Improved dielectric properties of Ba0.5Sr0.5TiO3–ZnAl2O4 composite ceramics using double sintering

Ba_0.5Sr_0.5TiO₃–ZnAl₂O₄ composite ceramics were prepared by double sintering and conventional sintering. The results show that the double sintering can effectively reduce the ion diffusion between Ba_0.5Sr_0.5TiO₃ and ZnAl₂O₄ phases. The double sintered samples exhibit higher density and more uniform grain size distribution than the conventional sintered samples. The dielectric permittivity of double sintered samples is lower than that of conventional sintered samples. Impedance spectrum analysis shows that the oxygen vacancy content and grain boundary resistance of the double sintered samples is lower than that of the conventional sintered samples, which indicates that the Q value of the double sintered samples is higher than that of the conventional sintered samples. The optimum dielectric tunability and Q value of double sintered 60 wt%Ba_0.5Sr_0.5TiO₃-40 wt%ZnAl₂O₄ sample are 23.4% at 30 kV/cm and 276 at 2.257 GHz, respectively. Therefore, double sintering is a strategy that can effectively adjust the dielectric tunability and Q value of BST-ZA composite ceramics.     

Microwave dielectric properties of BaO–4.3TiO2–0.5ZnO ceramics with BaCu(B2O5)

Effect of BaCu(B₂O₅) (BCB) addition on microwave dielectric properties and sintering behaviors of BaO–4.3TiO₂–0.5ZnO system (BTZ) ceramics were investigated to develop middle-k dielectric composition with low sintering temperatures. When a small amount of BCB was added to BTZ system, the sintering temperature can be lowered from 1100 °C to 900 °C due to the formation of BCB liquid phase. The system added with 7 wt% BCB was sintered at 900 °C for 2 h and ?_r of 31, Q × f of 18,200 GHz and τ_f of 3.8 ppm/°C were obtained. The suitability of BTZ ceramics for tape casting and cofiring with Ag electrodes was investigated, and no evidence of chemical reaction between Ag and ceramics was observed. The dielectric properties of the stacked multilayer plate without any electrodes were also measured. The result shows that the as-prepared BTZ ceramics are suitable for low-temperature co-fired ceramics applications.     

Microwave dielectric properties of low-fired Li2MnO3 ceramics co-doped with LiF–TiO2

Li₂MnO₃ ceramics co-doped with 2 wt% LiF and x wt% TiO₂ (x=0, 3, 5, 7, 10) were prepared by solid-state reaction for low-temperature co-fired ceramics (LTCC) applications. The sintering temperatures of Li₂MnO₃ ceramics were successfully lowered to 925°C due to the formation of a LiF liquid phase. Their temperature stability was improved by doping with TiO₂. A typical Li₂MnO₃-2 wt% LiF-5 wt% TiO₂ sample with well-densified microstructures displayed optimum dielectric properties (ε_r=13.8, Q×f= 23,270 GHz, τ_f=1.2 ppm/°C). Such sample was compatible with Ag electrodes, which suggests suitability of the developed material for LTCC applications in wireless communication systems.     

Effect of ZnO on Mg2TiO4–MgTiO3–CaTiO3 microwave dielectric ceramics prepared by reaction sintering route

ZnO-doped Mg₂TiO₄–MgTiO₃–CaTiO₃ microwave dielectric ceramics were successfully prepared by the reaction sintering route. The compact samples consisted of MgTiO₃, Mg₂TiO₄ and CaTiO₃, which was confirmed by X-ray diffraction and energy-dispersive spectra. ZnO efficiently lowered the sintering temperature and promoted the densification, as well as the improvements in the dielectric constant and the quality factor. At the level of ZnO?=?1 wt-%, the ceramics exhibited optimum microwave dielectric properties: a dielectric constant of 20.3, a high quality factor of 64,740 GHz (at 9.9 GHz) and a near-zero temperature coefficient of resonant frequency (–1.3 ppm/^oC) after sintering at 1320^oC for 4 h.     

