Effect of Ba(Zn1/3Ta2/3)O3 and SiO2 ceramic fillers on the microwave dielectric properties of butyl rubber composites

Butyl rubber–Ba(Zn_1/3Ta_2/3)O₃ (BR–BZT) composites and butyl rubber–silica (BRS) composites were prepared by sigma mixing. The dielectric properties at 1 MHz and 5 GHz of BR–BZT and BRS composites were investigated as a function of ceramic loading and were found to be improved with filler loading. For a optimum BZT loading of 0.26 v_f, the BR–BZT composite have ε_r = 4.88, tanδ = 0.0022 (at 5 GHz), coefficient of thermal expansion (CTE) = 112 ppm/°C, thermal conductivity (TC) = 0.30 Wm^?1 K^?1 and water absorption = 0.047 vol%. The BRS composites attained ε_r = 2.79, tanδ = 0.0039 (at 5 GHz), CTE = 102 ppm/°C, TC = 0.40 Wm^?1 K^?1 and water absorption = 0.078 vol% for the same loading of silica. The stress–strain curves of both composites showed good flexibility of the composite. The measured relative permittivity and TC of both composites were compared with different theoretical approaches.     

The dielectric and thermal properties of Mn-doped (1 − x) ZrTi2O6–xZnNb2O6 filled PTFE composites

High dielectric constant and low loss (1 ? x) ZrTi₂O₆–xZnNb₂O₆ ceramic fillers have been prepared by the conventional solid-state reaction technique. Ceramic filled polytetrafluoroethylene (PTFE) microwave composite substrates were fabricated through the hot-pressing process. The microwave dielectric properties of (1 ? x) ZrTi₂O₆–xZnNb₂O₆/PTFE composites were measured using stripline resonator method. The relative dielectric constant (ε _r) and loss tangent (tan δ) of the composites increase with an increase of x in the (1 ? x) ZrTi₂O₆–xZnNb₂O₆ ceramic at an optimum filler loading of 46vol%. As the x in the (1 ? x) ZrTi₂O₆–xZnNb₂O₆ ceramic increase, the coefficient of thermal expansion and temperature coefficient of dielectric constant decrease. 0.55ZrTi₂O₆–0.45ZnNb₂O₆ filled PTFE composite exhibits a dielectric constant of 7.32 with a loss tangent of 0.0015 (10 GHz) and a temperature coefficient of dielectric constant of ?84 ppm/^oC at an optimum filler loading of 46 vol%.     

The dielectric properties and dielectric mechanism of perovskite ceramic CLST/PTFE composites

Polytetrafluorethylene (PTFE) composites filled with perovskite (Ca,Li,Sm)TiO₃ (CLST) dielectric ceramic of various volume fractions filler up to 60% were prepared. The effects of volume fraction of ceramic filler on the microstructure and dielectric properties of the composites have been investigated. A comparative study of dielectric properties of experiment and modeling analysis has been carried out at high frequencies for the CLST/PTFE composites. The results indicate that both the dielectric constant and the dielectric loss increase with the filler. The CLST/PTFE composite with 40% ceramic has exhibited good dielectric properties: ε _r?=?7.92 (~10 GHz), tan δ?=?1.2?×?10^?3 (~10 GHz), and τ _f?=??45 ppm/°C. The dielectric properties are obviously better than most composites reported previously at high frequencies in the aspects of dielectric loss and thermal stability. The dielectric constant and dielectric loss of composites predicted by the Rother–Lichtenecker equation and the general mixing model are in good agreement with the experiment data when the volume fraction of ceramic is less than 40%. When the volume fraction of the ceramic is more than 40%, the deviation occurs. By introducing the correction factor, the theoretical values of the dielectric constant agrees well with the experimental values.     

Microstructures and dielectric properties of Ba[(Co0.7Zn0.3)1/3Nb2/3]O3-based ceramics prepared by aqueous gelcasting-assisted solid-state method

The aqueous gelcasting-assisted solid-state method (AGAS) and traditional solid-state reaction method (TSSR) were used to prepare Ba[(Co_0.7Zn_0.3)_1/3Nb_2/3]O₃ (BCZN)-based ceramics. The effects of different powder-preparation methods on the microstructures and dielectric properties of the BCZN-based ceramics were investigated. X-ray diffraction analysis showed completely the same phase compositions regardless of the preparation method adopted. The relative permittivity (ε _r) did not significantly vary between the two methods. However, BCZN with CeO₂-added ceramics prepared by AGAS had higher and more uniform density (6.374 g/cm³) and high quality factor of resonant frequency (Q × f) value (75,843 GHz) than those prepared by TSSR because of the more uniform microstructures, as shown by scanning electron microscopy images. The temperature coefficients of resonant frequency (τ _f  = 7.4 ppm/°C) of the ceramics prepared by AGAS were also closer to zero than those prepared by TSSR.     

