Polyvinylpyrrolidone modified barium zirconate titanate /polyvinylidene fluoride nanocomposites as self-powered sensor

Highly flexible biocompatible nanocomposites comprising of Polyvinylpyrrolidone (PVP) modified Barium Calcium Zirconate Titanate (BCT-BZT) /Polyvinylidene fluoride (PVDF) were fabricated. The crystalline BCT-BZT powders were synthesized by a simple sol-gel method. Rietveld refinement analysis confirmed the coexistence of orthorhombic and tetragonal phase in the synthesized powders. The structural, dielectric and ferroelectric properties of the composites were analysed. Addition of PVP modified BCT-BZT powders was observed to enhance the polar phase in PVDF matrix. The piezoelectric output response as a function of different weight percentage of ceramic powders in the PVDF matrix was investigated. The optimal device with 60?wt% PVP modified BCT-BZT powders exhibited maximum peak to peak voltage of 23?V when tested for harnessing waste biomechanical energy (human hand palm force). The nanogenerator was easily scaled up to 4?×?4?cm and the stored power was utilized for powering fifty five LEDs. The fabricated device is flexible, light- weight and eco-friendly. Therefore, it can be explored as a potential candidate for application as self powered sensor.     

Resistivity behaviour of barium titanate (BaTiO3)/polyvinylidene fluoride (PVDF) composites

The resistivity behaviour of Barium Titanate (BaTiO₃) / Polyvinylidene Fluoride (PVDF) composites studied by changing the wt. fraction of BaTiO₃. The resistivity behaviour of composites followed that of PVDF up to 50% wt. fraction of BaTiO₃ in the composite. The resistivity of the composite with 70% wt. fraction of BaTiO₃ varied one order. The results are correlated with SEM studies on the composites. At a lower wt. fraction of BaTiO₃ in composites, PVDF formed an insulating layer over BaTiO₃ grans, which is not significant at higher wt. fractions of BaTiO₃ in the system     

Effect of polyvinylidene fluoride on the fracture microstructure characteristics and piezoelectric and mechanical properties of 0-3 barium zirconate titanate ceramic-cement composites

Barium zirconate titanate (40−60 vol.%; BZT), Portland cement (PC) and polyvinylidene fluoride (0−7 vol.%; PVDF) were used as raw materials to produce 0–3 piezoelectric cement-based composites. The highest piezoelectric charge coefficient (d₃₃∼26-27 pC/N) was found at 50−60 vol.% BZT with 5 vol.% PVDF. Moreover, the composite with 50 vol.% BZT and 5 vol.% PVDF had the highest piezoelectric voltage coefficient (g₃₃ = 16.0 × 10⁻³ V·m/N). Scanning electron microscopy was used to investigate the morphology of the fracture surface of the composite. When PVDF was used in the composite, it was observed to fill some pores at the interface zone and within the cement phase. The elastic behaviour of PVDF could also be seen in the fracture surface, where it appeared as a stretched material different from both the BZT ceramic and cement, which are brittle materials. In addition, increasing the PVDF content led to increased fracture toughness.     

Doping influence on structural ferroelectric phase transitions and electrical features of barium calcium titanate

We comprehensively report Sr, Cr, Mn, and Mg doping ions' influence on structural and dielectric properties of barium calcium titanate (BCT) ceramics over a wide temperature and frequency range. X-ray diffraction and electrical studies showed the phase transition (PT) from paraelectric (PE) to ferroelectric (FE) phase. The linear and nonlinear susceptibility measurement identified the discontinuous PT of BCT and Sr-doped BCT. Moreover, this measurement also distinguished diffused PE-FE PT features induced in BCT by the Cr and Mn ions. Exceptionally, the Mg ion doping caused the relaxor-like features in BCT. Distribution of relaxation times indicated a mixed order-disorder and displacive character of PT. The doping of Cr, Mn, and Mg ions shortened the relaxation times related to the B-sublattice ions jumping. We also confirmed low-temperature FE-FE PT via linear and nonlinear dielectric susceptibility and pyroelectric measurements. We showed that non-zero net polarization could be induced by an applied electric field.     