Microwave dielectric properties of BiNbO4 ceramics with CuO–V2O5 addition

BiNbO₄ ceramics were developed by using CuO–V₂O₅ as a liquid phase sintering agent. The resultant dielectric properties were analyzed in terms of the densification and the amount of CuO–V₂O₅ sintering agent. The addition of 0.8 wt.% CuO–V₂O₅ as its sintering agent was observed to perform most satisfactory. At 850 °C, uniform and enhanced microstructure was observed for the BiNbO₄ specimen with 0.8 wt.% CuO–V₂O₅ addition. Furthermore, the effect of CuO–V₂O₅ addition on the microwave dielectric properties of BiNbO₄ was also investigated. As the sintering temperature increased to 900 °C, the dielectric constant increased but nearly constant and the quality factor (QF) showed a maximum at 850 °C and then decreased for all compositions of the 900 °C sintered specimens. With an increase in CuO–V₂O₅ content, the temperature coefficient of frequency (TCF) increased in accordance with the dielectric mixing rule and microstructural behavior.     

Microwave dielectric characteristics of 0.75(Al1/2Ta1/2)O2–0.25(Ti1−xSnx)O2 ceramics

The microwave dielectric characteristics of 0.75(Al_1/2Ta_1/2)O₂–0.25(Ti_1−xSn_x)O₂ ceramics were investigated. The microwave dielectric properties of 0.75(Al_1/2Ta_1/2)O₂–0.25TiO₂ sintered at 1450 °C exhibited a dielectric constant (ϵ_r) of 31.2, a Q·f₀ of 54,590 GHz, and the temperature coefficient of resonant frequency (τ_f) of +12.8 ppm/°C. To control of the τ_f and enhance the Q·f₀ for 0.75(Al_1/2Ta_1/2)O₂–0.25TiO₂, Sn⁴⁺ was substituted for Ti⁴⁺. With an increase of Sn content from 5 to 50 mol%, the ε_r slightly decreased, the Q·f₀ increased and the τ_f shifted from positive to negative value. The τ_f within ±10 ppm/°C of zero was realized for the Sn content below 30 mol% and the microwave dielectric properties had the ε_r value of 31.2–26.3, the Q·f₀ of 54,600–70,700 GHz, and τ_f of +12.8–−9.3 ppm/°C for this compositions. The relationship between microstructure and microwave dielectric characteristics was investigated.     

Microwave dielectric properties of (1−x)ZnAl2O4–xCaTiO3 compound ceramic with controlled temperature coefficient

In this study, microwave dielectric properties of (1?x)ZnAl₂O₄?xCaTiO₃ samples with controlled temperature coefficient feature are analyzed. The crystal structures of all the compositions were refined by X-ray diffraction. A homogeneous distribution of cations within instrument sensitivity in all the samples was observed using scanning electron microscopy, coupled with energy dispersive X-ray analysis. ZnAl₂O₄ and CaTiO₃ could coexist when the x content was less than 0.1, whereas Al₂O₃ and Ca₃Al₂O₆ phases were observed in composite ceramics. As expected, the dielectric constant (ε_r) of the composite ceramics increased with the increasing x content, and the quality factor (Qf) generally decreased with increasing x-content because of the low Qf of the CaTiO₃ phases. The temperature coefficient of resonant frequency (τ_f) could be controlled by varying the CaTiO₃ content and could lead to zero τ_f value. The 0.92ZnAl₂O₄?0.08CaTiO₃ ceramic exhibited ε_r of 10.8, Qf of 32,300 GHz, and τ_f of 0 ppm/°C.     

Phase evolution and microwave dielectric properties of SrTiO3 added ZnAl2O4–Zn2SiO4–SiO2 ceramics

Phase evolution and microwave dielectric properties of SrTiO₃ added ZnAl₂O₄–3Zn₂SiO₄–2SiO₂ ceramics system were investigated. With the addition of SrTiO₃, the sintering temperature for dense ceramic is reduced from 1320 °C to 1180–1200 °C. According to the nominal composition ZnAl₂O₄–3Zn₂SiO₄–2SiO₂-ySrTiO₃, phase evolution is revealed by XRD patterns and Back Scattering Electron images: Zn₂SiO₄, ZnAl₂O₄ and SiO₂ phases coexist at y = 0; SrTiO₃ reacts with ZnAl₂O₄ and SiO₂ to form SrAl₂Si₂O₈, TiO₂ and Zn₂SiO₄ at y = 0.2 to 0.8, and SiO₂ phase disappears at y = 0.8; new phase of Zn₂TiO₄ is obtained at y = 1. The existence of TiO₂ has important effect on the dielectric properties. The optimized microwave dielectric properties are obtained at y = 0.6 and the ceramics show low dielectric constant (7.16), high-quality factor (57, 837 GHz), and low temperature coefficient of resonant frequency (−30 ppm °C⁻¹).     