Electrical and thermal properties of PTFE-Sr<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> composites

A new polymer-ceramic composite was prepared using PTFE and low loss Sr₂ZnSi₂O₇. The dielectric properties of the composite were studied in the microwave and radiofrequency ranges. The relative permittivity (ε_r) and dielectric loss (tan δ) increased with the filler loading from 0.10 to 0.50 volume fractions (v_f). The observed values of ε_r, thermal conductivity and coefficient of thermal expansion (CTE) were compared with the corresponding theoretical predictions. The ability of the composite towards moisture absorption resistance was studied as a function of filler loading. It was also found that the variation of ε_r was less than 2% in the temperature range 25–90 °C, at 1 MHz. For a filler content of 0.50 v_f, the PTFE/Sr₂ZnSi₂O₇ composite exhibited ε_r = 4.4_, tan δ = 0.003 (at 4–6 GHz), CTE = 38.3 ppm/°C, thermal conductivity = 2.1 W/mK and moisture absorption = 0.09 wt%.     

Phase structures and microwave dielectric properties of xCaTiO3–(1 − x)Sm0.9Nd0.1AlO3 ceramics

The xCaTiO₃–(1 ? x)Sm_0.9Nd_0.1AlO₃ (0.25 ≤ x ≤ 0.85) microwave dielectric ceramics were prepared by conventional solid state reaction method. The phase structures were characterized by X-ray diffraction, scanning electron microscope and Raman spectra. Solid solutions with the orthorhombic perovskite structure with octahedral tilting were formed from the x range of 0.25 to 0.85. Microwave dielectric properties of xCaTiO₃–(1 ? x)Sm_0.9Nd_0.1AlO₃ ceramics were investigated systematically. The optimum property of the ceramics was obtained for x = 0.65 sintered at 1,415 °C for 3 h: relative permittivity ε_r = 39.70, Q × f = 50,012 GHz, τ _f  = ?6.8 ppm/°C. xCaTiO₃–(1 ? x)Sm_0.9Nd_0.1AlO₃ ceramics provide a new promising material for application in the microwave technology with relative permittivity lying within the range from 39 to 44, high quality factor and near-zero τ _f .     

(1 − x)CaTiO3–x(Li0.5Nd0.5)TiO3 for ultra-small dielectrically loaded antennas

Microwave (MW) dielectric ceramics based on the solid solution (1 ? x)CaTiO₃–x(Li_0.5Nd_0.5)TiO₃ (0.25 ≤ x ≤ 1.0) were prepared by conventional solid-state synthesis using the mixed oxide route. Compositions closest to zero τ_f (+65 ppm/°C) were obtained at x = 0.8 where ε_r = 110 and the microwave quality factor, Qf ₀ ? 2600 GHz for samples sintered at 1300 °C. To reduce the sintering temperature and compensate for any Li₂O loss during fabrication, ≤0.5 wt% 0.5Li₂O–0.5B₂O₃ was added as a sintering aid in the form of raw oxides (LBR) and also as a pre-reacted glass (LBG). 0.5 wt% LBR was the most effective, reducing the temperature to achieve optimum density by ~50 °C with no significant deterioration of microwave properties (ε_r = 115, τ_f = +65 ppm/°C and Qf ₀ ? 2500 GHz). The high permittivity and relatively low sintering temperatures (1250 °C) are ideal for the development of low cost ultra-small dielectric loaded antenna, assuming the system can be tuned closer to zero by fractionally increasing x.     

Microwave dielectric properties of flexible silicone rubber – Ba(Zn1/3Ta2/3)O3 composite substrates

Silicone rubber composites filled with Ba(Zn_1/3Ta_2/3)O₃ (BZT) were prepared by hot pressing and the effect of filler content on the microwave dielectric, mechanical and thermal properties as well as on moisture absorption were investigated. The observed relative permittivity (ɛ_r) was compared with different theoretical models. Among the different theoretical models Jayasundere Smith and Modified Lichtenecker were in good agreement with experimental values of ɛ_r. The study of the mechanical property showed that the silicone rubber – BZT composites were flexible and stretchable. The coefficient of thermal expansion and specific heat capacity decreased whereas thermal conductivity, thermal diffusivity and the moisture absorption increased with increase in filler loading.     

