Dielectric properties and spatial distribution of polarization of ceramic + polymer composite sensors

Thin films ceramic + polymer composite sensors with mixed connectivities possess high values of piezo- and pyroelectric coefficients and the formability and flexibility which are not attainable in a single-phase ferroelectric material, i. e., an electroceramic or a polymer. The efficiency and the piezo- and pyroelectric figure of merit (FOM) are influenced by the temperature dependence of the dielectric properties and the nature of the spatial distribution of polarization of the composite material. We report the results of a study of dielectric properties of calcium – modified lead titanate (PTCa) and a polar copolymer, polyvinylidene fluoride and trifluoroethylene P(VDF-TrFE) and PTCa and epoxy in a wide frequency range. Each of the two composites was fabricated with two different volume fractions of the constituent phases. Furthermore, the spatial distribution of polarization was determined by the laser intensity modulation method (LIMM) for each composite sensor in order to assess the polarization distribution of the sensors. These results are also reported in this work. Received: 6 November 2000 / Reviewed and accepted: 7 November 2000     

Dielectric properties of epoxy/short carbon fiber composites

The dielectric properties of epoxy/short carbon fiber composites at different concentrations 0, 5, 10 and 15% by weight, different thicknesses 2 and 4 mm, and frequency in the range from 20 Hz to 1 MHz were characterized. Scanning electron microscopy and differential scanning calorimetry were utilized. The alternating current (ac) electrical properties (complex impedance, dielectric constant, dielectric loss, real part of electric modulus, imaginary part of electric modulus, electrical conductivity, and relaxation time) were determined. It was found that the applied frequency, filler concentrations, and composite thickness affected the ac electrical properties of the epoxy/carbon fiber composites. The dielectric behaviors of the interfacial polarization between epoxy matrix and carbon fibers could be described by the Maxwell–Wagner–Sillars relaxation. The analysis of the complex electric modulus in the frequency range from 20 Hz to 1 MHz revealed that the interfacial relaxation followed the Cole–Davidson distribution of relaxation times. The universal power-law of ac conductivity was observed in the epoxy/carbon fiber composites. The calculated power exponent (near unity) is physically acceptable within this applied model.     

Characterisation of proton irradiated Ba0.65Sr0.35TiO3/P(VDF-TrFE) ceramic–polymer composites

Barium strontium titanate/poly (vinylidene fluoride-trifluoroethylene)70/30 (Ba_0.65Sr_0.35TiO₃/P(VDF-TrFE) 70/30) composite with high dielectric permittivity was developed by integrating high dielectric permittivity ceramic powder with proton irradiated polymer matrix. The composite after irradiation behaves as a relaxor ferroelectric material and this behaviour is similar to that of irradiated P(VDF-TrFE) 70/30 co-polymer. Due to the irradiation, dielectric peaks broadened and moved towards the lower temperature, creating high relative permittivity values in a broad temperature range. Ba_0.65Sr_0.35TiO₃/P(VDF-TrFE) composite with 0.5 ceramic volume fraction with a dosage of 80 Mrad can reach a relative permittivity of 160 at room temperature (at 1 kHz), which is about 14 times higher than that of pure copolymer. Polarization-electric field hysteresis loops of composites are strongly depended on the ceramic powder volume fraction and the effects of irradiation is less apparent in composites with higher ceramic powder volume fraction.     

Enhanced ferroelectric and dielectric properties of the P(VDF-TrFE)/Ag nanoparticles composite thin films

The scope of the present work was the synthesis of homogeneously dispersed silver (Ag) nanoparticles (NPs) in P(VDF-TrFE) polymer by N,N-dimethylformamide’s reducing reaction on silver nitrate and the study on the surface micromorphology, crystalline phases, electrical and optical properties of the P(VDF-TrFE)/Ag NPs composite thin films. The results demonstrate that incorporating appropriate concentration of Ag NPs improve the ferroelectric and dielectric properties with an increase of 38 % in the remanent polarization and 47 % in dielectric constant respectively compared with the pristine P(VDF-TrFE) films. The reasons for the improved properties are explained by the effective compensation to the bounding charges provided by the appropriate amount of the Ag NPs fillers and Ag NPs’ acting as micro capacitors in P(VDF-TrFE) matrix. Furthermore, the surface plasmon resonance absorption in the composite films thin films is observed at the wavelength of ~415 nm, whose intensity is dependent on the density of the Ag NPs.     