Electrical behavior and positive temperature coefficient effect of graphene/polyvinylidene fluoride composites containing silver nanowires

Polyvinylidene fluoride (PVDF) composites filled with in situ thermally reduced graphene oxide (TRG) and silver nanowire (AgNW) were prepared using solution mixing followed by coagulation and thermal hot pressing. Binary TRG/PVDF nanocomposites exhibited small percolation threshold of 0.12 vol % and low electrical conductivity of approximately 10^-7 S/cm. Hybridization of TRGs with AgNWs led to a significant improvement in electrical conductivity due to their synergistic effect in conductivity. The bulk conductivity of hybrids was higher than a combined total conductivity of TRG/PVDF and AgNW/PVDF composites at the same filler loading. Furthermore, the resistivity of hybrid composites increased with increasing temperature, giving rise to a positive temperature coefficient (PTC) effect at the melting temperature of PVDF. The 0.04 vol % TRG/1 vol % AgNW/PVDF hybrid exhibited pronounced PTC behavior, rendering this composite an attractive material for making current limiting devices and temperature sensors.     

Theoretical and experimental studies on the gas transport properties of mixed matrix membranes based on polyvinylidene fluoride

The effects of the impregnation of three types of inorganic fillers into polyvinylidene fluoride (PVDF) polymer membranes on the gas permeability and selectivity of these membranes were studied theoretically and experimentally. Permeabilities of He, CO₂, O₂, and N₂ through three types of mixed matrix membranes (MMMs) based on PVDF, that is, PVDF/SiO₂, PVDF/MCM‐41, and PVDF/4A MMMs, were experimentally measured and theoretically predicted using Maxwell, Higuchi, Bruggeman, and Bottcher‐Landauer models. Theoretical permeabilities of the PVDF/SiO₂ MMMs using the above four models predicted the results in the following order: Maxwell model>Bruggeman model>Bottcher model>Higuchi model. However, this sequence was reversed for PVDF/MCM‐41 MMMs. The nonporous SiO₂, mesoporous MCM‐41 and zeolite 4A inorganic fillers had effects on the permeabilities of the challenge gases for the PVDF/SiO₂, PVDF/MCM‐41, and PVDF/4A MMMs but had no effects on the selectivities of the MMMs. The experimental permeabilities of the MMMs showed that there were no significant differences among the three types of MMMs despite that the inorganic fillers, that is, SiO₂, MCM‐41, and zeolite 4A, had distinct dissimilar properties such as pore structures and particle sizes. Density measurements indicated that some voids were present in the polymer/particle interfaces. Based on the density measurement results, the void volume fractions of the resulting MMMs were calculated. An equation is derived to determine the void thickness of the MMM in terms of its physical properties and hence this proposed equation can substitute the difficult task of measuring such void thickness through any microscopy techniques. The Maxwell, Higuchi, Bruggeman, and Bottcher‐Landauer models could not predict the actual gas permeabilities of the PVDF MMMs. By taking the effects of crystallinity and immobilization factor on gas permeability into consideration, the extended modified Maxwell model showed good agreement with the experimental gas permeabilities of the resulting MMMs, indicating that the model did capture the essence of the gas transport behaviors through the MMMs. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4715–4726, 2013     

Effect of heat treatment on the electrical properties of lead zirconate titanate/poly (vinylidene fluoride) composites