Dielectric,thermal and mechanical properties of Sr<Subscript>2</Subscript>ZnSi<Subscript>2</Subscript>O<Subscript>7</Subscript> based polymer/ceramic composites

Polymer/Sr₂ZnSi₂O₇ (SZS) ceramic composites suitable for substrate applications have been developed using the polymers polystyrene (PS), high density polyethylene (HDPE) and Di-Glycidyl Ether of Bisphenol A (DGEBA). The dielectric, thermal and mechanical properties of the composites are investigated as a function of various concentrations of the ceramic filler. The obtained values of relative permittivity, dielectric loss tangent, thermal conductivity and coefficient of thermal expansion of the composites are compared with the corresponding theoretical predictions. The relative permittivity of the polymer/ceramic composites increases with filler loading. The dielectric loss tangent also shows the same trend except for DGEBA/SZS composites. The major advantages of the ceramic loading are improvement in thermal conductivity and a decrease in the coefficient of thermal expansion. The tensile strength of the composites decreases with increase in filler content, whereas an improvement is observed in microhardness. The variation of relative permittivity (at 1 MHz) of the composites is also studied as a function of temperature.     

Phase composition and microwave dielectric properties of Mg-excess MgTiO3 ceramics

The phase composition and microwave dielectric properties of Mg-excess MgTiO₃ (Mg/Ti = 1, 1.02, 1.04, 1.05, 1.07) ceramics prepared via the conventional solid-state reaction route were investigated. A slight deviation from stoichiometry does not practically affect the relative permittivity and temperature coefficient of resonant frequency of the specimen. However, the Q _f value is very sensitive to the composition and it shows a non-linear variation corresponding to a relative amount of Mg. A very high Q _f can be achieved for specimen with single MgTiO₃ phase, which can be obtained within the suitable composition. As the increasing of Mg content, the MgTi₂O₅ phase which was derived from Mg/Ti = 1 was disappeared, and when it exceeded 1.02, the phase of Mg₂TiO₄ emerged. Along with the augmentation of Mg/Ti, the bulk density and Q _f showed an initial increase, followed by a decrease, but ε_r had been declining. The specimen with single MgTiO₃ phase was obtained at the level of Mg/Ti = 1.02. A high Q _f of 357,400 GHz (at 10 GHz) together with an ε_r = 17 and τ _f  = ?51 ppm/°C for MgTiO₃ ceramics (Mg/Ti = 1.02) were obtained at 1,390 °C sintered for 4 h.     

A new microwave dielectric ceramics for LTCC applications: Li2Mg2(WO4)3 ceramics

A novel microwave dielectric ceramics Li₂Mg₂(WO₄)₃ (LMW) for low-temperature co-fired ceramics (LTCC) application were prepared by the conventional solid-state sintering method. Densification, phases, microstructure and microwave dielectric properties of the Li₂Mg₂(WO₄)₃ ceramics were investigated. The optimal sintering temperature of dense Li₂Mg₂(WO₄)₃ ceramic approximately ranges from 825 to 875 °C for 3 h. The ceramic specimens fired at 875 °C for 3 h exhibits excellent microwave dielectric properties: ε _r  = 7.72, Q × f = 29,600 GHz (f = 6.0 GHz), and τ _f  = ?15.5 ppm/°C. Moreover, the Li₂Mg₂(WO₄)₃ ceramics has a chemical compatibility with Ag during cofiring, which makes it a promising ceramic for LTCC technology application.     

Effect of borosilicate glasses on the microwave dielectric properties of ZnO–Nb2O5–Ta2O5 system

(1 ? y)[0.5ZnNb₂O₆–0.5Zn₃Nb₂O₈]–yZnTa₂O₆ with y = 0.91 (ZNT) ceramic have been prepared by conventional solid state ceramic route. The effect of glass additives on the microstructure, densification, and microwave dielectric properties of the ZNT ceramic for low temperature co-fired ceramic applications was investigated. Different weight percentages of quenched glass such as ZnO–B₂O₃–SiO₂, BaO–B₂O₃–SiO₂, LiO–B₂O₃–SiO₂ and MgO–B₂O₃–SiO₂ were added to ZNT powder. The crystal structure of the ceramic–glass composites was studied by X-ray diffraction and microstructure by scanning electron microscopy. The microwave dielectric properties such as relative permittivity (ε_r), quality factor (Q_uxf) and co-efficient of temperature variation of resonant frequency (τ_f) of the ceramics have been measured in the frequency range 4–6 GHz. The 5 wt% ZnO–B₂O₃–SiO₂ added ZNT ceramic sintered at 900 °C showed: ε_r = 28.1, Q_uxf = 32820 GHz (at 4.92 GHz), and τ_f = ?7.7 ppm/^oC respectively.     

