Ca1-x（Li1/2Sm1/2）xTiO3体系微波介质陶瓷的低温烧结研究

采用传统陶瓷制备工艺,制备了添加10 wt%NCB(Na2O-CaO-B3O3)复合氧化物的Ca1-x(Li1/2Sm1/2)xTiO3(x=0.700～0.875)(CLST-x)体系陶瓷,研究了添加NCB后CLST-x体系的晶相组成、显微结构、烧结性能及微波介电性能与组成关系.研究结果表明,添加复合氧化物NCB后,CLST-x体系各组成主晶相仍呈斜方钙钛矿结构,没有其它杂相.添加10wt%NCB后,CLST-x体系陶瓷均可在950℃下烧结致密,在此温度下材料具有较佳的微波介电性能,其中CLST-0.875陶瓷在950℃保温5 h烧结后具有良好的微波介电性能:εr=63.6,Qf=1591 GHz,τ f=0 ppm/℃,可满足高介多层微波器件的设计要求.     

Ca（0.2）（Li（1/2）Sm（1/2））（0.8）TiO3微波介质陶瓷低温烧结研究

以Ca0.2(Li1/2Sm1/2)0.8TiO3(CLST-0.8)为基料,添加质量分数10%的CaO-B2O3-SiO2(CBS)复合氧化物、4%的Li2O-B2O3-SiO2-CaO-Al2O3(LBSCA)玻璃料和0～2%的CuO氧化物为复合烧结助剂,研究了CuO含量的变化对CLST-0.8陶瓷的低温烧结行为及微波介电性能的影响.随着CuO添加量的增加,陶瓷体积密度、介电常数εr、无载品质因数与谐振频率乘积Qf值,都呈先增加后降低,谐振频率温度系数τf则呈先降低后升高的趋势.添加10%CBS、4.0%LBSCA和1.0%CuO的CLST-0.8微波介质陶瓷,可在900℃下保温5h烧结,并具有较佳的微波介电性能:εr=58.36,Qf=2011GHz, τf=3.44 ppm/℃.     

低温烧结Ca[(Li1/3Nb2/3)0.8Ti0.2]O3-σ微波介质陶瓷掺杂改性

本文研究了ZnO对低温烧结Ca[(Li1/3Nb2/3)0.8Ti0.2]O3-σ烧结特性、介电性能的影响。研究表明:ZnO对Ca[(Li1/3Nb2/3)0.8Ti0.2]O3-σ陶瓷的烧结无明显促进作用;适当的ZnO可提高Ca[(Li1/3Nb2/3)0.8Ti0.2]O3-σ的品质因子Qf值,w(ZnO)含量从0%变化到3%,Qf值从8730GHz增至11228GHz;随ZnO含量的增加,εr减小,τf向负频率温度系数方向移动,Qf值先增后减;添加3wt%ZnO的Ca[(Li1/3Nb2/3)0.8Ti0.2]O3-σ陶瓷,在920℃烧结4h,获得介电性能为:εr=37,Qf=11228GHz,τf=0的低温烧结微波介质陶瓷材料。     

低温烧结微波介质陶瓷的研究现状及展望

微波介质陶瓷是现代通讯技术中关键基础材料,综述了低温烧结微波陶瓷的研究现状,介绍了几种重要的低温烧结微波陶瓷体系,指出了改善低温烧结的微波介质陶瓷性能的途径和预期进展.     

微波介质陶瓷及其低温烧结研究进展

微波介质陶瓷是现代通讯技术中的关键基础材料，它的应用日益受到人们的重视。本文简要介绍了四类微波介质陶瓷的研究现状．着重评述了微波介质陶瓷在低温烧结方面的最新研究进展。     

高介电常数微波介质陶瓷及其低温烧结的研究进展

高介电常数微波介质材料是实现现代微波通信器件要求的微型化、集成化发展趋势的重要材料,针对多层结构设计的器件要求,需要微波介质陶瓷能与高电导率电极实现低温共烧。本文综述了近年来高介电常数微波介质陶瓷及其低温烧结研究的最新进展,指出进一步提高陶瓷的介电常数和研究新型低温烧结助剂是今后发展的趋势。     

固有烧结温度低的微波介质陶瓷

微波介质陶瓷是现代通讯技术中的关键基础材料。在制备多层微波介质片时,为了使用Cu、Ni等低熔点电极,必须降低微波介质陶瓷的烧结温度。开发固有烧结温度低(<1060℃)同时具有良好性能的微波介质材料成为必然的选择。本文简要介绍了7类固有烧结温度低的微波介质陶瓷的烧结特性与微波介电性能,同时也指出了研究中存在的一些问题。     

