ZrO2添加对BaO-La2O3-TiO2介质陶瓷介电性能的影响

BaO-La2O3-TiO2(BLT)是典型的高介电常数微波介质陶瓷,其作为微波谐振器与滤波器的关键材料,在微波通讯技术上有着重要的应用. 选用ZrO2对BLT进行改性研究,当ZrO2的加入量z＜0.5mol时,烧结体的主晶相为Ba6-3xLa8 2x(Ti1-zZrz)18O54(x=1/2)钨青铜结构(TB)固溶体,随ZrO2加入量的增多,烧结体中产生第二相,当z＝1.0mol时,烧结体的主晶相为La2Zr2O7和BaZrO3,这与结构许容因子的变化密切相关,获得较优介电性能如下εr=103.71,Q·f=4862.53 GHz,τf=168.97×10-6/℃,优于不添加ZrO2时烧结体介电性能(εr=139.73,Q·f=1238.96 GHz,τf=179.97×10-6/℃) ,说明少量ZrO2的加入可以改善BLT陶瓷的品质因数和频率温度系数,略降低介电常数. SEM分析表明,少量ZrO2的加入没有改变烧结体的微观形貌,改性前后烧结体内部均为典型的柱状TB固溶体形貌.     

Li2O-Na2O-B2O3-SiO2烧结助剂对BaAl2Si2O8陶瓷结构与介电性能的影响

采用传统固相反应工艺,按化学计量比合成BaO-Al_2O3-SiO_2(BAS)-x%(w/w) Li_2O-Na_2O-B_2O3-SiO_2(LNBS)(x=0,1,2,3,4)陶瓷。研究不同LNBS烧结助剂添加量对BAS系微波介质陶瓷的结构和介电性能的影响。通过Clausius-Mossotti公式计算讨论了BAS理论与实验介电常数(εr)的差异。研究结果表明:LNBS烧结助剂中Li+进入钡长石Al3+位或单四元环(S4R)间隙,并产生了O_2-空位或Ba2+空位,从而促进BAS六方相向单斜相的转变。添加适量的LNBS烧结助剂后,BAS陶瓷的烧结温度从1 400℃降低到1 325℃,同时BAS陶瓷样品密度、品质因数(Qf)值以及频率温度系数(τf)得到改善。当x=1,烧结温度为1 325℃时,可获得综合性能相对较好的BAS陶瓷,其介电性能:Qf=35 199 GHz,εr=6.37,τf=-1.613×10-5℃-1。     

掺杂Sm_2O_3的Y_2O_3-2TiO_2系微波介质陶瓷的性能研究

以具有中介电常数的新型Y2O3-2TiO2系微波介质陶瓷为基体,选用Sm2O3作为掺杂改性剂,通过传统固相法制备成陶瓷。重点研究了不同Sm2O3掺杂量对基体Y2O3-2TiO2微波介质陶瓷物相组成和介电性能的影响。采用X射线衍射和扫描电子显微镜分别对其物相组成和显微结构进行了分析,用阻抗分析仪和网络分析仪测试其介电性能。结果表明:掺杂Sm2O3未改变材料的主晶相,仍为A2B2O7烧绿石结构,Sm3+取代Y3+占据A位;掺杂有效降低了陶瓷的烧结温度,掺杂量为5%(质量分数)时,烧结温度为1330℃,材料的综合性能最佳,εr=23,tanδ=0.0046,Q×f=6713 GHz。     

A位取代对(Ca0.61Nd0.26)TiO3陶瓷烧结特性和介电性能的影响

采用常规固相反应法,以(Ca0.61Nd0.26)TiO3体系为基体成分,研究了A位取代对(Ca0.61Nd0.26)TiO3陶瓷的烧结特性和介电性能的影响规律。结果表明:Zn,Mg的A位取代,促使(Ca0.61Nd0.26)TiO3陶瓷烧结温度从1350℃降至1250℃。Zn,Mg在一定范围内A位取代(Ca0.61Nd0.26)TiO3中的Ca可形成钙钛矿结构的固溶体,Zn、Mg最大固溶度(x(Zn),y(Mg))分别不超过0.1和0.15mol。当取代量超过固溶度后,分别形成Ca2Zn4Ti15O36和MgTi2O5第二相。随Zn和Mg取代量的增加,陶瓷介电常数(εr)和谐振频率温度系数(τf)减小。陶瓷品质因数(Qf)值随Zn取代量先增后减,而随Mg取代量增加,其Qf值一直增大。Zn,Mg最佳取代分别为x(Zn)=0.15和y(Mg)=0.25,在1250℃烧结2h,[(Ca0.85Zn0.15)0.61Nd0.26]TiO3的介电性能:εr=93.60,Qf=12454GHz,τf= 150.3ppm·℃-1,[(Ca0.75Mg0.25)0.61Nd0.26]TiO3的介电性能:εr=72.48,Qf=14622GHz,τf= 108ppm·℃-1。     

