B位(Mg_(1/3)Ta_(2/3))~(4+)置换对新型Sr基(Sr,Nd,Ca)TiO_3微波陶瓷结构及介电性能的影响
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摘要
采用固相反应法合成了(Sr_(0.2)Nd_(0.208)Ca_(0.488))Ti_(1-x)(Mg_(1/3)Ta_(2/3))_xO_3(0.2≤x≤0.5,SNCTMTx)系微波介质陶瓷,分析了SNCTMTx(0.2≤x≤0.5)陶瓷的相组成、显微结构、烧结特性和微波介电性能之间的关系。XRD晶体结构分析表明:当x=0.2时,SNCTMTx陶瓷为单一正交钙钛矿结构,当x值增为0.3~0.5时,陶瓷体呈现正交钙钛矿相、SrO与未知相多相共存状态。随着(Mg_(1/3)Ta_(2/3))~(4+)含量的增加,体系中第二相的出现及含量的改变导致εr先增后减,而Q×f值出现先降后升的原因是B位离子1:2有序度的出现与范围的增加抑制了第二相进一步恶化品质因子;此外,τf逐渐向近零方向偏移与氧八面体的畸变程度密切相关。当x=0.5时,在1530℃烧结4 h得到的SNCTMTx陶瓷微波介电性能较优:ε_r=55.3,Q×f≈7400 GHz,τf≈23.6×10~(–6)/℃。
(Sr_(0.2)Nd_(0.208)Ca_(0.488))Ti_(1-x)(Mg_(1/3)Ta_(2/3))_xO_3(0.2≤x≤0.5,SNCTMTx) ceramics were prepared by solid sate reaction technique.Wherein,the relation between phase compositions,microstructures,sintering properties,and microwave dielectric properties of the SNCTMTx(0.2≤x≤0.5) ceramic systems were studied.The XRD results indicated that a single phase with orthorhombic perovskite-like structure was formed in the sample with x = 0.2,and a mixed phase system was formed in the samples with given compositional range x = 0.3 – 0.5 composed of orthorhombic perovskite phase,Sr O phase and unknown second phase.Additionally,the εr first increased and then decreased,affected by the appearance and the content of the second phase.Meanwhile,the Q×f value showed down first and then up with the increase of(Mg_(1/3)Ta_(2/3))~(4+) content because the increasing degree of 1:2 ordering could suppress the reduction in quality factor.Moreover,the τf gradually shifted to near-zero direction,which resulted from the variation of the oxygen octahedral distortion.The SNCTMTx(x=0.5) ceramic sintered at 1530℃ for 4 h showed better microwave dielectric properties with εr = 55.3,Q×f ≈ 7,400 GHz and τf ≈ 23.6×10~(–6)/℃.
(Sr_(0.2)Nd_(0.208)Ca_(0.488))Ti_(1-x)(Mg_(1/3)Ta_(2/3))_xO_3(0.2≤x≤0.5,SNCTMTx) ceramics were prepared by solid sate reaction technique.Wherein,the relation between phase compositions,microstructures,sintering properties,and microwave dielectric properties of the SNCTMTx(0.2≤x≤0.5) ceramic systems were studied.The XRD results indicated that a single phase with orthorhombic perovskite-like structure was formed in the sample with x = 0.2,and a mixed phase system was formed in the samples with given compositional range x = 0.3 – 0.5 composed of orthorhombic perovskite phase,Sr O phase and unknown second phase.Additionally,the εr first increased and then decreased,affected by the appearance and the content of the second phase.Meanwhile,the Q×f value showed down first and then up with the increase of(Mg_(1/3)Ta_(2/3))~(4+) content because the increasing degree of 1:2 ordering could suppress the reduction in quality factor.Moreover,the τf gradually shifted to near-zero direction,which resulted from the variation of the oxygen octahedral distortion.The SNCTMTx(x=0.5) ceramic sintered at 1530℃ for 4 h showed better microwave dielectric properties with εr = 55.3,Q×f ≈ 7,400 GHz and τf ≈ 23.6×10~(–6)/℃.