低温烧结Mg_4Nb_2O_9-0.75wt%V_2O_5-1.5wt%Li_2CO_3微波介质陶瓷及其性能研究

采用高能球磨法制备陶瓷,研究了0.75wt%V2O5和1.5wt%Li2CO3共掺杂对Mg4Nb2O9陶瓷的烧结性能和微波介电性能的影响。实验结果表明0.75wt%V2O5和1.5wt%Li2CO3共掺杂有助于Mg4Nb2O9陶瓷在烧结过程中形成液相,促进低温致密化烧结,进而降低陶瓷的烧结温度。900℃烧结Mg4Nb2O9陶瓷,结构致密、组织均匀,平均粒径0.75μm,εr=12.58,Q×f=5539 GHz。随烧结温度升高,晶粒长大,密度升高,εr和Q×f值增大。微波介电性能表征表明Mg4Nb2O9-0.75wt%V2O5-1.5wt%Li2CO3陶瓷在950℃下低温烧结,获得εr=13.07,Q×f=10858GHz的亚微米级陶瓷,其优良的微波介电性能使其有望成为新一代低温烧结低介高频微波介质基板材料。     

Li2O对AlN陶瓷低温烧结的影响

利用XRD，SEM和TEM研究了Li2O-CaF2-Y2O3在AlN陶瓷低温烧结中的作用机理，研究发现，添加Li2O的AlN陶瓷有着更低的收缩开始温度和更大的收缩率，这种收缩来自于Li玻璃相与CaYAlO4液相的共同作用。在烧结过程中，Li2O不仅改变了AlN烧结过程中的相组成，而且改善了液上的性质。由于Li2O的Al2O3在1100℃以下反应生成含Li玻璃相，使得AlN开始收缩的温度大为降低。在1600℃以下，含Li玻璃相分解散失，有利于AlN晶界的纯化，同时，CaYAl3O7向CaYAlO4的转变以及液相CaYAlO4在烧结过程中稳定存在，保证了含Li玻璃相散失后AlN的持续收缩。     

低温烧结中介电常数微波介质陶瓷材料的研究进展

中介电常数微波介质陶瓷是现代通讯技术中4GHz～8GHz频率范围内的关键基础材料,综述了低温烧结中介电常数微波陶瓷的研究现状,介绍了几种重要的低温烧结中介电常数微波陶瓷体系,指出了几种体系材料存在的问题以及努力的方向和预期进展.     

Microwave Dielectric Ceramics Li2MO4−TiO2 (M = Mo,W) with Low Sintering Temperatures

In this work, novel series of (1 ? x)Li₂MO₄–xTiO₂ (M = Mo, W; x = 0.3, 0.4, 0.45, 0.5, 0.6) ceramics were developed for microwave dielectric application. They were prepared via the mixed‐oxide process and the phase composition, microstructures, sintering behaviors, and microwave dielectric properties were investigated. The X‐ray diffraction (XRD) pattern and scanning electron microscope analysis indicated that the Li₂MO₄ (M = Mo, W) did not react with rutile TiO₂ and a stable two‐phase composite system Li₂MO₄–TiO₂ (M = Mo, W) was formed. The XRD pattern of cofired ceramics revealed that some parts of Li₂MoO₄ phase and very small part of Li₂WO₄ phase react with Ag to form Ag₂MoO₄ phase and Ag₂WO₄ phase, respectively. At x = 0.45–0.5, temperature stable microwave dielectric materials with low sintering temperature (700°C–730°C) were obtained: ε_r = 10.6–11.0, Qf = 30 060–32 800 GHz, and temperature coefficient of resonant frequency ~0 ppm/°C.     

H3BO3对Li2Zn3Ti4O12微波介质陶瓷低温烧结与微波介电性能的影响

采用传统固相反应法制备了添加H3BO3助烧剂的Li2Zn3Ti4O12 (LZT)陶瓷,分别通过XRD、SEM、排水法及网络分析仪等方法研究了不同H3BO3添加量对所得陶瓷的物相、微观形貌、烧结特性与微波介电性能的影响.结果表明在LZT陶瓷中添加3wt% H3BO3可有效降低烧结温度,在900 ℃/2 h烧结条件下可以获得高致密性及优异的微波介电性:ρ=4.15 g/cm3,εr=17.916,Q×f=61200 GHz,Tf=-52.87×10-6/℃.     

Dielectric properties of Sr0.5Ca0.5TiO3: x Pr3+ ceramics

The frequency dependent dielectric and AC conductivity properties of different concentrations of Pr³⁺ doped Sr_0.5Ca_0.5TiO₃ ceramics were investigated for the frequency range 100 Hz to 2 MHz at different temperatures. The morphology of the prepared samples was analyzed by using Field-Emission Scanning Electron Microscope images. The value of dielectric constant and dielectric loss decreases with increase in the frequency of the applied signal in all the samples. Also, the value of dielectric constant and dielectric loss decreased with doping of different concentrations of Pr³⁺ ions. The conductivity of the samples obeys Jonscher's power-law and shows a decrease with increasing doping concentration of Pr³⁺ ions. The higher value of real and imaginary part of impedance at lower frequency indicates the space charge polarization of the material and its absence at higher frequencies was confirmed from the low value of impedance at higher frequency region. The Cole- Cole parameters of the samples were calculated and the semi-circle observed indicates a single relaxation process and can be modeled by an equivalent parallel RC circuit. At lower frequency region, the value of dielectric constant and dissipation factor increases with increase in the temperature. Also the value of conductivity increases with temperature at high frequency region, due to the enhanced mobility of charge carriers.     