Ceramic/polymer composites are attracting increasing interest in materials research and practical applications due to the combination of excellent electric properties of piezoelectric ceramics and good flexibility of polymer matrices. In this case, the crystallization of the polymer has a significant effect on the electric properties of ceramic/polymer composites. Based on different heat treatment methods, the crystallization of poly(vinylidene fluoride) (PVDF) in composites of lead zirconate titanate (PZT) and PVDF can be controlled effectively. PZT/PVDF composites with various PVDF crystallizations exhibit distinctive dielectric and piezoelectric properties. When the crystallization of PVDF is 21%, the PZT/PVDF composites show a high dielectric constant (ε) of 165 and a low dielectric loss (tan δ) of 0.03 at 10³ Hz, and when the crystallization of PVDF reaches 34%, the piezoelectric coefficient (d₃₃) of PZT/PVDF composites can be up to ca 100 pC N^?1. By controlling the crystallization of PVDF, PZT/PVDF composites with excellent dielectric and piezoelectric properties were obtained, which can be employed as promising candidates in high‐efficiency capacitors and as novel piezoelectric materials. Copyright © 2010 Society of Chemical Industry     

Effect of holmium substitution on structural and electrical properties of barium zirconate titanate ferroelectric ceramics

The holmium substituted Ba_1−3x/2Ho_xZr_0.025Ti_0.975O₃ (x=0.01, 0.02, 0.025, 0.05) compositions were synthesized by the solid state reaction technique. The synthesized specimens were characterized for their structural and electrical properties using X-ray diffractometer, scanning electron microscopy, impedance analyzer and loop tracer. Phase analysis shows the formation of secondary phase Ho₂Ti₂O₇ for Ho≥2.5 mol% substitution. The microstructural investigation shows that the holmium substitution significantly reduces the grain size. The substitution of holmium increases the Curie temperature for x≤0.02 whereas Curie temperature decreases for x≥0.025. The maximum dielectric constant at transition temperature is observed for x=0.02. The solubility limit is 2 mol% and for x≥0.025 some of the holmium atoms enter B-sites and forms the secondary phase. An increase is observed in the coercive field of the specimens with the increasing holmium content.     

Enhanced high temperature dielectric polarization of barium titanate/magnesium aluminum spinel composites and their potential in microwave absorption

Antioxidant materials with high permittivity are highly desirable for thin, microwave-absorbing materials at high temperature (MAMHT) due to their great impedance matching. In this work, composite ceramics composed of BaTiO₃ and MgAl₂O₄ (BTMAS) synthesized by a traditional solid-state sintering method have been studied for their high temperature microwave dielectric properties. When the temperature rose between 473 K–573 K, the real part of permittivity (ε’) of BTMAS increased significantly relative to room temperature. As the temperature increased further to 873 K, ε’ gradually fell. Based on the collection of permittivities obtained by the inverse resolution of specific reflectivity, BT36 (36 mol % BaTiO₃) was suitable for 1.1 mm thick microwave-absorbing materials from 300 K – 873 K. The envisaged material had an absorption bandwidth of 2 GHz (RL<-5 dB) which could move between microwave X-band as the temperature changed. Therefore, there is great potential for BTMAS in reducing the thickness of MAMHT.     

Thermal effects on the percolation behavior of polyvinylidene fluoride/nickel composites

Percolation theory predicts the ideal percolation threshold (P_C) for insulator/conductor composites (ICC) to be at 0.16 of the conductor volume fraction in the composite. In this article, we have investigated the percolation behavior in polyvinylidene fluoride/nickel (Ni) composites by varying the Ni concentration. It is observed that the thermal effect/time of heat treatment play a crucial role in changing the value of P_C in a simple random continuum percolative ICC. The effect is attributed to decrease in: (i) intercluster distance, (ii) viscosity of the polymer, and (iii) wetting of the polymer to metal. The heat energy helps the polymer matrix to be melted as a result the metal particles/clusters come closure, that causes an increase in the cluster size of the metal particles. The overall effect is lowering of P_C mainly due to decrease in intercluster distance. A drastic enhancement in the dielectric permittivity with increase of metal content is explained using boundary layer capacitive effect arising due to Maxwell–Wagner–Sillars interfacial polarization of accumulated charges at the metal–polymer interfaces and blocking of charge carriers at the insulating boundary. The substantial enhancement of ac conductivity at the P_C is attributed to leakage of charge carriers across the insulating barrier. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Lead-free pyroelectric infrared detector based on (Bi1/2Na1/2)TiO3-BaTiO3 ferroelectric ceramics