Microwave dielectric properties of CaWO4–Li2TiO3 ceramics added with LBSCA glass for LTCC applications

In this work, 0.86CaWO₄–0.14Li₂TiO₃ ceramics were prepared via a traditional solid-state process. The effects of Li₂O–B₂O₃–SiO₂–CaO–Al₂O₃ (LBSCA) addition on the phase formation, sintering character, microstructure and microwave dielectric properties of the ceramics were investigated. A small amount of LBSCA addition could effectively lower the sintering temperature of the ceramics. X-ray diffraction analysis revealed that CaWO₄ and Li₂TiO₃ phases coexisted without producing any other crystal phases in the sintered ceramics. The dielectric constant and Qf values were related to the amount of LBSCA addition and sintering temperatures. All specimens could obtain near-zero temperature coefficient (τ_f) values through the compensation of the positive τ_f of Li₂TiO₃ and the negative τ_f of CaWO₄. The 0.86CaWO₄–0.14Li₂TiO₃ ceramic with 0.5 wt% LBSCA addition and sintered at 900 °C for 3 h exhibited excellent microwave dielectric properties of ε_r=12.43, Qf=76,000 GHz and τ_f=−2.9 ppm/°C.     

Microwave dielectric properties of high dielectric tunable - low permittivity Ba0.5Sr0.5TiO3–Mg2(Ti0.95Sn0.05)O4 composite ceramics

Ba_0.5Sr_0.5TiO₃–Mg₂(Ti_0.95Sn_0.05)O₄ composite ceramics have been synthesized by the solid-state reaction. Phase structure, microstructure and microwave dielectric properties have been systematically characterized. The permittivity is tailored to a certain extent with the addition of Mg₂(Ti_0.95Sn_0.05)O₄. Both X-ray diffraction (XRD) and back electric image (BEI) analysis show the co-existence of two-phase structures of ABO₃ perovskite and A₂BO₄ spinel structure. A high dielectric tunablity can be obtained and a high Q value can be achieved at microwave frequency. The composition 30 wt.%Ba_0.5Sr_0.5TiO₃–70 wt.%Mg₂(Ti_0.95Sn_0.05)O₄ exhibits good dielectric properties with ? of 79, Q of 152 (at 2.997 GHz) and T of 15.8% (30 kV/cm & 10 kHz) at room temperature, which make it a promising candidate for tunable microwave device applications in the wireless communication system.     

Phase analysis and microwave dielectric properties of BaO–Nd2O3–5TiO2 composite ceramics using variable size TiO2 reagents

There are significant inconsistencies in published literature surrounding the phase analysis and physical properties of ceramics with the nominal composition BaO–Nd₂O₃–5TiO₂ (BNT125). A careful phase analysis investigation of BNT125 ceramics using variable size TiO₂ reagents was therefore undertaken using XRD, FESEM and EPMA with corresponding dielectric properties characterised over 2–3 GHz. Three distinct phases were consistently formed: Ba_6?3xNd_8+2xTi₁₈O₅₄ (x ～ 0.67), Ba₂Ti₉O₂₀ and TiO₂. The use of nano-scale TiO₂ reagents significantly reduced porosity and improved the dielectric properties of the composite ceramics, while markedly reducing processing times. Structural and crystal chemical indications as to the origin of this system's physical properties are discussed, with these results providing new insights into optimisation paths for microwave dielectric materials of this type.     

Microwave dielectric properties of (1−x)ZnTa2O6−xMgNb2O6 ceramics

Single phase MgNb₂O₆ and ZnTa₂O₆ powders were synthesized by solid-state method, and the high quality factor composite ceramics of (1?x)ZnTa₂O₆?xMgNb₂O₆ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25 and 1.0) were prepared using the as-synthesized powders. The microwave dielectric properties, microstructure, phase transition and sintering behavior of the composite ceramics were investigated. The X-ray diffraction analysis revealed that solid solution between ZnTa₂O₆ and MgNb₂O₆ phases appeared in the composite ceramic. SEM results show that the grain sizes of the composite ceramics increased with increasing x values. The temperature coefficient of resonant frequency of (1?x)ZnTa₂O₆?xMgNb₂O₆ composite ceramics reaches near-zero of 1.02 ppm/°C with ε_r=35.58 and a high quality factor of 65500 GHz when x=0.20 and sintered at 1350 °C for 2 h.     