CaTiO3∶Zn溶胶-凝胶法制备、结构及介电性能

采用溶胶-凝胶法制备了CaTiO3∶Zn纳米粒子,透射电镜图显示平均粒径为25 nm。Zn的掺杂位置对于陶瓷相组成和烧结特性有很大影响。Ca1-xZnxTiO3和CaTiO3+zZnO样品的Zn以Zn2TiO4相形式存在;而CaZnyTi1-yO3-δ(y=0.01)样品中的Zn进入Ti位形成固溶体,无明显的降温效果,当Zn量增至0.05和0.1时,出现ZnO相。ZnO和Zn2TiO4第二相的存在均能明显促进陶瓷烧结。CaTiO3∶Zn超细粉体可在较低温度下致密烧结(≤1 250℃)。1 250℃烧结的CaZnyTi1-yO3-δ(y=0.01)陶瓷具有较好的介电性能:介电常数ε=157,品质因数Q×f=6 819 GHz,谐振频率温度系数τf=7.51×10-4℃-1。     

CaTiO3:Zn溶胶-凝胶法制备、结构及介电性能

采用溶胶-凝胶法制备了CaTiO3:Zn纳米粒子,透射电镜图显示平均粒径为25 nm.Zn的掺杂位置对于陶瓷相组成和烧结特性有很大影响.Ca1-xZnxTiO3和CaTiO3+zZnO样品的Zn以Zn2TiO4相形式存在;而CaZnyTi1-yO3-δy=0.01)样品中的Zn进入Ti位形成固溶体,无明显的降温效果,当Zn量增至0.05和0.1时,出现ZnO相.ZnO和Zn2TiO4第二相的存在均能明显促进陶瓷烧结.CaTiO3:Zn超细粉体可在较低温度下致密烧结(≤1 250 ℃).1 250℃烧结的CaZnyTi1-yO3-δ(y=0.01)陶瓷具有较好的介电性能:介电常数ε=157,品质因数Q×f=6 819 GHz,谐振频率温度系数(τ)f=7.51×10-4℃-1.     

B2O3-Bi2O3-ZnO-Al2O3玻璃助烧剂对BaTiO3陶瓷烧结条件、晶体结构和介电性能的影响

通过调节B₂O₃-Bi₂O₃-ZnO-Al₂O₃(BBZA)玻璃的添加量研究其对钛酸钡(BaTiO₃)陶瓷烧结条件、晶体结构和介电性能的影响。结果表明：添加适量的BBZA玻璃能够有效地将BaTiO₃陶瓷烧结温度由1 350℃降至950℃,并使其致密化。同时,添加BBZA玻璃后,BaTiO₃的晶体结构随着烧结温度的升高而发生转变(立方相→四方相)。另外,BBZA玻璃的引入使BaTiO₃陶瓷的居里峰得到了有效的抑制和拓宽。陶瓷微观形貌显示,玻璃相均匀分布在BaTiO₃晶粒表面。优化的BaTiO₃陶瓷制备条件如下：BBZA添加量(质量分数)为2.0%,烧结温度为950℃。在该条件下制备的BaTiO₃陶瓷介电常数达到1 364,介电损耗低至1.2%。     

