The effect of filler on the temperature coefficient of the relative permittivity of PTFE/ceramic composites

High permittivity and low-loss ceramic fillers have been prepared by means of the solid state ceramic route. Ceramic-filled composites were prepared by the Sigma Mixing, Extrusion, Calendering, which was followed by the Hot pressing (SMECH) process. The microwave dielectric properties of the composites were studied using X-band waveguide cavity perturbation technique. The temperature coefficient of the relative permittivity of the composites was investigated in the 0-100 °C temperature range using a hot and cold chamber coupled with an impedance analyzer. The temperature coefficient of the relative permittivity of the composites showed strong dependence on the temperature coefficient of the relative permittivity of the filler material. In the present study, a high-permittivity polymer/ceramic composite, having τ_εr ∼63 ppm/K, has been realized. This composite is suitable for outdoor wireless applications.     

Study of the structural, dielectric and magnetic properties of Bi2O3 and PbO addition on BiFeO3 ceramic matrix

In this paper we studied the effects of Bi₂O₃ and PbO addition on BiFeO₃ (BFO) ceramic matrix. The structural, dielectric and magnetic properties of fifteen BFO samples were discussed in view of possible applications in RF and microwave devices. The present work also reports the preparation of the samples. Polyvinyl alcohol (PVA) and tetraethyl orthosilicate (TEOS) were also added as a binder in the fabrication procedure. The samples have been studied by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and magnetic hysteresis measurements. Further, a study based on impedance spectroscopy also has been done. Dielectric permittivity (ε′) and dielectric loss (tan δ) were measured at room temperature in the frequency range 100 Hz-10 MHz, as well as a.c. conductivity. The -Im[Z(f)] versus Re[Z(f)] plot has been obtained. The samples were investigated in view of possible applications like miniaturized filters, diplexers and dielectric resonator antennas (DRA). In the RF and MW frequency region, the application of magneto-dielectric and multiferroic perovskite composite materials is desirable for the miniaturization of components.     

Magnetic and electromagnetic properties of composites of iron oxide and Co-B alloy prepared by chemical reduction

Magnetic and electromagnetic properties were investigated on the composites of iron oxide and Co-B alloy, which were prepared by a modified chemical reduction method. The composites are characterized by scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDXA), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and vibrating sample magnetometry (VSM). The complex electromagnetic parameters (permittivity ε_r=ε_r′+jε_r″ and permeability μ_r=μ_r′+jμ_r″) of paraffin mixed composite samples (paraffin:composites=1:1 in mass ratio) were measured in the frequency range 2-18 GHz by vector network analyzer. The measured real part (ε_r′) and imaginary part (ε_r″) of the relative permittivity show two resonant peaks in the range of 2-18 GHz. The imaginary parts of relative permeability (μ_r″) of all samples exhibited one broad resonant peak over the 2-8 GHz range. The μ_r″ of samples with higher molar ratio of Co to Fe (C and D) shows negative values within 13-18 GHz, which exhibit resonant and antiresonant permeabilities simultaneously. Calculation results indicated that the reflection loss values of the composites and paraffin wax mixtures are less than −10 dB with frequency width of about 6 GHz at the matching thickness.     

Microstructure and magneto-dielectric properties of ferrimagnetic composite GdIGX:YIG1−X at radio and microwave frequencies

The gadolinium iron garnet (GdIG, Gd₃Fe₅O₁₂) and yttrium iron garnet (YIG, Y₃Fe₅O₁₂), and their GdIG_X:YIG_1−X composites, were obtained by a new solid-state procedure. The microstructure of the samples was studied by X-ray powder diffraction and Rietveld refinement, Vickers microhardness and scanning electron microscopy. The density and microhardness behavior were studied as a function of the lattice parameters for the composite samples. In the present work, the magnetic and dielectric properties of the GdIG_X:YIG_1−X composite at radio and microwave frequencies were also studied. The magnetic permeability and dielectric permittivity and loss properties for the composite GdIG_X:YIG_1−X showed good potential for use in components, when one is looking for moderate ε_r′ and μ_r′ materials with low loss in the radio-frequency and microwave range.     