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.     

The Role of Microstructure on Microwave Dielectric Properties of (Ba,Sr)TiO3 Ceramics

Microstructural effects on the microwave dielectric properties of (Ba_0.4Sr_0.6)TiO₃ (BST) polycrystalline ceramics were investigated, focusing on the grain size. Sintering temperatures between 1350°C and 1500°C have a strong effect on the permittivity (880 < ε_r < 990), quality factor (570 GHz < Q×f < 1150 GHz), and temperature coefficient of resonant frequency (3920 ppm/°C < τ_f < 4560 ppm/°C) at microwave frequency (≈1.4 GHz). The tunable permittivity characteristics (measured at 10 kHz), were also found to be sensitive to the sintering process, demonstrating the possibility of tailoring material property by designed processing. In addition, the effect of the sintering process on grain structure was investigated by XRD calculation and Raman scattering characterization. Less confined phonons were believed to contribute to the enhanced microwave performance as an intrinsic effect (grain size effect), for samples with higher sintering temperature and longer dwell time. On the contrary, the macroscopic properties tend to saturate (or deteriorate), for samples at intensified sintering condition, being thought to be dominated by the extrinsic factors (such as the abundant defects in large grains), as confirmed by the SEM observations.     

Li2Zn3(1-x)Ca3xTi4O12微波陶瓷介电性能研究

本文以Li2CO3,ZnO,CaCO3,TiO2为原料,采用固相反应法制备了Li2Zn3(1-x)Ca3xTi4O12(x=0,0.05,0.1,0.15)陶瓷,并研究了CaTiO3固溶量对其显微结构和微波介电性能的影响.结果表明:Li2Zn3Ti4O12晶相中固溶CaTiO3相,晶胞参数会增大;少量CaTiO3相固溶于Li2Zn3Ti4O12陶瓷后,提高了Li2Zn3Ti4012陶瓷的烧结温度及其介电常数,但降低了其品质因素,可增大其温频系数.在1100℃/2 h烧结条件下,Li2Zn2.7Ca0.3Ti4O12陶瓷微波介电性能达到:εr=24,Q×f=50000 GHz,Tf=-25×10-6/℃.     

Sr(Ga0.5Nb0.5)1−xTixO3 Low‐Loss Microwave Dielectric Ceramics with Medium Dielectric Constant

The microwave dielectric properties of Sr(Ga_0.5Nb_0.5)_1?xTi_xO₃ (x = 0, 0.1, 0.2 and 0.3) ceramics have been investigated together with their microstructures. Single‐phase solid solutions are achieved in this series of ceramics. The ordering features are comprehensively analyzed by transmission electron microscopy and Raman spectroscopy. Local 1:1 ordering in B‐site leads to a double‐cubic structure with space group , while Ti substitution disrupts this 1:1 ordering between Ga and Nb, and the metastable ordering between Ti and (Ga + Nb) is speculated to form due to their large size difference. The dielectric constant and temperature coefficient of resonant frequency increase nonlinearly as x increases, while the Qf value decreases gradually. The variation trend of Qf value is mainly attributed to the intrinsic loss because of the increasing vibrational anharmonicity by Ti substitution. The ordering transition from short coherence, long‐range ordering to short‐range ordering with increasing Ti content has an agreeable and weak effect on the Qf value. The best combination of microwave dielectric properties is achieved for the composition of x = 0.3: ε_r = 46.6, Qf = 42 200 GHz and τ_f = 5.0 ppm/°C.     

低温烧结微波介质陶瓷（1－x）Ba3（VO4）2-xLi2 MoO4的微波性能研究

采用固相反应制备了（1－x）Ba3（VO4）2-xLi2MoO4微波介质陶瓷,研究了掺入不同质量比的Li2MoO4对Ba3（VO4）2的微观结构和微波介质性能影响,X线衍射（XRD）测试结果表明,Ba3（VO4）2和Li2MoO4二者兼容性良好,无第二相产生。添加具有低熔点及相反（负）频率温度系数的Li2 MoO4能有效降低Ba3（ VO4）2的烧结温度,并随着添加剂Li2 MoO4的增加,此复合陶瓷的相对体密度、介电常数εr 和品质因数Q ×f呈现出先增加随后又降低的趋势,而谐振频率里面温度系数τf逐渐降低。当烧结温度为660℃且添加量30wt％Li2 MoO4的复合微波介质陶瓷获得了最佳的微波介电性能：εr ＝11．99, Q ×f＝39700 GHz,τf ＝－24 ppm／℃。     

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).