In this paper, we theoretically and experimentally reported a lead-free pyroelectric infrared (PIR) detector using (Bi_1/2Na_1/2TiO₃)-BaTiO₃(BNT-BT) ferroelectric ceramics as the sensitive material. The variation of noise density, voltage response rate (R_V), and specific detection rate (D*) with the modulation frequency under the current mode amplification circuit was investigated, and it was found that the lead-free PIR detector showed high R_V in the low frequency band. The R_V and D* reached 1.51 × 10⁵ V/W and 2.02 × 10⁸ cmHz^1/2W⁻¹ at 10 Hz, respectively. The results were much superior to the PIR based on traditional commercial pyroelectric ceramics, indicating that BNT-BT lead-free ceramics have great potential in application to PIR detectors.     

Fabrication and characterization of electrolyte membranes based on organoclay/tripropyleneglycol diacrylate/poly(vinylidene fluoride) electrospun nanofiber composites

Utilizing polymer electrospinning technology, novel electrolyte membranes based on poly(vinylidene fluoride) (PVDF)/organomodified clay (OC)/tripropyleneglycol diacrylate (TPGDA) composite nanofibers with a diameter of 100–400 nm were fabricated for application in lithium batteries. Ultraviolet photo‐polymerization of electrospun PVDF/OC/TPGDA nanofibers generated chemically crosslinked TPGDA‐grafted PVDF/OC nanofibers exhibiting robust mechanical and electrochemical properties. The prepared fibrous PVDF/OC/TPGDA electrolytes were characterized in terms of morphology, crystallinity, electrochemical stability, ionic conductivity and cell cycleability. Based on differential scanning calorimetry analysis, the crystallinity of PVDF decreased by ca 10% on employing the OC and TPGDA. Compared with pure PVDF film‐based electrolyte membranes, the TPGDA‐ and OC‐modified PVDF electrolyte membranes exhibited improved mechanical properties and various electrochemical properties. The OC‐ and TPGDA‐modified microporous membranes are promising candidates for overcoming the drawbacks of the lower mechanical stability of fibrous‐type electrolytes with further improvement of electrochemical performance. Copyright © 2009 Society of Chemical Industry     

SiO2/Al2O3 ratio dependence of microstructures and dielectric properties in barium strontium titanate glass ceramics

(Ba, Sr)TiO₃-Al₂O₃-SiO₂ glass ceramic system with various SiO₂/Al₂O₃ ratios was investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), dielectric spectroscopy and impedance spectroscopy. The XRD results demonstrated that the proper SiO₂/Al₂O₃ ratio could promote the crystallization of the major crystalline phase from the glass matrix. The dielectric property investigations showed that the dielectric constant passes through a maximum value while the dielectric breakdown strength has a minimum value with increasing SiO₂/Al₂O₃ ratio. Meanwhile, the complex impedance analyses suggest the resistance of the glass-crystal interface rapidly decreases and the capacitance of the crystal slightly decreases with the increase of SiO₂/Al₂O₃ ratio. The relaxation mechanisms of the (Ba, Sr)TiO₃ glass ceramics changed from localized relaxation to long range conductivity as the SiO₂/Al₂O₃ ratio was increased from 1.43 to 1.83. The variations in the dielectric response and the activation energy of the glass-crystal interface in the (Ba, Sr)TiO₃ glass ceramics with the ratio of 2.40 could be attributed to the crystallization of fresnoite phase.     

