shows the schematic images of how tensile-strain affects the Bi2S3 nanorods distribution in polymer composites. The (a) and (a′) are disoriented and oriented samples at low content filling, while (b) and (b′) are disoriented and oriented samples at high content filling, respectively. Because the Bi2S3 nanorod was an anisotropic rod material with a large aspect ratio, the nanorods are rearranged along the tensile-strain direction when the Bi2S3/PVDF composites are stretched. This mechanism has been verified by the SEM micrographs as shown in Fig. 1.
It is well known that the enhancement of the dielectric constant in the low frequency range is mainly due to the contribution of interfacial polarization associated with the entrapment of space charges at the interfaces of the fillers and matrix. Therefore, the anisotropic dielectric constant could be ascribed to the anisotropic intensity of interfacial polarization. According to the theory of dielectrics, the polarization intensity P is defined as31
(1) |
As shown in Fig. 3, after stretching, the distance between the Bi2S3 nanorods is greatly reduced in the direction perpendicular to the tensile strain. Therefore, the displacement l of the oriented samples is obviously higher than that of the disoriented samples in the perpendicular direction, which leads to the stronger intensity of interfacial polarization and a higher dielectric constant. Simultaneously, with the increase of Bi2S3 nanorods, a fast increase of dielectric constant can be found in the disoriented samples (see Fig. 4a).
Fig. 4 At 1048 Hz, the dependence of (a) dielectric constant, and the inset in (a) presents the best fitting of dielectric constants of disoriented samples according to eqn (1); (b) dielectric loss and (c) conductivity of the oriented and disoriented Bi2S3/PVDF composites on the fBi2S3, measured at room temperature. |
According to percolation theory, when fBi2S3 is less than fc, the dielectric constant (ε) near the percolation threshold can be characterized by the power law,20,37 as follows:
ε(fBi2S3) ∝ (fc − fBi2S3)−s as fBi2S3 < fc | (2) |
It can be seen from Fig. 4 that, at 1048 Hz, with increasing concentration of Bi2S3 nanorods, the differences in dielectric constant and dielectric loss between the oriented and disoriented composites become more significant. At 1048 Hz, for fBi2S3 = 4 vol%, the dielectric loss of the disoriented sample is 0.21472 which is about 3 times higher than that of oriented sample (0.05561). However, when fBi2S3 increases to 10 vol%, the dielectric loss of the disoriented sample is 1.672, which is almost 9 times of that of the oriented sample (0.1975).
The conductive network is very important to improve the dielectric constant as well as the dielectric loss of composites. When fBi2S3 is low, most of the Bi2S3 nanorods are fully dispersed in the matrix without serious aggregation, which may be due to the solvent evaporation process. Tensile strain cannot do much under these circumstances, so the change of the dielectric properties of these two series composites is not obvious (see Fig. 4). However, the Bi2S3 nanorods begin to connect to each other and form a conductive network with increasing volume content. In this case, the conductive network is destroyed by the tensile strain, because the Bi2S3 nanorods prefer to stay along the tensile strain direction and parallel to each other when the tensile strain is employed, which decreases their chance to connect each other.
There is a gradual enhancement of dielectric constant with increasing fBi2S3 with low loading of Bi2S3 nanorods. However, when fBi2S3 > 0.08, both the dielectric constant and dielectric loss of the disoriented composites have a dramatic enhancement, while the oriented composites don’t have. With the increasing Bi2S3 nanorods, the conductive phase Bi2S3 nanorods began to connect, and form the conductive network where the dielectric constant abruptly increases. When the conductive network formed, the leakage current increased dramatically, so the dielectric loss also abruptly increased. Because of the tensile strain, the phenomenon of oriented composites did not appear. The oriented composites need many more Bi2S3 nanorods to form the conductive network, which means the hot-stretching process delayed the percolation threshold of the composites. This could be explained by the rearrangement of Bi2S3 nanorods in the composites which destroyed the network structures. In this case, numerous clusters were broken off, and subsequently the Bi2S3 nanorods were rearranged along the tensile-strain direction in a preferential orientation. That is, numerous Bi2S3 nanorods in the composites were parallel to the tensile-strain direction after stretching. As a result, the dielectric constant and conductivity of the Bi2S3/PVDF nanocomposites decreased significantly.
The change in dielectric constant with the filled content of Bi2S3 nanorods at different frequencies is shown in Fig. 5. The dielectric constant increases with increasing fBi2S3 at all considered frequencies, which is due to the conductivity increase of semiconductive Bi2S3 nanorods. As the frequency increases, the dielectric constant increases slowly for these two kinds of composites. At low frequency, the molecules have enough time for polarization. However, at high frequency, the polarization of molecules does not have enough time to catch up with the change in electrical field frequency, which leads to the weak dependence of dielectric constant on the filled content.29 Comparing Fig. 5a with 5b, we can conclude that the dielectric constant of the D-S deceased more intensely than that of O-S, as we have mentioned before.
Fig. 5 The change in dielectric constant with the filled content of Bi2S3 nanorods at different frequencies. |
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