溶胶-凝胶法制备(Ba0.85Ca0.15)(Ti0.9Zr0.1)O3无铅压电陶瓷研究

锆钛酸钡钙基无铅压电陶瓷由于具有较好的压铁电性能且环境友好而备受研究者关注,但其存在烧结温度高(>1450℃)、居里温度低等缺点。为降低锆钛酸钡钙基压电陶瓷的预烧及烧结温度,并优化其电学性能,本研究采用溶胶-凝胶法成功合成了(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃无铅压电陶瓷的前驱粉体,并在预烧温度为1000℃、烧结温度为1420℃时成功制备了(Ba_0.85Ca_0.15)(Ti_0.9Zr_0.1)O₃陶瓷,相较于传统固相法,陶瓷的预烧温度降低了250℃,烧结温度降低了30℃,成功改善了陶瓷的烧结行为,得到了铁电性能、介电性能和压电性能优良且致密性良好的低温烧结陶瓷。     

低温烧结NaBi(WO4)2陶瓷的介电性能

采用固相合成法制备了NaBi(WO₄)₂(NBW)陶瓷,研究了NBW陶瓷的相结构、形貌、烧结特性和微波介电性能。NBW陶瓷在625～800℃烧结1～4 h能够致密化。X射线衍射表明在625～800℃烧结2 h的NBW陶瓷均为四方晶系白钨矿结构的单相陶瓷。随着烧结温度的提高,NBW陶瓷的介电常数、品质因数(Qf值)先增加后降低,谐振频率温度系数逐渐降低。经650℃烧结2 h获得的NBW陶瓷的介电常数为14.36,Qf值为16 503 GHz,谐振频率温度系数为-1.055×10^-5℃^-1。NBW陶瓷与银共烧反应生成Ag₂W₂O₇相,而与Au、Al共烧具备化学兼容性。     

纳米CaMgSi2O6粉体的低温合成与微波介电性能

以硝酸锂、偏钒酸铵、硝酸钙、硝酸镁、正硅酸乙酯为原料，采用溶胶-凝胶法低温合成纳米CaMgSi₂O₆微波介质陶瓷粉体，研究了不同粒径粉体的烧结行为与微波介电性能。结果表明，通过在钙镁硅溶胶中引入锂钒烧结助剂可大大降低陶瓷粉体的晶相合成温度，干凝胶在750 ℃煅烧后可获得主晶相为CaMgSi₂O₆、分散性良好、粒径为78～98 nm的陶瓷粉体，可满足微型片式元器件用超薄陶瓷介质层的制备要求;该粉体在890 ℃烧结后获得致密结构的陶瓷，具有良好的微波介电性能:介电常数为7.68，品质因数为24 542 GHz，频率温度系数为-57.25×10^-6 ℃^-1。     

高介电常数TiO2纳米晶的表面态研究

将钛酸四丁酯和硬脂酸在熔融状态下混合均匀后置于冷水浴中,使其凝固成凝胶,通过控制烧结过程中氧气的含量,成功地制备出粒度均匀、介电性能好的纳米晶TiO2.通过采用X射线光电子能谱和表面光电压谱对纳米晶TiO2表面状态的分析发现,材料表面存在大量的氧空位缺陷,暴露在粒子表面上的主要是一些金属Ti4+.纳米材料的这种表面状态对其极化性质具有重要的影响,使其在接近静态条件下的低频介电常数远大于常规材料的介电常数.     

微波介质材料BaEu2Ti4O12的交流阻抗谱表征

采用交流阻抗谱技术对微波介质材料BaEu2Ti4O12进行了表征。分析了lgε/lgf, Z″/Z′和Y′/lgf等图谱的特征与材料性能的关系.研究结果表明：1）阻抗谱测试得到的介电常数与所发表的微波测试结果有很好的一致性,高频下得到的介电常数实际上是晶粒和晶界的净结果,高质量烧结的材料应具有薄的晶界，因而应表现出较大的介电常数; 2）如果将材料从高温下缓慢降温或在O2气氛中退火，材料的导电性都会下降，其原因可以理解为这样处理的材料氧空位浓度降低，进而可以推测这有利于降低材料的介电损失.     

