添加Er_2O_3及煅烧温度对固相反应制备CaTiO_3材料的影响
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摘要
为提高合成CaTiO_3材料的烧结性能,以分析纯的CaO和TiO_2为原料,以Er_2O_3为添加剂,按照CaO、TiO_2反应的化学计量比配料,在混合粉末中分别外加质量分数1%、2%、3%和4%的Er_2O_3进行球磨混合,通过固相反应烧结法合成钛酸钙材料。利用X射线衍射仪、扫描电子显微镜、能谱仪分别对试样的物相组成、显微形貌及组成进行了分析表征。用衍射仪配套软件X’Pert High Score Plus计算钛酸钙晶胞参数,分析了离子间取代行为和晶胞体积变化的关系。结果表明:伴随Er_2O_3的少量添加,Er3+与Ti4+之间优先发生置换反应,致使CaTiO_3的晶胞结构发生畸变,晶胞体积增大。当进一步提高Er_2O_3添加量时,取代反应在Er3+与Ca2+之间发生,CaTiO_3晶胞发生收缩,晶胞体积呈减小趋势。Er_2O_3与CaTiO_3的固溶造成的晶格畸变促进了离子间的扩散,加速了固相反应烧结,造成的结构缺陷促进了CaTiO_3晶粒的生长。同时,随着煅烧温度的升高,结构中热缺陷数量增多,提高了钛酸钙材料的烧结性能。
CaTiO_3 materials were prepared using analytically pure CaO and TiO_2 as starting materials,and Er_2O_3 as an additive to improve the sintering characteristics. After ball milling the stoichiometric CaO and TiO_2,and extra-added Er_2O_3( 1%,2%,3%,and 4%,by mass),the mixtures were synthesized into CaTiO_3 materials by the solid reaction sintering method. The phase composition,microstructure and element composition of the products were investigated by XRD,SEM and EDS. The cell parameters were determined by X'Pert High Score Plus software to analyze the relationship between ionic substitution and cell volume. The results indicate that when adding a little Er_2O_3,the displacement reaction between Er3 +and Ti4 +happens preferentially,the CaTiO_3 cell structure distorts,thus the cell volume increases. When the addition of Er_2O_3 increases,the displacement reaction between Er3 +and Ca2 +happens,the CaTiO_3 cell shrinks,thus the cell volume decreases. The lattice distortion caused by the solid solution of Er_2O_3 and CaTiO_3 accelerates the ion diffusion and promotes the sintering of CaTiO_3 material,and the occurred structure defects accelerate the growth of CaTiO_3 grains. With the calcining temperature rising,thermal defects increase,and the sintering property of synthesized CaTiO_3 is promoted.
CaTiO_3 materials were prepared using analytically pure CaO and TiO_2 as starting materials,and Er_2O_3 as an additive to improve the sintering characteristics. After ball milling the stoichiometric CaO and TiO_2,and extra-added Er_2O_3( 1%,2%,3%,and 4%,by mass),the mixtures were synthesized into CaTiO_3 materials by the solid reaction sintering method. The phase composition,microstructure and element composition of the products were investigated by XRD,SEM and EDS. The cell parameters were determined by X'Pert High Score Plus software to analyze the relationship between ionic substitution and cell volume. The results indicate that when adding a little Er_2O_3,the displacement reaction between Er3 +and Ti4 +happens preferentially,the CaTiO_3 cell structure distorts,thus the cell volume increases. When the addition of Er_2O_3 increases,the displacement reaction between Er3 +and Ca2 +happens,the CaTiO_3 cell shrinks,thus the cell volume decreases. The lattice distortion caused by the solid solution of Er_2O_3 and CaTiO_3 accelerates the ion diffusion and promotes the sintering of CaTiO_3 material,and the occurred structure defects accelerate the growth of CaTiO_3 grains. With the calcining temperature rising,thermal defects increase,and the sintering property of synthesized CaTiO_3 is promoted.
引文
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[2]韩明洁,张玲,杨健,等.钛酸钙加入量对Mg O-Ca O材料性能的影响[J].耐火材料,2016,50(3):208-211.
[3]杨健,张玲,纪嘉宁,等.合成Ca Ti O3粉加入量对烧结镁砖性能的影响[J].耐火材料,2017,51(2):136-139.
[4]MANIK S K,PRADHAN S K.Microstructure characterization of ball milled prepared monocrystalline perovskite Ca Ti O3by Rietveld method[J].Mater Chem Phy,2004,86(2):284-292.
[5]BASSOLI M,BUSCAGLIA M T,BOTTINO C,et al.Defect chemistry and dielectric properties of Yb3+Ca Ti O3perovskite[J].J Appl Phys,2008,103(1):225-241.
[6]MARI B,SINGH K C,CEMBRERO-COCA P,et al.Red emitting MTi O3(M=Ca or Sr)phosphors doped with Eu3+or Pr3+with some cations as co-dopants[J].Displays,2013,34(4):346-351.
[7]TALANTIKITE D,TAIBI-BENZIADA L.Phase transitions of Ca Ti O3ceramics sintered with the aid of Na F and Mg F2[J].Solid State Sci,2009,11(1):151-155.
[8]LUO X D,XIE Z P,ZHENG L J,et al.Effect of adding Cr2O3/Fe2O3on aluminum titanate properties[J].Refra Indus Ceram,2015,56(4):337-343.
[9]罗旭东,曲殿利,谢志鹏,等.Cr2O3和煅烧温度对铝钛渣制备钛酸铝材料性能影响[J].人工晶体学报,2015,44(3):756-763.
[10]BUSCAGLIA M T,VIVIANI M,BUSCAGLIA V,et al.Incorporation of Er3+into Ba Ti O3[J].J Am Ceram Soc,2002,85(6):1569-1575.
[11]HIROSHI K,NORIYUKI K,JUNICHI S,et al.Effect of rare-earth(La,Sm,Dy,Ho and Er)and Mg on the microstructure in Ba Ti O3[J].J Eur Ceram Soc,1999,19(6-7):1043-1046.
[12]蒲永平,宁叔帆,陈维,等.Dy2O3掺杂对Ba Ti O3陶瓷结构与性能的影响[J].西安交通大学学报,2004,38(4):424-427.