引文
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[3]REANEY I M,IDDLES D.Microwave dielectric ceramics for resonators and filters in mobile phone networks.J.Am.Ceram.Soc.,2006,89:2063–2072.
[4]WISE P L,REANEY I M,LEE W E,et al.Structure-microwave property relations in(SrxCa1–x)n+1TinO3n+1.J.Eur.Ceram.Soc.,2001,21:1723–1726.
[5]HSUN C H,TSAI S H.Dielectric characteristics of Sr substitution on Ca0.4Sm0.4Ti O3 ceramics at microwave frequency.Ceram.Int.,2014,40:10111–10114.
[6]LI J M,QIU T.Microwave dielectric properties of(1-x)Ca0.6La0.267 Ti O3-x Ca(Sm0.5Nb0.5)O3 ceramics.Ceram.Int.,2012,38:4331–4335.
[7]FU M S,LIU X Q,CHEN X M.Structure and microwave dielectric characteristics of Ca1-xNd2x/3Ti O3 ceramics.J.Eur.Ceram.Soc.,2008,28:585.
[8]LIU F,YUAN C L,LIU X Y,et al.Microstructures and dielectric properties of(1–x)Sr Ti O3-x Ca0.61Nd0.26Ti O3 ceramic system at microwave frequencies.J.Mater.Sci.:Mater.Electron.,2015,26(1):128–133.
[9]KIM E S,CHUN E S,KANG D H.Effects of structural characteristics on microwave dielectric properties of(1-x)Ca0.85Nd0.1Ti O3-x Ln Al O3(Ln=Sm,Er and Dy)ceramics.J.Eur.Ceram.Soc.,2007,27:3005–3010.
[10]BRESE N E,O'KEEFFE M.Bond-valence parameters for solids.Acta.Cryst.,1991,B47:192–197.
[11]HAKKI B W,COLEMAN P D.A dielectric resonator method of measuring inductive capacities in the millimeter range.IRE.Trans.Microw.Theory.Tech.,1960,8:402–410.
[12]NISHIKAWA T,WAKINO K,TAMURA H.Precise measurement method for temperature coefficient of microwave dielectric resonator material.IEEE.MTT-S.Int.Microw.Symp.Dig.,1987,3:277–280.
[13]HONG K S,KIM I T,KIM C D.Order-disorder phase formation in the complex perovskite compounds Ba(Ni1/3Nb2/3)O3 and Ba(Zn1/3 Nb2/3)O3.J.Am.Ceram.Soc.,1996,79(12):3218–3224.
[14]WANG CHUN-XIN,SHI FENG.Crystal structure of(Ba1-xSrx)(Zn1/3Nb2/3)O3 solid solutions system.J.Rare Metal Materials and Engineering,2008,37(6):1108–1110.
[15]SHANNON R D.revised effective ionic radii and systematic studies of interatomic distances in halides and Chalcogenides.Acta.Cryst.,1976,A32:751–767.
[16]BIAN JIAN-JIANG,ZHAO MEI-YU,YAO YAO,et al.Sinterability,microstructure and microwave dielectric properties of Ba[Mgl/3Ta2/3(1+x)]O3.Journal of Inorganic Materials,1998,13(6):831–834.
[17]SHANNON R D.Dielectric poparizabilities of ions in oxides and flucorides.J.Appl.Phys.,1993,73(1):348–366.
[18]CHATTERJEE C,VIRKAR A N,PAUL A.Effects of Sr O addition on densification and dielectric properties of barium nano titanate.J.Mater.Sci.Lett.,1990,9:1049–1051.
[19]ICHINOSE N,SHIMADA T.Effect of grain size and secondary phase on microwave dielectric properties of Ba(Mg1/3Ta2/3)O3 and Ba[(Mg,Zn)1/3Ta2/3]O3 systems.J.Eur.Ceram.Soc.,2006,26(10/11):1755–1759.
[20]COLLA E L,REANEY I M,SETTER N.Effect of structure changes in complex perovskites on the temperature coefficient of the relative permittivity.J.Appl.Phys.,1993,74(5):3414–3425.