钐掺杂对钛酸钡锶陶瓷结构和介电性能的影响

采用溶胶-凝胶法制备了系列Sm掺杂的Ba(0.8-3x/2)SmxSr0.2TiO3(x=0,0.001,0.003,0.006,0.008 and 0.010)粉体及陶瓷。利用X射线粉末衍射、扫描电子显微镜和精密阻抗分析表征了样品的结构和性质。X射线衍射结果表明Ba(0.8-3x/2)SmxSr0.2TiO3粉体在800℃预烧2 h后为单一的钙钛矿结构;通过对陶瓷微观形貌研究发现,Sm掺杂可以明显地抑制陶瓷晶粒生长,随着Sm掺杂量的增加,晶粒尺寸由40μm减小到2μm;居里温度随着Sm掺杂量的增加而线性降低,移动速率为10℃/mol%,室温下介电常数呈现先增加后减小的趋势,并在x=0.006时达到最大值7800。     

Bi4(Ti1/3Sn2/3)3O12掺杂BaTiO3基X8R陶瓷微观结构与介电性能

研究了Bi4(Ti1/3Sn2/3)3O12掺杂对钛酸钡基陶瓷微观结构和介电性能影响。结果表明,掺杂Bi4(Ti1/3Sn2/3)3O12后钛酸钡基陶瓷晶粒明显长大,同时烧结温度可由1 280℃降低至1 180℃。系统的介电性能和Bi4(Ti1/3Sn2/3)3O12的掺杂量有密切关系。当Bi4(Ti1/3Sn2/3)3O12的掺杂量从0.5mol%增加到2mol%,体系的居里峰被明显压低和展宽,当掺杂量为2mol%时居里峰变得不明显。当Bi4(Ti1/3Sn2/3)3O12的掺杂量从0.5mol%增加到2mol%,系统的居里温度由131℃升高至139℃。当Bi4(Ti1/3Sn2/3)3O12的掺杂量为1mol%时,钛酸钡基陶瓷介电常数为1 930,介电常数温度变化率为5%(-55℃),13%(134℃),-8%(150℃),满足X8R标准。     

Low Dielectric Thermoset from Redistributed Poly(phenylene oxide)

A curable low-molecular-weight poly(phenylene oxide) (PPO) was prepared by the redistribution of regular PPO with bisphenol-A (BPA) followed by etherification of the redistributed-PPO (BPA-PPO) with N,N-diallyl-2-chloroacetamide. The redistributed-PPO with allyl group (AL-PPO) was characterized by proton nuclear magnetic resonance, and Fourier transform infrared spectroscopy. The AL-PPO oligomers with reactive double bounds were cured with triallylisocyanurate (TAIC) and/or phosphorus-containing allyl-functionalized monomer (allyl-DOPO). The glass transition temperatures were measured by dynamic mechanical analysis (DMA). Electrical properties of cured resins were studied using dielectric analyzer (DEA). The flame retardancy was determined by a UL-94 vertical test. The effects of curing accelerator, amount of TAIC and allyl-DOPO incorporated into the network on the glass transition temperatures, dielectric properties, and flame retardancy of the resulting systems were investigated. The results indicated that AL-PPO cured with TAIC exhibited high glass-transition temperature (162–198°C), low dielectric constants (2.36–2.57 at 1 GHz) and dissipation factors (0.0039–0.0043 at 1 GHz). The AL-PPO/TAIC copolymerized with allyl-DOPO could achieve a flame retardancy rating of UL-94 V-0 at about 1.35% phosphorus content. The AL-PPO/TAIC resins have potential applications in the fabrication of printed circuit board.     

Dielectric spectroscopy of polyazomethine with vinylene moieties in the main chain

We have explored the dielectric properties of polyazomethine with vinylene moieties in the main chain (PAZ-PV). The dialdehyde 2,5-bis(hexyloxy)-1,4-bis[(2,5-bis(hexyloxy)-4-formyl-phenylenevinylene]benzene was polymerised in solid-state with the diamine poly(1,4-butanediol)bis(4-aminobenzoate). The polymer obtained exhibited liquid crystal properties. The molecular dynamics and phase transitions including the liquid crystal phase of PAZ-PV were investigated by dielectric spectroscopy. The dielectric constant decreases with a decrease in the temperature, except in the nematic phase region, where a slight increase was observed. The temperatures of the phase transitions were well seen and were compared with differential scanning calorimetry (DSC) and polarised optical microscopy experiments. All values determined from dielectric data were a few degrees higher than those obtained in previous measurements (DSC).     

