Dielectric Properties and Low‐Temperature Sintering of the Ba0.6Sr0.4TiO3 Ceramics with B2O3/CuO Additions

The sintering behaviors and dielectric properties of Ba_0.6Sr_0.4TiO₃ ceramics were investigated as a function of B₂O₃ and CuO content. The addition of both B₂O₃ and CuO reduced the sintering temperature of Ba_0.6Sr_0.4TiO₃ about 500°C. It was suggested that a liquid phase BaCu(B₂O₅) was formed and assisted the densification of Ba_0.6Sr_0.4TiO₃ ceramics. Ba_0.6Sr_0.4TiO₃ ceramics co‐doped with 3.0 mol% B₂O₃, and 2.0 mol% CuO, sintered at 950°C for 5 h, had a dense microstructure and showed good microwave dielectric properties of a moderate dielectric constant (ε = 1048), low dielectric loss (0.0090) and high tunability (42.2%) at dc electric field of 30 kV/cm.     

Low‐Temperature Synthesis of CoNb2O6 Microwave Dielectric Ceramics

Low‐fired cobalt niobate (CoNb₂O₆) microwave dielectric ceramics were prepared through a developed sol–gel process using Nb₂O₅·nH₂O as starting source. A metal‐dioxo‐bridged complex precursor was described on the basis of FT‐IR spectrum. The crystalline phases of calcined powders were characterized by X‐ray diffraction. Nanosized CoNb₂O₆ particles with orthorhombic α‐PbO₂‐type structure were obtained above 750°C. There was no subsequent phase change upon sintering, and all compounds sintered to at least 94% of theoretical density. At 1000°C/4 h, CoNb₂O₆ ceramics exhibited ε_r ~ 21.9, Q × f ~ 66 140 GHz (at 8.9 GHz) and τ_f ~ ?39.7 ppm/°C, having a good potential for low‐temperature cofired ceramic applications.     

Low‐Temperature Sintering Microwave Characteristics of B2O3‐doped CaLa4Ti4O15 Dielectric Ceramics

Preparation and microwave dielectric properties of B₂O₃‐doped CaLa₄Ti₄O₁₅ ceramics have been investigated. X‐ray diffraction data show that CaLa₄Ti₄O₁₅ ceramic has a trigonal structure coupled with a second phase of CaLa₄Ti₅O₁₇. The CaLa₄Ti₄O₁₅ ceramic with addition of 0.5 wt% B₂O₃, sintered at 1220°C for 4 h, exhibits microwave dielectric properties with a dielectric constant of 45.8, Q × f value of 24,000 GHz, and temperature coefficient of resonant frequency (τ_f) of ?19 ppm/^°C. B₂O₃‐doped CaLa₄Ti₄O₁₅ ceramics, which have better sintering behavior (decrease in sintering temperature ~ 330°C) and dielectric properties than pure CaLa₄Ti₄O₁₅ ceramics, are candidates for applications in microwave devices.     

Low‐Temperature Sintering and Microwave Dielectric Properties of (Mg0.95Zn0.05)2(Ti0.8Sn0.2)O4–(Ca0.8Sr0.2)TiO3 Composite Ceramics

0.9(Mg_0.95Zn_0.05)₂(Ti_0.8Sn_0.2)O₄–0.1(Ca_0.8Sr_0.2)TiO₃ (MZTS–CST) ceramics were prepared by a conventional solid‐state route. The MZTS–CST ceramics sintered at 1325°C exhibited ε_r = 18.2, Q × f = 49 120 GHz (at 8.1 GHz), and τ_f = 15 ppm/°C. The effects of LiF–Fe₂O₃–V₂O₅ (LFV) addition on the sinterability, phase composition, microstructure, and microwave dielectric properties of MZTS–CST were investigated. Eutectic liquid phases 0.12CaF₂/0.28MgF₂/0.6LiF and MgV₂O₆ were developed, which lowered the sintering temperature of MZTS–CST ceramics from 1325°C to 950°C. X‐ray powder diffraction (XRPD) and energy dispersive spectroscopy (EDS) analysis revealed that MZTS and CST coexisted in the sintered ceramics. Secondary phase Ca₅Mg₄(VO₄)₆ as well as residual liquid phase affected the microwave dielectric properties of MZTS–CST composite ceramics. Typically, the MZTS–CST–5.3LFV composite ceramics sintered at 950°C showed excellent microwave dielectric properties: ε_r = 16.3, Q × f = 30 790 GHz (at 8.3 GHz), and τ_f = ?10 ppm/°C.     