Effect of sintering temperature on structure and nonlinear dielectric properties of Ba0.6Sr0.4TiO3 ceramics prepared by the citrate method

Ba_0.6Sr_0.4TiO₃ ceramics were prepared by a citrate precursor method. The structure and nonlinear dielectric properties of the resulting ceramics were investigated within the sintering temperature range 1200-1300 °C. Adopting fine Ba_0.6Sr_0.4TiO₃ powder derived from the citrate method was confirmed to be effective in reducing the sintering temperatures required for densification. The ceramic specimens sintered at 1230-1280 °C presented relative densities of around 95%. A significant influence of sintering temperature on the microstructure and nonlinear dielectric properties was detected. The discrepancy in nonlinear dielectric behavior among the specimens sintered at different temperatures was qualitatively interpreted in terms of the dielectric response of polar micro-regions under bias electric field. The specimens sintered at 1230 and 1250 °C attained superior nonlinear dielectric properties, showing relatively low dielectric losses (tan δ) of 0.24% and 0.22% at 10 kHz together with comparatively large figure of merits (FOM) of 121 and 142 at 10 kHz and 20 kV/cm, respectively.     

Structural and dielectric properties of polyvinyl alcohol/barium zirconium titanate polymer–ceramic composite

The polyvinyl alcohol (PVA)/barium zirconium titanate Ba[Zr_0.1Ti_0.9]O₃ (BZT) polymer–ceramic composites with different volume percentage are obtained from solution mixing and hot-pressing method. Their structural and electrical properties are characterized by X-ray diffraction (XRD), Rietveld refinement, cluster modeling, scanning electron microscope and dielectric study. XRD patterns of PVA/BZT polymer–ceramics composite (with 50% volume fractions) indicate no obvious differences than the XRD patterns of pure BZT which shows that the crystal structure is still stable in the composite. The scanning electron micrograph indicates that the BZT ceramic is dispersed homogeneously in the polymer matrix without agglomeration. The dielectric permittivity (ε_r) and the dielectric loss (tan δ) of the composites increase with the increase of the volume fraction of BZT ceramic. Theoretical models are employed to rationalize the dielectric behavior of the polymer composites. The dielectric properties of the composites display good stability within a wide range of temperature and frequency. The excellent dielectric properties of these polymer–ceramic composites indicate that the BZT/PVA composites can be a candidate for embedded capacitors.     

Magnetic and dielectric properties of Ni0.8Co0.1Cu0.1Fe2O4+PZT composites

Magnetoelectric composites of Ni_0.8Co_0.1Cu_0.1Fe₂O₄ and Lead Zirconate Titanate (PZT) were prepared by using conventional ceramic method. The measured values of saturation magnetization (M_s) and magnetic moments (μ_B) are in accordance with the volume fraction of ferrite content in the composite. The dielectric constant of the composites decreases with frequency. The plots of dielectric constant () against temperature (T) show a peak at their respective transition temperatures. The ME output was measured by varying dc bias magnetic field. A large ME output signal of 776 mV/cm was observed for 35% ferrite +65% ferroelectric composite. The magnetoelectric (ME) response is found to be dependent on the content of ferrite phase.     

A novel high-k ‘Y5V’ barium titanate ceramics co-doped with lanthanum and cerium

Structural, dielectric, and ferroelectric properties of a novel high-k ‘Y5V’ (Ba_1−xLa_x)(Ti_1−x/4−yCe_y)O₃ ceramics (where x=0.03 and y=0.05, denoted by BL3TC5) with the highest ‘Y5V’ dielectric response (ε′>10 000) among rare-earth-doped BaTiO₃ ceramics to date are investigated in detail using SEM, TEM, XRD, DSC, EPR, Raman spectroscopy (RS), temperature and frequency, electric field dependences of dielectric permittivity (ε′), and temperature and electric field dependences of ferroelectric hysteresis loops. The BL3TC5 diffusion of ferroelectric phase transition occurs around dielectric peak temperatures (T_m) near a room temperature characteristic of dielectric thermal relaxation. Powder XRD data and defect complex model were given. “Relaxor” behavior associated with an order/disorder model and formation of a solid solution were discussed. The EPR results provided the evidence of Ti vacancies as compensating for lattice defects. High-k relaxor nature of BL3TC5 is characterized by an average cubic structure with long-range lattice disordering and local polar ordering; a slow change of the ε′ (T) and P_r(T) curves around T_m; no phase transition observed by DSC; and a broad, red-shifted A₁ (TO₂) Raman phonon mode at 251 cm⁻¹ accompanying the disappearance of the “silent” mode at 305 cm⁻¹ and a clear anti-resonance effect at 126 cm⁻¹ at room temperature.     