Temperature stable dielectric properties of Mg2TiO4–MgTiO3–CaTiO3 Ceramics Over a Wide Temperature range

The zero resonant frequency temperature coefficient (τ_f) of microwave dielectric ceramics (MWDCs) at high and low temperature have attracted great attention in the development of microwave communication equipment. In this work, the Mg₂TiO₄–MgTiO₃–CaTiO₃ (MMC) ceramics with meeting the application requirements of 5G communication were prepared by traditional solid-phase sintering after investigating the relationship among phase compositions of xMg₂TiO₄-(0.931-x)MgTiO₃-0.069CaTiO₃ and 0.34Mg₂TiO₄-0.591MgTiO₃-yCaTiO₃, sintering process, and dielectric properties in detail. The results show that the dielectric properties of MMC ceramics are strongly affected by the phase relative contents of MgTiO₃, Mg₂TiO₄ and CaTiO₃. For instance, MMC ceramics with approximate τ_f = 0 is contributed by mutual compensation of Mg₂TiO₄ and MgTiO₃, in which the Mg₂TiO₄ phase plays an important role in decreasing the τ_f value; and the increase of CaTiO₃ will greatly increase the ε_r value for MMC ceramics, while has a negative effect in the Q × f value. After three-phase regulation, the 0.32Mg₂TiO₄-0.611MgTiO₃-0.069CaTiO₃ microwave dielectric ceramic has a better dielectric temperature stability, associated with dielectric properties of ε_r = 19.7, Q × f = 55,400 GHz (at 8.43 GHz), τ_f- = 4.5 ppm/°C (?40 °C–25 °C), and τ_f+ = ?5.1 ppm/°C (25 °C–90 °C).     

Microwave dielectric properties of Mn-doped BaO–(Nd0.7,Sm0.3)2O3–4TiO2 ceramic sintered in a reducing atmosphere

The effect of MnCO₃ doped from 0 to 55 mol% into BaO–(Nd_0.7Sm_0.3)₂O₃–4TiO₂ (BNST) sintered in a reducing atmosphere on the microstructure and electrical properties was studied. Mn³⁺ completely substituted into Ti⁴⁺-sites of BNST to form a solid solution, so there is no second phase until 42 mol% which is the maximum solubility. Mn (<42 mol%)-doped BNST sintered in a reducing atmosphere is in a semi-conducing state because the concentration of free electron is higher than that of the acceptors. On the other hand, when Mn content doped into BNST exceeds a critical value (>43 mol%), the second Mn-rich phase due to excess of Mn³⁺ substituted into Ti⁴⁺-site, corresponding to original BaO–(Nd_0.7Sm_0.3)₂O₃–4TiO₂ (1 1 4) phase, is formed. Mn (>43 mol%)-doped BNST sintered in a reducing atmosphere is in an insulating state because the concentration of the acceptors is higher than that of liberated free electron, so the insulation resistance becomes high and tan δ becomes low. The formation of the second Mn-rich phase affects Q × f factor and temperature coefficient of capacitance (T.C.C.) of BNST significantly.     

Microwave dielectric properties of (Ba1−xSrx)(Mg0.5W0.5)O3 ceramics

The densification, microstructural evolution and microwave dielectric properties of (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics with x=0, 0.25, 0.5 and 0.75 are investigated in this study. The sintering temperature of the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ is significantly reduced from 1575 °C to 1400 °C as the x value increases from 0 to 0.25 and 0.50; this result is accompanied by the formation of the (Ba_1−ySr_y)WO₄ phase and a small quantity of second phase surrounding the grains. The grain size of the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics is increased by raising the Sr²⁺ content, which significantly lowers the sintering temperature. The microstructure of the (Ba_0.75Sr_0.25)(Mg_0.5W_0.5)O₃ ceramic displays the smallest average grain size of approximately 0.8 μm, with a narrow grain size distribution. Without long annealing time, very high Q×f values are obtained for the (Ba_1−xSr_x)(Mg_0.5W_0.5)O₃ ceramics sintered at 1400–1575 °C for a duration of only 2 h. The (Ba_0.75Sr_0.25)(Mg_0.5W_0.5)O₃ ceramic sintered at 1400 °C results in the best microwave dielectric properties, including ε_r of 20.6, Q×f of 152,600 GHz and τ_f of +24.0 ppm/°C.     