Structure‐Dependent Microwave Dielectric Properties and Middle‐Temperature Sintering of Forsterite (Mg1–xNix)2SiO4 Ceramics

The crystal structure, microstructure, and microwave dielectric properties of forsterite‐based (Mg_1–xNi_x)₂SiO₄ (x = 0.02–0.20) ceramics were systematically investigated. All samples present a single forsterite phase of an orthorhombic structure with a space group Pbnm except for a little MgSiO₃ secondary phase as x > 0.08. Lattice parameters in all axes decrease linearly with increasing Ni content due to the smaller ionic radius of Ni²⁺ compared to Mg²⁺. The substitution of an appropriate amount of Ni²⁺ could greatly improve the sintering behavior and produce a uniform and closely packed microstructure of the Mg₂SiO₄ ceramics such that a superior Q × f value (152 300 GHz) can be achieved as x = 0.05. The τ_f value was found to increase with increasing A‐site ionic bond valences. In addition, various additives were used as sintering aids to lower the sintering temperature from 1500°C to the middle sintering temperature range. Excellent microwave dielectric properties of ε_r~6.9, Q × f~99800 GHz and τ_f~?50 ppm/°C can be obtained for 12 wt% Li₂CO₃‐V₂O₅‐doped (Mg_0.95Ni_0.05)₂SiO₄ ceramics sintered at 1150°C for 4 h.     

BaCu(B_2O_5)助烧对CaO-BaO-Li_2O-Sm_2O_3-TiO_2微波介质陶瓷低温烧结和介电性能的影响

研究了BaCu(B_2O_5)(简写为BCB)掺入对14CaO-4BaO-8Li_2O-12Sm_2O_3-63TiO_2(简写为CBLST)微波介质陶瓷介电性能的影响.用XRD和SEM研究其相组成及微观形貌.结果表明:BaCu(B_2O_5)掺入能显著降低CBLST陶瓷的烧结温度,由1325 ℃降至1100 ℃.1100 ℃烧结2 h后,仍包含正交钙钛矿相和棒状的BST相.掺入6wt% BaCu(B_2O_5)的CBLST陶瓷取得了较好的介电性能:Kr=87.76,tanδ=0.018,TCF=-4.27 ppm/℃(1 MHz).     

Low‐Temperature Sintering and Microwave Dielectric Properties of CaMoO4‐Based Temperature Stable LTCC Material

The CaMoO₄–xY₂O₃–xLi₂O ceramics were prepared by the solid‐state reaction method. The sintering behavior, phase evolution, microstructure, and microwave dielectric properties were investigated. CaMoO₄ solid solution was obtained when x = 0.030, and two‐phase system including tetragonal CaMoO₄ phase and cubic Y₂O₃ phase formed when 0.066 ≤ x ≤ 1.417. A temperature stable CaMoO₄‐based microwave dielectric ceramic with ultralow sintering temperature (775°C) was obtained in the CaMoO₄–xY₂O₃–xLi₂O system when x = 0.306, which showed good microwave dielectric properties with a low permittivity of 9.5, a high Q_f value of 63 240 GHz, and a near‐zero temperature coefficient of resonant frequency of +7.2 ppm/°C.     

B2O3-CuO掺杂CSLST微波介质陶瓷介电性能研究

选用B2O3-CuO(BC)低熔点复合氧化物作为烧结助剂,采用固相法制备(Ca0.9375Sr0.0625)0.25(Li0.5Sm0.5)0.75TiO3(CSLST)陶瓷,研究了不同含量的BC对CSLST陶瓷的晶相组成、烧结性能及微波介电性能的影响.研究结果表明:随BC添加量的增多,CSLST陶瓷的烧结温度降低,陶瓷的微波介电常数εr和谐振频率温度系数(Τ)f下降,品质因素Qf明显降低.当BC添加量为5wt％时,在1000℃保温5h可烧结,此时陶瓷具有较佳的微波介电性能:εr=80.4,Q×f=1380 GHz,(Τ)f=- 32.89×10-6/℃.     

Structure,Microwave Dielectric Properties,and Novel Low‐Temperature Sintering of xSrTiO3–(1−x)LaAlO3 Ceramics with LTCC Application

xSrTiO₃–(1?x)LaAlO₃ ceramics with ZnO–B₂O₃ sintering aid were prepared by solid‐state reaction method leading to a significant decrease in sintering temperature from 1550°C to 1050°C. The structure, microwave dielectric properties, and low‐temperature sintering behavior were systematically investigated. The results revealed the relationships among ionic size, ionic polarizability and cell volume. With increasing additive, chemical ordering of B‐site cations was indicated with selected area electron diffraction (SAED) patterns, HRTEM images and Raman spectrum, which contributed to the greatly enhanced microwave dielectric properties. Particularly, the 0.7Sr_0.85 Mg_0.15TiO₃–0.3LaAlO₃ ceramics modified with 10 wt % ZnO‐B₂O₃ can further decrease the sintering temperature down to 950°C without deteriorating its performance. Thermal tests implied ceramics featured good chemical compatibility with Cu/Ag electrode. Thus, they can be cofired with internal Cu/Ag electrodes in special patterns to fulfill different electrical functions for LTCC (low‐temperature cofired ceramic) application.     