Large dielectric constant in zirconia polypyrrole hybrid nanocomposites

Zirconia nanoparticles have been synthesized by a novel two-reverse emulsion technique and combined with polypyrrole (PPY) to form ZrO2-PPY nanocomposites. Complex impedance and dielectric permittivity of ZrO2-PPY nanocomposite have been investigated as a function of frequency and temperature for different compositions. The composite samples are characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy. The composites reveal ordered semiconducting behaviour. Polypyrrole is the major component in electrical transport process of the samples. A very large dielectric constant of about 12,000 at room temperature has been observed. The colossal dielectric constant is mainly dominated by interfacial polarization due to Maxwell-Wagner relaxation effect. Two completely separate groups of dielectric relaxation have been observed. The low frequency dielectric relaxation arises from surface defect states of zirconia nanoparticles. The broad peak at high frequency is due to Maxwell-Wagner type polarization.     

Dielectric and magnetic properties of Ca(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>/NiZn ferrite composites

Dense Ca(Zn_1/3Nb_2/3)O₃/NiZn ferrite composites with homogeneously fine microstructures were prepared through conventional solid-state method. The powder XRD patterns confirm the coexistence of the two phases. The dielectric properties in the low frequency range (100 Hz–1 MHz) follow the rule of Maxwell–Wagner interfacial polarization. The dielectric and magnetic properties in the high frequency range (10 MHz–1 GHz) are also reported. The results show that this kind of magnetic–dielectric composites could be used in high-frequency communications for the capacitor-inductor integrating devices such as electromagnetic interference filters and antennas.     

The effect of processing conditions on the morphology, thermomechanical, dielectric, and piezoelectric properties of P(VDF-TrFE)/BaTiO3 composites

In this study (0–3) P(VDF-TrFE)/BaTiO₃ composites containing up to 60 vol% of ceramic phase were prepared by solvent casting or compression molding. Their thermomechanical, dielectric, and piezoelectric properties were investigated, and discussed in the light of the properties of the basic components, the processing route and the resulting morphology. The crystalline structure of the P(VDF-TrFE) matrix was found to be highly dependent on the processing route, while the structure of BaTiO₃ was not affected by any of the processing steps. The mechanical properties of the solvent cast materials showed a maximum at 30 vol% BaTiO₃, while they increased monotonically with BaTiO₃ content for compression molded materials. This difference was attributed to a higher amount of porosity and inhomogeneities in the solvent cast composites. Permittivity as high as 120 and piezoelectric coefficient d ₃₃ up to 32 pC/N were obtained for compression molded composites, and the observed decrease in d ₃₃ with aging time was attributed to the effect of mechanical stress release in the polymer matrix.     

Ultrahigh field induced strain and polarization response in electron irradiated poly(vinylidene fluoride-trifluoroethylene) copolymer

 The influence of electron dosage on the field induced strain, dielectric constant, and polarization response has been investigated in electron irradiated poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) 50/50 copolymer. It was found that under suitable electron dosage an ultrahigh electrostrictive strain can be achieved. Interestingly, material after irradiation exhibits many features resembling those of relaxor ferroelectrics, suggesting that the electron irradiation breaks up the coherent polarization domain in normal ferroelectric P(VDF-TrFE) copolymer into nano-polar regions that transform the material into a relaxor ferroelectric. In addition, many of the material properties including the field induced polarization, the electrostrictive strain, and elastic modulus exhibit irregular change (non-monotonical) with electron dosage, indicating a complex relation among the crosslinking density, crystallinity, crystallite size, and molecular conformation in determining the material responses. Received: 10 June 1998 / Accepted: 30 July 1998     

Analysis on dielectric loss characteristics of polyvinylidene fluoride and its composites