Microwave dielectric properties and microstructures of Nd(Mg0.5Sn0.5−xTix)O3 ceramics

This study elucidates the microwave dielectric properties and microstructures of Nd(Mg_0.5Sn_0.5?xTi_x)O₃ ceramics with a view to their potential for microwave devices. The Nd(Mg_0.5Sn_0.5?xTi_x)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the Nd(Mg_0.5Sn_0.4Ti_0.1)O₃ ceramics revealed no significant variation of phase with sintering temperatures. A dielectric constant (?_r) of 21.1, a quality factor (Q × f) of 50,000 GHz, and a temperature coefficient of resonant frequency (τ_f) of ?60 ppm/°C were obtained for Nd(Mg_0.5Sn_0.4Ti_0.1)O₃ ceramics that were sintered at 1550 °C for 4 h.     

Joining MgAl2O4 ceramics using ZnO–Al2O3–SiO2 glass ceramic with precipitated ZnAl2O4

In this work, crystallization, thermal expansion and wetting behavior of ZnO–Al₂O₃–SiO₂ (ZAS) glass were first investigated. The results showed that ZnAl₂O₄ was precipitated from ZAS glass after crystallization treatment. Crystallization increased the coefficient of thermal expansion (CTE) of ZAS glass ceramic due to the high CTE of ZnAl₂O₄. In addition, ZAS glass exhibited good wettability on the surface of MgAl₂O₄ substrate. On this basis, ZAS glass was used to join MgAl₂O₄ ceramic, and the microstructure and mechanical properties of joints obtained with different cooling methods were investigated. The flexural strength of joints was related to the content of ZnAl₂O₄ crystals in the brazing seams. Additional nucleation and crystallization treatment during cooling process improved the crystallinity of brazing seam, resulting in better matching of the CTE of brazing seam with that of MgAl₂O₄ ceramic. The maximum flexural strength of joints reached 201 MPa, which was equivalent to the strength of MgAl₂O₄ ceramic.     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.     

Ferroelectromagnetic characteristic of Na-doped 0.75BiFeO3–0.25BaTiO3 multiferroic ceramics

BiFeO₃-based materials are expected to have both ferroelectricity and ferromagnetism simultaneously. In this study, effects of Na-doping (0.5, 1.0, 3.0, and 5.0 mol%) on ferromagnetic and ferroelectric properties of 0.75BiFeO₃–0.25BaTiO₃ ceramics which have been fabricated by the solid state reaction technique are studied. The effects of Na-doped 0.75BiFeO₃–0.25BaTiO₃ ceramics on the crystal structure, and magnetic and electrical properties were investigated and discussed. Rhombohedrally distorted 0.75BiFeO₃–0.25BaTiO₃ showed weak ferromagnetic and ferroelectric properties. In addition, ferroelectric and ferromagnetic properties of 0.75BiFeO₃–0.25BaTiO₃ have been controlled by Na doping, and the maximum values of magnetization and polarization were observed at 5.0 mol%.     

Microwave sintering of IR-transparent Y2O3–MgO composite ceramics

A method for preparation of dense Y₂O₃–MgO composite ceramics by the microwave sintering was developed. The initial powders were obtained by glycine-nitrate self-propagating high-temperature synthesis (SHS) with different oxidant-to-fuel ratio. Density and IR-transmission of microwave sintered Y₂O₃–MgO ceramics increase with respect to dispersity of the SHS-powders and reach its maximum values for the powder prepared in a 20% fuel excess. The sintering behavior of Y₂O₃–MgO compacts was investigated by optical dilatometry and measuring an electric conductivity upon heating. Significant microwave radiation power surges at temperatures of 900–1000 °C, caused by the decomposition of magnesium carbonate, have been found. As a result of matching the conditions for the synthesis of powders and sintering modes, a transmission of composite ceramics of 78% at a wavelength of 6 μm was achieved at a maximum processing temperature of 1500 °C.