Frequency dispersive complex permittivity and permeability of ferromagnetic metallic granular composite at microwave frequencies

We experimentally studied the frequency dependent complex permittivity ε and permeability μ of composite composed of carbonyl iron powder (CIP) and epoxy resin in the frequency range 1-18 GHz. We found that the intrinsic ε and μ of CIP extracted from the measured ε and μ of composites follow the classical Maxwell equations and the Landau-Lifshitz-Gilbert (LLG) equation, respectively. The dependences of ε and μ of composites on the volume fraction of CIP (vf_CIP) were investigated using the two-exponent phenomenological percolation equation (TEPPE). We found that the TEPPE can fit the experimental results very well. Comparing the results of percolation parameters derived by experimental data at different frequencies, we show that the TEPPE is frequency independent for the composites at microwave frequencies. The results also show that the ε and μ spectrums of composites with definite vf_CIP can be correctly calculated by combining the TEPPE with the theoretical models of intrinsic ε and μ.     

Densification, microstructural evolution, and dielectric properties of CaTiO3-LaGaO3 microwave ceramics

The relations among the densification, microstructural evolution, and microwave dielectric properties of the (1−x)CaTiO₃-xLaGaO₃ ceramics with x=0.34 and 0.36 were investigated in this study. The results indicated that (1−x)CaTiO₃−xLaGaO₃ ceramics can be densified at 1300 °C with at least 97% of the theoretical value. The ceramics reported an orthorhombic perovskite structure, and no other detectable phases were found. Both ε_r and Q×f values can be improved by slowing the cooling rate during sintering. The ε_r and Q×f values of the 0.64CaTiO₃-0.36LaGaO₃ ceramics at cooling rates of >10 °C/min and 0.1 °C/min are 48.1 and 27,500 and 48.7 and 38,000, respectively. The higher densification obtained at a slower cooling rate plays an important role in improving the microwave dielectric properties.     

Characterization, sintering and dielectric properties of nanocrystalline zinc oxide prepared by a citric acid-based combustion route

Nanosized zinc oxide has been synthesized through a novel single step solution combustion route using citric acid as fuel. The X-ray diffraction (XRD) analysis revealed that the synthesized ZnO nanopowder has the pure wurtzite structure. The phase purity of the nanopowder has been confirmed using differential thermal analysis (DTA), thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FT-IR). The morphology and crystalline size of the as-prepared nanopowder characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the powder consisted of a mixture of nanoparticles and nanorods. The nanocrystalline ZnO could be sintered to ∼97% of the theoretical density at 1200 °C in 4 h. The dielectric constant (ε_r) and dielectric loss (ε_i) of sintered ZnO pellets at 5 MHz were 1.38 and 9×10⁻², respectively, at room temperature.     

Room temperature ferroelectric effect and enhanced dielectric permittivity in Rochelle salt/PVA percolative composite films

Rochelle salt (RS) filled polyvinyl alcohol (PVA) composite films have been prepared via a simple solution casting technique. The transport, dielectric and ferroelectric properties of the samples have been studied. The dielectric permittivity decreases slowly with increasing frequency and rise gradually with increasing temperature and RS contents in the composites. As the volume fraction of the RS reaches to percolation threshold (f_c ～0.0538), an abrupt increase in the dielectric permittivity (～403 almost 80 times higher compared to pure PVA with low loss ～0.18 at 1 kHz and room temperature) occurs in the RS/PVA composite film, which is attributed to the formation of the conductive network in the matrix. Ferroelectric loops up to room temperature (300 K) and the slight increase in Curie temperature from 297 to 300 K have also been observed for percolative composite film. The developed composite material with low loss high dielectric permittivity and room temperature ferroelectric behaviors might be applied in the technological fields.     