Crystal structure,microstructure and microwave dielectric properties of novel MgAl<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript> ceramic

In the present work, a novel MgAl₂Ti₃O₁₀ ceramic was obtained using a traditional solid-state reaction method. X-ray diffraction and energy dispersive spectrometer showed that the main MgAl₂Ti₃O₁₀ phase was formed after sintered at 1300–1450 °C. With rising the sintering temperature from 1300 to 1450 °C, the bulk density (ρ), relative permittivity (ε _r ) and Q?×?f value firstly increased, reached the maximum values (3.61 g/cm³, 14.9, and 26,450 GHz) and then decreased. The temperature coefficient of resonator frequency (τ _f ) showed a slight change at a negative range of ??94.6 to ??83.7 ppm/°C. When the sintering temperature was 1400 °C, MgAl₂Ti₃O₁₀ ceramics exhibited the best microwave dielectric properties with Q?×?f?=?26,450 GHz, ε _r ?=?14.9 and τ _f ?=???83.7 ppm/°C.     

Synthesis and properties of Ba(Zn1/3Ta2/3)O3 for microwave and millimeter wave applications

High dielectric materials have gained an important position in microwave electronics by reducing the size and cost of components for a wide range of applications from mobile telephony to spatial communications. Ba(Zn_1/3Ta_2/3)O₃ (BZT) is an A(B′B″)O₃ type perovskite material, showing ultra high values of the quality factor Q. Ceramic-based BZT dielectric materials were prepared by solid state reaction. The samples were sintered at temperatures in the range 1400 ÷ 1600 °C for 4 h. Compositional, structural and morphological characterization were performed by using XRD, SEM and EDX analysis. The dielectric properties were measured in the microwave range (6 ÷ 7 GHz). An additional annealing at 1400 °C for 10 h has improved some dielectric parameters. For samples sintered at temperatures higher than 1500 °C, the permittivity values were obtained in the interval 30 ÷ 35 and almost do not change the value after the annealing. The Q × f product substantially increases up to about 135,000 GHz, exhibiting a low temperature coefficient of the resonant frequency (τ_f) in microwaves. The best parameters were obtained for the samples sintered at 1600 °C with additional annealing. The achieved high values of the Q × f product recommend these materials for microwave and millimeter wave applications.     

Low temperature sintering and microwave dielectric properties of Zn<Subscript>3</Subscript>Mo<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramic

Crystal structure and dielectric properties of Zn₃Mo₂O₉ ceramics prepared through a conventional solid-state reaction method were characterized. XRD and Raman analysis revealed that the Zn₃Mo₂O₉ crystallized in a monoclinic crystal structure and reminded stable up to1020 °C. Dense ceramics with high relative density (~ 92.3%) were obtained when sintered at 1000 °C and possessed good microwave dielectric properties with a relative permittivity (ε _r ) of 8.7, a quality factor (Q?×?f) of 23,400 GHz, and a negative temperature coefficient of resonance frequency (τ _f ) of around ??79 ppm/°C. With 5 wt% B₂O₃ addition, the sintering temperature of Zn₃Mo₂O₉ ceramic was successfully lowered to 900 °C and microwave dielectric properties with ε _r ?=?11.8, Q?×?f?=?20,000 GHz, and τ _f = ??79.5 ppm/°C were achieved.     

Microwave dielectric properties of Li2ZnTi3O8 ceramics prepared by reaction-sintering process

Li₂ZnTi₃O₈ (LZT) microwave dielectric ceramics prepared by reaction-sintering process were investigated. Li₂CO₃, ZnO and TiO₂ powders were mixed, pressed and sintered directly into ceramic pellets without any calcination stage involved. Pure LZT phase was obtained after sintering at temperatures above 1,100 °C for 2 h. LZT ceramic with the maximum bulk density of 3.81 g/cm³ (96.2 % of the theoretical value) and excellent microwave dielectric properties of ? _r  = 25.8, Q × f = 78,216 GHz and τ _f  = ?10.5 ppm/°C was obtained after sintering at 1,100 °C for 2 h. The results show that the reaction-sintering process is a simple and effective method to produce LZT ceramics.     