Effects of ZnO and B2O3 on the Microstructure and Microwave Dielectric Properties of 5Li2O‐1Nb2O5‐5TiO2 Ceramics

The effects of ZnO and B₂O₃ addition on the sintering behavior, microstructure, and the microwave dielectric properties of 5Li₂O‐1Nb₂O₅‐5TiO₂ (LNT) ceramics have been investigated. With addition of low‐level doping of ZnO and B₂O₃, the sintering temperature of the LNT ceramics can be lowered down to near 920°C due to the liquid phase effect. The Li₂TiO₃ss and the “M‐phase” are the two main phases, whereas other phase could be observed when co‐doping with ZnO and B₂O₃ in the ceramics. And the amount of the other phase increases with the ZnO content increasing. The addition of ZnO does not induce much degradation in the microwave dielectric properties but lowers the τ_f value to near zero. Typically, the good microwave dielectric properties of ε_r = 36.4, Q × f = 8835 GHz, τ_f = 4.4 ppm/°C could be obtained for the 1 wt% B₂O₃ and 4 wt% ZnO co‐doped sample sintered at 920°C, which is promising for application of the multilayer microwave devices using Ag as internal electrode.     

Ca(Mg_(1–x)Co_x)Si_2O_6陶瓷的烧结性能与微波介电性能

通过Co2+对Mg2+的取代,探讨不同x值下Ca(Mg1–xCox)Si2O6陶瓷的物相组成、烧结性能、微观结构以及微波介电性能。结果表明:Co2+对Mg2+的取代,可将Ca(Mg1–xCox)Si2O6陶瓷的烧结温度从1300℃降低至1 175℃;Co2+在Ca(Mg,Co)Si2O6中的固溶极限在0.2~0.3之间,Mg2+在Ca(Co,Mg)Si2O6中的固溶极限在0.3~0.4之间,当x位于0.3~0.6之间时,出现Ca(Mg,Co)Si2O6与Ca(Co,Mg)Si2O6两相共存;无论是Co2+固溶入Ca Mg Si2O6,形成Ca(Mg,Co)Si2O6,还是Mg2+固溶进入Ca Co Si2O6,形成Ca(Co,Mg)Si2O6,陶瓷晶粒均随固溶度的增大,出现异常长大,进而恶化陶瓷的品质因数。当x=0.5时,Ca(Mg,Co)Si2O6与Ca(Co,Mg)Si2O6两相共存,有效细化了陶瓷晶粒尺寸,1 225℃烧结后,陶瓷的微波介电性能为εr=8.04,品质因数Q×f=59 108 GHz,谐振频率温度系数τf=–51.02×10–6/℃。     

Influence of Copper(II) Oxide Additions to Zinc Niobate Microwave Ceramics on Sintering Temperature and Dielectric Properties

The effect of CuO additions on the firing temperature of ZnNb₂O₆ ceramics was investigated using dilatometry, transmission electron microscopy, and X-ray diffractometry. A 5 wt% CuO addition to ZnNb₂O₆ ceramics significantly lowered the firing temperature from 1150° to ∼900°C. The presence of a CuO-rich intergranular phase in the specimen was observed and was evidence of the formation of a liquid phase during sintering. The composition of the liquid phase was (ZnCu₂)Nb₂O₈. In particular, the low-fired ZnNb₂O₆ ceramics had good microwave dielectric characteristics— Q × f = 59 500, ɛ_r= 22.1, τ_f=–66 ppm/^oC. These properties were correlated with the formation of a second phase, (ZnCu₂)Nb₂O₈.     

Properties of Low‐Temperature Sintering PNN–PMW–PSN–PZT Piezoelectric Ceramics with Ba(Cu1/2W1/2)O3 Sintering Aids

Piezoelectric ceramics Pb(Ni_1/3Nb_2/3)O₃–Pb(Mg_1/2W_1/2)O₃–Pb(Sb_1/2Nb_1/2)O₃–Pb(Zr_0.39Ti_0.61)O₃ with Ba(Cu_1/2W_1/2)O₃ sintering aids were fabricated using economical industrial oxide powders and their piezoelectric, dielectric, and ferroelectric properties were investigated in order to develop low‐temperature sintering ceramics for multilayer piezoelectric actuators. A quadratic formula and the Curie–Weiss law reveal that the ceramics are typical displacive‐type ferroelectric relaxors. The ceramics sintered as low as 900°C have good piezoelectric properties of d₃₃ = 551 pC/N, k_p = 0.52, ε_r = 3583, tgδ = 0.02, and T_C = 161°C, which is much promising to manufacture multilayer piezoelectric transducers.     