(K_(0.485)Na_(0.485)Li_(0.03))NbO_3-Pb(Zr_(0.53)Ti_(0.47))O_3陶瓷的介电铁电性能

采用传统电子陶瓷工艺制备新型钙钛矿体系(1-x)(K_(0.485)Na_(0.485)Li_(0.03))NbO_3-Pb(Zr_(0.53)Ti_(0.47))O_3陶瓷,研究了该体系陶瓷的介电铁电性能.X射线衍射分析表明:所有陶瓷样品都具有单一的钙钛矿结构,在0.65≤x≤0.75时,出现明显的正交相和四方相的准同型相界区.测试结果表明:陶瓷具有高介电常数.低介质损耗,良好的温度稳定性;获得了饱和的电滞回线,显示了优良的铁电性能.尤其在x=0.75时各项性能达到最佳,其中介电常数ε_r=1590,介电损耗tan δ=0.017,居里温度T_c=295℃,剩余极化强度P,=28.6 μC·cm~(-1),矫顽场强E_c=0.89 kV·mm~(-1).     

Highly Transparent and Colorless Polyimide Film with Low Dielectric Constant by Introducing Meta-substituted Structure and Trifluoromethyl Groups

An effective design strategy for preparing highly transparent polyimide film with low dielectric constant is presented. The key to the strategy is to simultaneously introduce meta-substituted structure and trifluoromethyl in polymer chains. By using this design strategy, a highly transparent polyimide film with low-k was synthesized from 3,5-diaminobenzotrifluoride(m-TFPDA) and 4,4′-(hexafluoroisopropylidene)diphthalic anhydride(6 FDA) through a two-step method. The obtained m-TFPDA/6 FDA(CPI) film(～30 μm) possesses high optical transparency(λ_(cutoff)=334 nm, T_(450nm)=85.26%, Haze=0.31) and is close to colorless(L*=96.03, a*=-0.34, b*=2.12, yellow index=3.96). The intrinsic k and dielectric loss value of the film are 2.27 and 0.0013 at 10 kHz, respectively. More importantly, such low dielectric performance could remain stable up to280 °C, and the film shows a low moisture rate(～0.51%), which helps to maintain the low-k property stability in different humid environments.Meanwhile, the film also shows good thermal stability and mechanical properties, with a glass transition temperature(T_g) of 296 °C and the 5 wt%decomposition temperature(T_(d,5%)) of 522 °C under N_2. The tensile strength and tensile modulus of the film are 85.1 MPa and 1.96 GPa,respectively. In addition, the film is soluble in common solvents, which allows simple solution processing and low-cost, continuous roll-to-roll processes. This design strategy is beneficial to improving the transparency, lightening yellow color, lowering the dielectric constant and meanwhile maintaining the comprehensive properties of polyimide films, which is mainly due to the introduced meta-substituted and trifluoromethyl structures effectively inhibiting the transfer of charge transfer complex(CTC) effects and increasing the free volume of film. This design strategy could also be extended to other high-performance polymer systems.     

类钙钛矿新铌酸盐Ba5NdTi2Nb3O18的合成、结构与介电特性

为满足现代通信技术的小型化、集成化与高可靠性的迫切要求,探索具有高介电常数、低介电损耗与低温度系数的微波介电材料引起了材料科学、化学、物理、电子等领域科学工作者的广泛关注,并已开发出复合钙钛矿结构Ba(Zn_(1/3)Ta_(2/3))O_3、钨青铜结     

278.15-313.15 K下糖-水二元体系的介电常数

测定了D-(-)-果糖、D-(+)-葡萄糖、D-(+)-半乳糖、D-(+)-木糖和D-(-)-核糖五种糖的水溶液在不同质量摩尔浓度和不同温度下的介电常数(D). 结果表明, 在一定温度下, 这些糖的水溶液介电常数对数值都随糖浓度的增大而减小; 在一定糖浓度时, 介电常数值随温度升高而减小. 果糖、葡萄糖、半乳糖和木糖水溶液的介电常数(D)随温度的变化均满足关系式: lgD=A1-B1(T-298.15), 而核糖水溶液则符合: lgD=A2-B2(T-298.15)+C2(T-298.15)2. 此外, 这五种糖的水溶液的介电常数与摩尔分数(x)满足关系式: lg(D/D0)=-B3x. 在相同温度和浓度时, 介电常数的大小顺序通常为: 水>半乳糖-水>果糖-水>葡萄糖-水≥木糖-水(而核糖较特殊).