The electrostrictive effect and dielectric properties of lead-free 0.5Ba(ZrxTi1−x)O3–0.5(Ba0.75Ca0.25)TiO3 ceramics

Lead-free 0.5Ba(Zr_xTi_1?x)O₃–0.5(Ba_0.75Ca_0.25)TiO₃ (x = 0.25, 0.30, 0.35, 0.40) ceramics have been synthesized by a conventional solid state sintering method. The room temperature ferroelectric and electrostrictive properties of these ceramics were studied. Based on the measured properties, these ceramics showed a typical relaxor behavior. The Curie temperature of BZT–BCT ceramics decreases with increasing the Zr content. The largest electrostrictive strain and electrostrictive coefficient are founded in BZT–BCT ceramic with x = 0.25, the value is 0.16 % and 0.079 m⁴ C^?2, respectively. The polarization, electrostrictive strain and electrostrictive coefficient (Q ₁₁) decrease with increase in Zr concentration. For samples with low Curie temperature, which have large room temperature dielectric constant (ε), electrostrictive coefficient increases (Q ₁₁) is smaller. Because doping can disrupt the long range cation order, and electrostrictive (Q ₁₁) coefficient increases with cation order from disordered, through partially-ordered, simple relaxor and then ordered perovskites, ferroelectrics with a disordered structure have a huge permittivity, but a small electrostrictive coefficient (Q ₁₁).     

Microwave dielectric properties and applications of Ba(Zn1/3Nb2/3)O3–Ca(Zn1/3Nb2/3)O3 composite ceramics by one-step synthesis method

(1 ? x) Ca(Zn_1/3Nb_2/3) O₃ ? xBa(Zn_1/3Nb_2/3)O₃ (short for CZN/BZN, x = 0–1.0) ceramics were prepared and investigated through the “one-step synthesis method” method. The structure of the system was analyzed using X-ray diffraction. The microstructure of the sintered pellet was analyzed using scanning electron microscopy. Dielectric constant (ε_r), temperature coefficient of resonant frequency (τ_f) and the unloaded quality factor (Q × f) were measured in the microwave frequency region. Two dielectric properties were firstly in the rising tendency and then decreasing with the increased x. On the other hand, a good combination of microwave dielectric properties (ε_r = 24, Q × f = 23,510 GHz τ_f = ?9 ppm/°C) were obtained at x = 0.1. The compositions have excellent microwave dielectric properties and hence are suitable for ceramic capacitors or dielectric resonators applications.     

Microstructure and microwave dielectric properties of Ba(Mg1/3Nb2/3)O3–MgO composite ceramics with nano-silica added

Ba(Mg_1/3Nb_2/3)O₃–MgO composite ceramics were prepared by solid-phase method. The ceramic exhibited the 1:2 ordered structure. By adding a proper amount of MgO, the permittivity decreased rapidly compared with other Ba(Mg_1/3Nb_2/3)O₃-based ceramics. The Q?×?f values of the samples were greatly improved by nano-silica. Raman spectra showed that the permittivity and Q?×?f value showed a strong correlation with Raman shift and full width at half maximum of the A_1g(O) phonon mode, respectively. The Raman shift of A_1g(O) was consistent with the variation trend of permittivity. And the full width at half maximum of the A_1g(O) phonon mode had a negative correlation with the Q?×?f value. The results showed that upon adding 1.5 wt% nano-silica to the ceramics, the ceramics sintered at 1550 °C for 5 h had the lowest Raman shift and the narrowest full width at half maximum, achieving the best microwave dielectric properties: ε_r?=?22.22, Q?×?f?=?80,436 GHz, τ_f?=?–?5.89 ppm/°C.

     

Microwave dielectric properties of Bi(Sc<Subscript>1/3</Subscript>Mo<Subscript>2/3</Subscript>)O<Subscript>4</Subscript> ceramics for LTCC applications

A novel microwave dielectric ceramics Bi(Sc_1/3Mo_2/3)O₄ with low firing temperature were prepared via the solid reaction method. The specimens have been characterized using scanning electron microscopy, X-ray diffraction, Raman spectroscopy and DC conductivity. The Bi(Sc_1/3Mo_2/3)O₄ ceramics showed B-site ordered Scheelite-type structure with space group C2/c. Raman analysis indicated that prominent bands were attributed to the normal modes of vibration of MoO₄ ^2? tetrahedra. The dielectric loss of Bi(Sc_1/3Mo_2/3)O₄ ceramics can be depended strongly the bulk conductivity by DC measurement. The superior microwave dielectric properties are achieved in the Bi(Sc_1/3Mo_2/3)O₄ ceramic sintered at 875 °C/4 h, with dielectric constant?~?25, Q?×?f ~?51,716 GHz at 6.4522 GHz and temperature coefficient of resonance frequency ~???70.4 ppm/°C. It is a promising microwave dielectric material for low-temperature co-fired ceramics technology.