Dielectric characteristics and polarization response of lead-free ferroelectric (Bi0.5Na0.5)0.94Ba0.06TiO3-P(VDF-TrFE) 0-3 composites

Bismuth sodium barium titanate/poly(vinylidene fluoride-trifluoroethylene) 70/30 [(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-P(VDF-TrFE)] 0-3 composites were prepared by a hot-press method for different volume fractions of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ ceramic powder in a P(VDF-TrFE) 70/30 copolymer matrix. The relative permittivity and dielectric loss of the composites increased with increase in the volume fraction of the ceramics, which well follows the Bruggeman model. The polarization responses of the composites were strongly dependent on the ceramic volume fraction. The composites with a higher ceramic volume fraction showed an increase in remanent polarization. At room temperature, a 0.3(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃-0.7P(VDF-TrFE) composite showed a relative permittivity ε_r=30, remanent polarization and coercive field      

Low-temperature sintering and microwave dielectric properties of Ca2Zn4Ti15O36 ceramics

The sintering behavior, microstructures, and microwave dielectric properties of Ca₂Zn₄Ti₁₅O₃₆ ceramics with B₂O₃ addition were investigated. The crystalline phases and microstructures of Ca₂Zn₄Ti₁₅O₃₆ ceramics with 0-10 wt% B₂O₃ addition were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDS). The sintering temperature of Ca₂Zn₄Ti₁₅O₃₆ ceramic was lowered from 1170 to 930 °C by 10 wt% B₂O₃ addition. Ca₂Zn₄Ti₁₅O₃₆ ceramics with 8 wt% B₂O₃ addition sintered at 990 °C for 2 h exhibited good microwave dielectric properties, i.e., a quality factor (Qf) 11,400 GHz, a relative dielectric constant (ε_r) 41.5, and a temperature coefficient of resonant frequency (τ_f) 94.4 ppm/°C.     

Maxwell-Wagner characterization of dielectric relaxation in Ni0.8Zn0.2Fe2O4/Sr0.5Ba0.5Nb2O6 composite

Dense composites were prepared through incorporating the dispersed Ni_0.8Zn_0.2Fe₂O₄ ferromagnetic particles into Sr_0.5Ba_0.5Nb₂O₆ ferroelectric matrix. Extrinsic dielectric relaxation and associated high permittivities of the materials are reported in the composites. We used an ideal equivalent circuit to explain electrical responses in impedance formalism. A Debye-like relaxation in the permittivity formalism was also found. Interestingly, real permittivity (ε′) of the sample containing 30% Ni_0.8Zn_0.2Fe₂O₄ shows obvious independence of the temperature at 100 kHz. Dielectric relaxation and high-ε′ properties of the composites are explained in terms of the Maxwell-Wagner (MW) polarization model.     

Magnetic and dielectric properties of low vanadium doped nickel-zinc-copper ferrites

The new spinel-type of general formula Ni_0.6+xZn_0.2Cu_0.2V_xFe_2−2xO₄ with 0.0≤x≤0.25 was synthesized by the usual ceramic method. Structure of the prepared ferrites was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX). Room temperature magnetic hysteresis loops were measured using magnetic field strength up to 6 kOe. Saturation magnetization (M_s) increased with vanadium content up to x=0.05 and then decreased. Variation of (M_s) as a function of x is explained in terms of cation redistribution between A and B sublattices. Coercive force (H_c), remanent induction (B_r) and squareness of the hysteresis loop (B_r/M_s) as functions of x are presented. Dielectric permittivity (ε′, ε″) and dielectric loss tangent (tan δ) were measured as functions of frequency and temperature. These parameters were found to be strongly dependent on V₂O₅ concentration. The variation of dielectric loss tangent with frequency at different temperatures shows abnormal behavior, where more than one relaxation peaks were observed at low and high temperatures. This behavior could be attributed to the collective contribution of two types of carriers (p and n) to polarization.     

A study of thermal, dielectric and magnetic properties of strontium malonate crystals

Crystals of strontium malonate (SrC₃H₂O₄) were grown in silica gel by the single diffusion technique. The thermo gravimetric (TG), differential thermal analysis (DTA) and differential scanning calorimetric (DSC) studies were carried out to investigate the thermal stability of the crystal. The dielectric behavior of the title compound crystal was investigated by measuring the dielectric parameters - dielectric constant, dielectric loss and AC conductivity as a function of four frequencies −1 kHz, 10 kHz, 100 kHz and 1 MHz at temperatures ranging from 50 to 170 °C. Results indicate that the title compound is thermally stable up to about 409 °C and is a promising low ε_r-value dielectric material. The magnetic behavior of the crystal was also explored using a vibrating sample magnetometer.     