Low‐Temperature Sinterable (1−x)Ba3(VO4)2–xLiMg0.9Zn0.1PO4 Microwave Dielectric Ceramics

The novel low‐temperature sinterable (1 ? x)Ba₃(VO₄)₂–xLiMg_0.9Zn_0.1PO₄ microwave dielectric ceramics were prepared by cofiring the mixtures of pure‐phase Ba₃(VO₄)₂ and LiMg_0.9Zn_0.1PO₄. The phase structure and grain morphology of the ceramics were evaluated using X‐ray diffraction, Raman spectra, and scanning electron microscopy. The results indicated that Ba₃(VO₄)₂ and LiMg_0.9Zn_0.1PO₄ phases can well coexist in the sintered body. Nevertheless, a small amount of LiZnPO₄ and some vanadate phases with low melting points were observed, which not only can influence the microwave dielectric properties of the ceramic but also can obviously improve the densification behavior at a relatively low sintering temperature. The near‐zero temperature coefficients of the resonant frequency (τ_f) could be achieved by adjusting the relative content of the two phases owing to their opposite τ_f values and simultaneously a desirable quality factor Q × f value can be maintained. No chemical reaction between the matrix ceramic phase and Ag took place after sintering at 800°C for 4 h. The ceramics with 45 vol% LiMg_0.9Zn_0.1PO₄ can be well sintered at only 800°C and exhibit excellent microwave dielectric properties of ε_r ~ 10, Q × f ~ 64 500 GHz, and τ_f ~ ?2.1 ppm/°C, thus showing a great potential as a low‐permittivity low‐temperature cofired microwave dielectric material.     

Dielectric Properties of Ultra‐Low Sintering Temperature Al2O3–BBSZ Glass Composite

Ceramic composites of B₂O₃–Bi₂O₃–SiO₂–ZnO (BBSZ) glass mixed with Al₂O₃ (10–50 vol%) were sintered at 450°C, and their microstructural and dielectric properties investigated. Dense structures were obtained when the Al₂O₃ content was lower than 30 vol%. Raman, XRD, and FESEM showed the existence of a secondary phase, Bi₂₄Si₂O₄₀, in all samples. The dielectric properties of the composite with 30 vol% addition of Al₂O₃ showed good dielectric properties with ε_r of 14.8 and 20.8 and 32.5 at 100 kHz and 100 MHz and 1 GHz, respectively. The tanδ values at the same frequencies were 0.004 and 0.006 and 0.016. The results show that BBSZ glass with different amounts of Al₂O₃ exhibit widely applicable relative permittivity values and affordable loss and are thus promising candidates for ultra‐low sintering temperature applications.     

Fabrication and Microwave Dielectric Properties of Mg2SiO4‐LiMgPO4‐TiO2 Composite Ceramics

Complete solid solutions between Mg₂SiO₄ and LiMgPO₄ are confirmed by the XRD results. The phase constitution of 0.5Mg₂SiO₄‐0.5LiMgPO₄ is found to be dependent on firing temperature. The chemical compatibility between Mg₂SiO₄ and rutile phase at sintering temperature is modified by incorporating LiMgPO₄. The microwave dielectric properties of (1?y)(0.5Mg₂SiO₄‐0.5LiMgPO₄)‐yTiO₂ (y = 0–0.3) composite ceramics have been investigated. The optimized microwave dielectric properties for 0.35Mg₂SiO₄‐0.35LiMgPO₄‐0.3TiO₂ ceramics sintered at 1050°C show low dielectric constant (11.4), high‐quality factor (31 800 GHz), and low‐temperature coefficient of resonant frequency (?4 ppm/°C).     