Effect of magnesium titanate content on microstructures,mechanical performances and dielectric properties of Si3N4-based composite ceramics

Silicon nitride-based composite ceramics with different contents of magnesium titanate have been fabricated via gas pressure sintering method. The phase compositions, microstructure, mechanical performances and dielectric properties of the composite ceramics were investigated. The density of the Si₃N₄-based composite ceramics firstly increased with additive of magnesium titanate powder up to 5 wt% and then gently decreased, and the mechanical properties firstly increased and then declined. Besides, the dielectric constant and dielectric loss increased with the increase of magnesium titanate contents. For the Si₃N₄-based composite ceramics with 5 wt% magnesium titanate powders, the flexural strength, elastic modulus, dielectric constant and dielectric loss reached 451 MPa, 274 GPa, 7.65, 0.0056, respectively. These results suggested that the magnesium titanate was beneficial for the improvement of mechanical performances and dielectric constant of Si₃N₄-based composite ceramics.     

Structure and morphology of composites based on polyvinylidene fluoride filled with BaTiO3 submicrometer particles: Effect of processing and filler content

Composites based on polyvinylidene fluoride filled with barium titanate (PVDF/BT) submicrometric particles were prepared. To uniformly disperse BT particles within PVDF, high‐energy ball cryomilling was used. The effect of processing and the presence of BT particles on the structure and morphology of the composites were analyzed by Fourier transformed infrared spectroscopy, X‐ray diffraction, differential scanning calorimetry, and atomic force microscopy. In terms of the structure, it can be concluded/stated that after milling the α‐ and γ‐PVDF crystalline phases are reduced, whereas the content in the β phase is increased. On the other hand, after film formation, the α phase was recovered. It was demonstrated that the milling process is the most important factor to increase the amount of β phase, being favored by the presence of BT particles. In terms of the morphology, it was observed that the PVDF lamellar aspect ratio increases with the amount of BT in cryomilled samples processed as films. Besides, the crystallization kinetics is highly affected by the milling process and the presence of BT, being the relative crystallization rate slower with the presence of BT. POLYM. COMPOS., 34:2094–2104, 2013. © 2013 Society of Plastics Engineers     

Effects of Sm-substitution on dielectric,ferroelectric, and piezoelectric properties of 0.36(Bi1-xSmx)ScO3-0.64PbTiO3 ceramics

Dielectric, ferroelectric, and piezoelectric properties of 0.36(Bi_1-xSm_x)ScO₃-0.64PbTiO₃ (BSPT-xSm) ceramics were investigated to assess effects of Sm-substitution on 0.36BiScO₃-0.64PbTiO₃ for high temperature piezoelectric device application. Optimal sintering was achieved at 1200°C when the BSPT-xSm ceramics were fully densified and crystallized with a perovskite structure without any secondary phase. The substitution of Bi³⁺ with Sm resulted in degradation of rhombohedral side in BSPT-xSm ceramics having morphotropic phase boundary. In addition, variations of grain size and ferroelectric behavior after Sm-substitution were insignificant. However, dielectric constant (ε^T₃₃/ε₀) was significantly enhanced with an increasing of amount of Sm to 5%. Although a slight decrease of relative density in case of x exceeding 3% led to deterioration of piezoelectric values of d₃₃, k_p, and d₃₃*, the BSPT-3%Sm ceramic exhibited excellent values of d₃₃ of 628 pC/N, k_p of 62.4%, and d₃₃* of 718 pm/V at 4.5 kV/mm, along with a high ferroelectric transition temperature of 421°C. The highly increased diffusion coefficient of 1.909 also implies that the Sm-substitution contributed to relaxor-like ferroelectric behavior of BSPT ceramics.     

Effect of the ceramic particle size on the microstructure and dielectric properties of barium titanate/polystyrene composites

Excellent dielectric properties are a key factor for the technology of capacitors. Some ceramics, such as barium titanate (BaTiO₃ or BT), have high dielectric constants, although they are hard to process. Polymers that often display low dielectric permittivities are easy to fabricate into all kinds of shapes. So the preparation of one composite material consisting of polymer and ceramic particles may be an excellent solution for satisfying the processing requirements. In this study, fresh polystyrene (PS) was synthesized and subsequently used to prepare BT/PS composites with a ball‐grinding mixture technology. The microstructure and dielectric properties of the BT/PS composites at different frequencies and different temperatures were studied. The results show that the dielectric permittivities of the composites with BT with a particle diameter of approximately 700 nm (BT‐07) were obviously higher than those of the composites with BT with a particle diameter of approximately 100 nm (BT‐01) at the same concentration of BT. Moreover, the dielectric permittivities of the composites with BT‐01 displayed better stabilization than those made with BT‐07 at the different temperatures. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of composition and grain size on dielectric,ferroelectric and induced strain behavior of PLZT/ZrO2 composites