Electron hopping mechanism in hematite (α-Fe2O3)

The frequency dependence of the real (?′) and imaginary (?″) parts of the dielectric constant of polycrystalline hematite (α-Fe₂O₃) has been investigated in the frequency range 0-100 kHz and the temperature range 190-350 K, in order to reveal experimentally the electron hopping mechanism that takes place during the Morin transition of spin-flip process. The dielectric behaviour is described well by the Debye-type relaxation (α-dispersion) in the temperature regions T<233 K and T>338 K. In the intermediate temperature range 233 K<T<338 K a charge carrier mechanism takes place (electron jump from the O²⁻ ion into one of the magnetic ions Fe³⁺) which gives rise to the low frequency conductivity and to the Ω-dispersion. The temperature dependence of relaxation time (τ) in the −ln τ vs 10³/T plot shows two linear regions. In the first, T<238 K, τ increases with increasing T implying a negative activation energy −0.01 eV, and in the second region T>318 K τ decreases as the temperature increases implying a positive activation energy 0.12 eV. The total reorganization energy (0.12-0.01) 0.11 eV is in agreement with the adiabatic activation energy 0.11 eV given by an ab initio model in the literature. The temperature dependence of the phase shift in the frequencies 1, 5, 10 kHz applied shows clearly an average Morin temperature T_Mo=284±1 K that is higher than the value of 263 K corresponding to a single crystal due to the size and shape of material grains.     

Magnetoelectric characterization of xNi0.75Co0.25Fe2O4-(1−x)BiFeO3 nanocomposites

Magnetoelectric (ME) nanocomposites containing Ni_0.75Co_0.25Fe₂O₄-BiFeO₃ phases were prepared by citrate sol-gel process. X-ray diffraction (XRD) analysis showed phase formation of xNi_0.75Co_0.25Fe₂O₄-(1−x)BiFeO₃ (x=0.1, 0.2, 0.3 and 0.4) composites on heating at 700 °C. Transmission electron microscopy revealed the formation of powders of nano order size and the crystal size was found to vary from 30 to 85 nm. Dispersion in dielectric constant (ε) and dielectric loss (tan δ) in the low-frequency range have been observed. It is seen that nanocomposites exhibit strong magnetic properties and a large ME effect. On increasing Ni_0.75Co_0.25Fe₂O₄ contents in the nanocomposites, the saturation magnetization (M_S) and coercivity (H_C) increased after annealing at 700 °C. The large ME output in the nanocomposites exhibits strong dependence on magnetic bias and magnetic field frequency. The large value of ME output can be attributed to small grain size of ferrite phase of nanocomposite being prepared by citrate precursor process.     

A new, lead free, family of perovskites with a diffuse phase transition: NaNbO3-based solid solutions

(1−x)NaNbO₃-(x)ABO₃ perovskite solid solutions belonging to group II according to the Krainik classification [Izv. Akad. Nauk SSSR, Ser. Phys. 28 (1964) 643] exhibit a dramatic diffusion of the dielectric permittivity ε′ maximum and relaxor-type behavior when the second component concentration exceeds a threshold value x₀. The concentration phase transition to this relaxor-like phase is abrupt (of the first order kind) that is seen from the step in the dependence of the ε′(T) maximum temperature, T_m, on x. Some relaxor-like properties appear even at x<x₀ in the course of cooling while disappear during the course of heating. Due to this fact and because of coupling of the antiferroelectric (AFE) and ferroelectric (FE) order parameters a giant (up to 100 K) temperature hysteresis of ε′(T) arises at AFE-AFE first order phase transition. The T_m values of all the known NaNbO₃-ABO₃ relaxor-type compositions are well below the room temperature and the dielectric permittivity maximal values, ε′_m, are much lower than in the case of Pb-containing relaxors. However both T_m and ε′_m values can be increased substantially by Li or K-doping leading to the formation of NaNbO₃-ABO₃-LiNbO₃ (KNbO₃) solid solutions.