Preparation and Microwave Dielectric Properties of Ultra‐low Temperature Sintering Ceramics in K2O–MoO3 Binary System

A series of microwave dielectric ceramics in the compositions of K₂Mo₂O₇, K₂Mo₃O₁₀, and K₂Mo₄O₁₃ in K₂O–MoO₃ binary system with ultra low sintering temperatures were prepared using the solid‐state reaction method. Their synthesis, phase composition, compatibility with metal electrodes, microstructures, and microwave dielectric properties were investigated. The K₂Mo₂O₇ ceramic sintered at 460°C with a triclinic structure has a relative permittivity of 7.5, a Q × f value of 22 000 GHz, and a τ_f value of ?63 ppm/°C. The X‐ray diffraction patterns indicate that K₂Mo₂O₇ does not react with Ag and Al electrodes at the co‐fired temperatures. The K₂Mo₃O₁₀ ceramic can be sintered well at 520°C with a relative permittivity of 5.6, a Q × f value of 35 830 GHz, and a τ_f value of ?92 ppm/°C. It has compatibility with Ag electrode. The K₂Mo₄O₁₃ ceramic sintered at 540°C possesses good microwave dielectric properties with a relative permittivity of 6.8, a Q × f value of 39 290 GHz and a τ_f value of ?67 ppm/°C and it is compatible with Al electrode. For K₂Mo₂O₇ and K₂Mo₄O₁₃, it is found that the grain sizes and the number of grain boundaries play an important role in the dielectric loss. From this study, it can be seen that the three ceramics in K₂O–MoO₃ system have good microwave dielectric properties, ultra‐low sintering temperatures, non‐toxic, and low‐cost characteristics. So they can be potentially applied to ultra‐LTCC devices.     

Sintering Mechanism and Microwave Dielectric Properties of Bi12TiO20 Ceramics

A homogeneous Bi₁₂TiO₂₀ phase was developed in a specimen that was calcined at 700°C without the formation of a secondary phase. A small amount of the Bi₁₂TiO₂₀ phase melted during sintering and assisted the densification of the specimen. The Bi₂O₃ and Bi₈TiO₁₄ secondary phases were found in all specimens. All the specimens that were sintered at temperatures ≥775°C exhibited high relative densities above 98% of the theoretical density. The Q × f value of the Bi₁₂TiO₂₀ ceramics was influenced by the grain size. The Bi₁₂TiO₂₀ ceramics sintered at 800°C for 5 h showed promising microwave dielectric properties of ε_r = 41, Q × f = 10 400 GHz, and τ_f = ?10.8 ppm/°C.     

Sintering Process and Microwave Dielectric Properties of Bi8TiO14 Ceramics

The formation of a homogeneous Bi₈TiO₁₄ phase was successfully achieved in a specimen calcined at 600°C. However, a Bi₄Ti₃O₁₂ secondary phase also developed in specimens calcined at temperatures higher than 600°C, probably because of Bi₂O₃ evaporation. For specimens sintered above 800°C, a small amount of the Bi₈TiO₁₄ phase melted during sintering, with the liquid phase contributing to the densification of the specimens; however, Bi₄Ti₃O₁₂ and Bi₁₂TiO₂₀ secondary phases were still formed in these specimens. The microwave dielectric properties of the Bi₈TiO₁₄ phase were considerably affected by variations in the microstructure of the specimens. When the sintering temperature exceeded 825°C, the amount of secondary phases increased, and this decreased the density and Q×f values of the specimens. Bi₈TiO₁₄ ceramics sintered at 825°C exhibited promising microwave dielectric properties, with ε_r = 47.4, Q×f = 5370 GHz, and τ_f = ?16.01 ppm/°C.     

Low‐Temperature Sintering of β‐Spodumene Ceramics Using Li2O–GeO2 as a Sintering Additive

Low‐temperature sintering of β‐spodumene ceramics with low coefficient of thermal expansion (CTE) was attained using Li₂O–GeO₂ sintering additive. Single‐phase β‐spodumene ceramics could be synthesized by heat treatment at 1000°C using highly pure and fine amorphous silica, α‐alumina, and lithium carbonate powders mixture via the solid‐state reaction route. The mixture was calcined at 950°C, finely pulverized, compacted, and finally sintered with or without the sintering additive at 800°C–1400°C for 2 h. The relative density reached 98% for the sample sintered with 3 mass% Li₂O–GeO₂ additive at 1000°C. Its Young's modulus was 167 GPa and flexural strength was 115 MPa. Its CTE (from R.T. to 800°C) was 0.7 × 10^?6 K^?1 and dielectric constant was 6.8 with loss tangent of 0.9% at 5 MHz. These properties were excellent or comparative compared with those previously reported for the samples sintered at around 1300°C–1400°C via melt‐quenching routes. As a result, β‐spodumene ceramics with single phase and sufficient properties were obtained at about 300°C lower sintering temperature by adding Li₂O–GeO₂ sintering additive via the conventional solid‐state reaction route. These results suggest that β‐spodumene ceramics sintered with Li₂O–GeO₂ sintering additive has a potential use as LTCC for multichip modules.