Lead lanthanum zirconate titanate ceramics (PLZT) are well known for their excellent dielectric, piezoelectric and ferroelectric properties. In this study, PLZT 9/70/30, 9/65/35 and 9/60/40 ceramics were prepared by vibro-milling mixed-oxide method. All compositions of powders were uniaxial pressed in pellets and sintered at the temperatures of 1200–1275 °C with various soaking times of 2, 4 and 6 h. The X-ray diffraction (XRD) patterns confirmed that all the PLZT samples had perovskite structure with ZrO₂ as a second phase and PLZT/ZrO₂ composite structure was formed. Dielectric behavior at the frequency of 1 kHz showed broad peak indicating relaxor ferroelectric behavior and the difference of the temperature at maximum dielectric at different frequencies increased when Zr:Ti ratio increased. Polarization with electric field (P-E loop) at room temperature showed that when Zr:Ti ratio increased, the coercive field decreased resulting from crystal structure change from tetragonal to rhombohedral. Induced strain with electric field depended on microstructure where the value of S_max/E_max tended to decrease with increasing grain size. It can be concluded that dielectric and ferroelectric behavior predominantly depended on composition of PLZT ceramics and induced strain behavior predominantly depended on grain size of PLZT ceramics.     

Preparation of LiNi1/3Co1/3Mn1/3O2/polytriphenylamine cathode composites with enhanced electrochemical performances towards reversible lithium storage

A series of LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine composites were successfully synthesized by ultrasound dispersion method. LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine (5.0?wt%) composite with small and homogeneous particle size exhibited excellent electrochemical performance, which delivered an initial discharge capacity of 223.7?mAh g^?1 with a capacity retention of 84.39% after 100 cycles in the voltage range of 2.5–4.5?V and at a current density of 0.2C. Moreover, an excellent specific discharge capacity of 127.3?mAh g^?1 at a current density 5C indicates a superior rate performance of the LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine (5.0?wt%) composite. The good electrochemical performances of the composite can be attributed to the introduction of polytriphenylamine, which increased electrical conductivity, decreased charge transfer resistance and increased Li⁺ ion diffusion ability. These noteworthy results demonstrated that LiNi_1/3Co_1/3Mn_1/3O₂/polytriphenylamine composites might be potential cathode materials for lithium ion batteries.     

Enhanced energy storage performances of Bi(Ni1/2Sb2/3)O3 added NaNbO3 relaxor ferroelectric ceramics

In the development of dielectric ceramic materials, the requirements of miniaturization and integration are becoming increasingly prominent. How to obtain greater capacitance in a smaller volume is one of the important pursuits. In this paper, lead-free (1-x)NaNbO₃-xBi(Ni_1/2Sb_2/3)O₃(xBNS) with high recoverable energy storage density (W_rec) and relatively high energy storage efficiency(η) were prepared by a solid state sintering method. Bi(Ni_1/2Sb_2/3)O₃ was introduced into the Sodium niobate ceramics(NN)-based ceramics to reduce the sintering temperature and increase the maximum breakdown field strength (E_b). Finally, 0.15BNS achieved a high E_b of 460 kV/cm, W_rec of 3.7 J/cm³ and η of 77%. In addition, the sample maintained excellent stability in the frequency range of 1–120 Hz. And the 0.15BNS ceramics also exhibited high power density (P_D = 36.4 MW/cm³), large current density (C_D = 520.8 A/cm²) and relatively fast charge-discharge rate (t_0.9 = 1050 ns). These results demonstrate the potential application value of xBNS ceramics in energy storage capacitors.