In this study, barium calcium zirconate titanate nanoparticles and nanofibers (denoted as BZT-BCT NPs and BZT-BCT NFs, respectively) were prepared by the sol–gel method and electrospinning, respectively. Under different temperatures and frequencies, the dielectric spectra of polyvinylidene fluoride (PVDF), BZT-BCT NPs, and BZT-BCT NFs composites were measured. On the basis of the experimental data, the polarisation activation energies of the polymer matrix interfacial polarisation and the dipole turn polarisation were calculated, and the basic polarisation characteristic parameters of the polymer matrix materials and fillers were obtained. Moreover, the effects of the filling phase and filling ratio on the dielectric properties of the composites were studied through applying BZT-BCT NPs and BZT-BCT NFs as the filling phases of the PVDF matrix and PVDF matrix composites. Furthermore, the double-layer low-density polyethylene (LDPE)/PVDF composites as well as the LDPE/PVDF composites uniformly mixed at a volume fraction of 1:1 were prepared, and the interfacial polarisation behaviours of the two materials were studied by dielectric spectroscopy to establish an effective analytical method so as to characterize interfacial polarisation established. The experimental results revealed as follows: interfacial polarisation was a significant mechanism of the polarisation behaviour of the composite materials; the fillers with different shape factors had varying effects on the dielectric constant of composites; meanwhile, the dielectric constant of the composite conformed to the predictions of the effective medium theory model.

     

Characterization of poly(vinylidene fluoride-trifluoroethylene) 50/50 copolymer films as a gate dielectric

Thin films of poly(vinylidene fluoride-trifluoroethylene) (P(VDF-TrFE)) 50/50 copolymer were prepared by spin coating on p-Si substrate. Thermal behavior of the film was observed by measuring the film thickness with ellipsometry as a function of the temperature and abrupt volume expansion was observed at 130–150 °C. Capacitance-voltage (C-V) and current-voltage (I-V) behavior of the aluminum/P(VDF-TrFE)/p-Si MIS (metal-insulator-semiconductor) structures were studied and dielectric constant of the P(VDF-TrFE) film was measured to be about 15.3 at optimum condition. No hysteresis was observed in the C-V curve for films as deposited and annealed (70–200 °C). Films annealed at temperatures higher than the volume expansion temperature showed substantial surface roughness due to the crystallization. Flat band voltage (V_FB) of the MIS structure with as deposited films was about −0.3 V and increased up to −2.0 V with annealing. This suggested that positive charges were generated in the film. Electronic properties of the annealed P(VDF-TrFE) film at above melting temperature were degraded substantially with larger shift in flat band voltage, low dielectric constant and low breakdown voltage. Organic thin film transistor with pentacene active layer and P(VDF-TrFE) as a gate dielectric layer showed a mobility of 0.31 cm²/V·s and threshold voltage of −0.45 V.     

Effect of zeolite content in the electrical, mechanical and thermal degradation response of poly(vinylidene fluoride)/NaY zeolite composites

Polymer based composites of a-PVDF doped with different NaY zeolite (Na53Al53Si139O384) content were investigated. A good dispersion of NaY zeolite within the polymer matrix is achieved. The introduction of NaY nanoparticles enhance the storage modulus and the dielectric constant at room temperature. The dielectric constant at room temperature increases up to the value of 500 for the 32 wt% composite, at 1 kHz. The increase of the dielectric constant is mainly attributed to interfacial polarization effects. For increasing zeolite content, the nanocomposite conductivity shows two conducting regimes separted by the so called breaking voltage, which is associated to an intrazeolite charge transport. Thermogravimetric results show that the introduction of zeolites affects the thermal degradation of the polymer for low zeolite contents and also indicate the presence of water that also plays an important role in the electrical response of the materials.     

Enhanced Dielectric Performance in Polymer Composite Films with Carbon Nanotube‐Reduced Graphene Oxide Hybrid Filler

The electrical conductivity and the specific surface area of conductive fillers in conductor‐insulator composite films can drastically improve the dielectric performance of those films through changing their polarization density by interfacial polarization. We have made a polymer composite film with a hybrid conductive filler material made of carbon nanotubes grown onto reduced graphene oxide platelets (rG‐O/CNT). We report the effect of the rG‐O/CNT hybrid filler on the dielectric performance of the composite film. The composite film had a dielectric constant of 32 with a dielectric loss of 0.051 at 0.062 wt% rG‐O/CNT filler and 100 Hz, while the neat polymer film gave a dielectric constant of 15 with a dielectric loss of 0.036. This is attributed to the increased electrical conductivity and specific surface area of the rG‐O/CNT hybrid filler, which results in an increase in interfacial polarization density between the hybrid filler and the polymer.     

A sol–gel preparation of silica coated zirconia microspheres as chromatographic support materials

Four silica–zirconia composites were prepared using a sol–gel process and compared with zirconia, which was prepared under the same conditions but without the addition of sodium metasilicate pentahydrate. Spherical particles (1–2 μm) resulted which were free from aggregation and hollow spheres. Raman spectroscopy, differential thermal analysis, thermal gravimetric analysis and electron microscopy were used to evaluate the properties of these composites. Addition of the silica onto the zirconia microspheres prevented the formation of monoclinic zirconia and increased the temperature of crystallization into the tetragonal form. Calcination of the composites at 1300°C produced zircon. This revised version was published online in November 2006 with corrections to the Cover Date.     

Effect of glass hybridization and staking sequence on mechanical behaviour of interply coir–glass hybrid laminate

The interest in fibre-reinforced polymer composites is growing rapidly due to its high performance in terms of mechanical properties, significant processing advantages, excellent chemical resistance, low cost, and low density. The development of composite materials based on the reinforcement of two or more fibre types in a matrix leads to the production of hybrid composites. In the present work, woven coir–glass hybrid polyester composites were developed and their mechanical properties were evaluated for different stacking sequences. Scanning electron micrographs of fractured surfaces were used for a qualitative evaluation of interfacial properties of woven coir–glass hybrid polyester composites. These results indicated that coir–glass hybrid composites offered the merits of both natural and synthetic fibres.     

Dielectric properties of carbon black and carbonyl iron filled epoxy–silicone resin coating

The dielectric properties of epoxy–silicone resin coatings containing carbon black (CB) and carbonyl iron (CI) particles as a function of frequency (2–18 GHz) and the CB volume content (0.2–1%) have been investigated. The complex permittivity of the coatings increased with increasing CB content, which mainly attributed to the interfacial polarization at the CB/resin/CI particles interfaces. The complex permittivity also decreased rapidly with increasing frequency in the low frequency range while decreased slowly in the high frequency range. The changes of dielectric properties with frequency and the CB volume content were discussed using the power-law decay and the concept of interfacial polarization.     

ZrO2/聚偏氟乙烯复合材料介电性能及松弛行为

通过熔融法制备了ZrO₂/聚偏氟乙烯（PVDF）复合材料,采用SEM、XRD和FTIR对其形貌和结构进行分析,结果表明,ZrO₂分布较为均匀,ZrO₂/PVDF复合材料主要含α相和少量γ相。采用宽频介电谱（BDS）测试,ZrO₂/PVDF复合材料介电常数ε'随ZrO₂含量的增加而增加,而介电损耗tanδ保持定值,表明ZrO₂的加入可以显著提高ZrO₂/PVDF复合材料的介电性能。经计算ZrO₂/PVDF复合材料介电模量M″和活化能,发现有玻璃化转变峰、缺陷峰和界面极化峰存在,而加入ZrO₂后,ZrO₂/PVDF复合材料活化能增加。      

Ba(Zn1/3Nb2/3)O3/Ni0.8Zn0.2Fe2O4 magneto-dielectric composite with large dielectric constant and high permeability

Ba(Zn_1/3Nb_2/3)O₃/Ni_0.8Zn_0.2Fe₂O₄ (BZN/NZO) composites were synthesized via the conventional solid-state reaction method. The phase composition and surface morphology of the composites were investigated using XRD and SEM, respectively. The dielectric and magnetic properties of the composites were studied. The results show that the BZN/NZO composites have large dielectric constants and very high permeabilities. For the 20%BZN/80%NZO composite, the dielectric constant and permeability in low frequency range are about 8,000 and 18, respectively. The large dielectric behavior of the BZN/NZO composites is mainly attributed to the Maxwell–Wagner polarization.     

Improved polymer nanocomposite dielectric breakdown performance through barium titanate to epoxy interface control

A composite approach to dielectric design has the potential to provide improved permittivity as well as high breakdown strength and thus afford greater electrical energy storage density. Interfacial coupling is an effective approach to improve the polymer-particle composite dielectric film resistance to charge flow and dielectric breakdown. A bi-functional interfacial coupling agent added to the inorganic oxide particles’ surface assists dispersion into the thermosetting epoxy polymer matrix and upon composite cure reacts covalently with the polymer matrix. The composite then retains the glass transition temperature of pure polymer, provides a reduced Maxwell-Wagner relaxation of the polymer-particle composite, and attains a reduced sensitivity to dielectric breakdown compared to particle epoxy composites that lack interfacial coupling between the composite filler and polymer matrix. Besides an improved permittivity, the breakdown strength and thus energy density of a covalent interface nanoparticle barium titanate in epoxy composite dielectric film, at a 5 vol.% particle concentration, was significantly improved compared to a pure polymer dielectric film. The interfacially bonded, dielectric composite film had a permittivity ∼6.3 and at a 30 μm thickness achieved a calculated energy density of 4.6 J/cm³.     

Preparation of high k expanded graphite/CaCuTi4O12/cyanate ester composites with low dielectric loss through controlling the interfacial action between conductors and ceramics

New composites with high dielectric constant and low dielectric loss, based on expanded graphite (EG), CaCuTi₄O₁₂ (sCCTO) and cyanate ester (CE) resin, were developed by controlling the interaction between EG and sCCTO. Difference from EG, surface modified EG (mEG) has an additional strong chemical interaction with sCCTO, this not only improves the dispersion of fillers, but also enhances the filler-matrix interfacial adhesion, leading to different micro-structures and dielectric properties. Specifically, the percolation thresholds of mEG/sCCTO/CE and EG/sCCTO/CE composites are 3.45 vol% and 2.86 vol%, respectively. When the loading of conductors approaches the percolation threshold, mEG/sCCTO/CE composite has much higher dielectric constant and lower dielectric loss than EG/sCCTO/CE composite. The nature behind these attractive data was revealed by building an equivalent circuit.     

Normal ferroelectric to ferroelectric relaxor conversion in fluorinated polymers and the relaxor dynamics

To elucidate the molecular origin of the polarization dynamics in the ferroelectric relaxor poly(vinylidene fluoride—trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) terpolymer, a broadband dielectric study was carried out in the frequency range from 0.01 Hz to 10 MHz and temperatures from −150°C to 120°C for the terpolymer and a normal ferroelectric P(VDF-TrFE) copolymer. The relaxation processes were also studied using dynamic mechanical analysis. It was shown that in the terpolymer, which was completely converted to a ferroelectric relaxor, there is no sign of the relaxation process associated with the ferroelectric-paraelectric transition which occurs in the P(VDF-TrFE) copolymer. In the copolymer, three additional relaxation processes have been observed. It was found that the relaxation process β_a, which was commonly believed to be associated with the glass transition in the amorphous phase, in fact, contains significant contribution from chain segment motions such as domain boundary motions in the crystalline region. In the temperature range studied, the terpolymer exhibits the latter three relaxation processes with the one (termed β_r) near the temperature range of β_a significantly enhanced. This is consistent with the observation that in conversion from the normal ferroelectric to a ferroelectric relaxor, the macro-polar domains are replaced by nano-polar-clusters and the boundary motions as well as the reorientation of these nano-clusters generate the high dielectric response. The experimental data also reveal a broad relaxation time distribution related for the β_r process whose distribution width increases with reduced temperature, reflecting the molecular level heterogeneity in the crystalline phase due to the random introduction of the CFE monomer in the otherwise ordered macro-polar domains. The random interaction among the nano-clusters as well as the presence of the random fields produces ferroelectric relaxor behavior in the terpolymer.