溶胶-凝胶法制备硅酸锆粉体及其表征
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摘要
通过溶胶-凝胶法制备ZrSiO4粉体,研究了煅烧温度、保温时间和催化剂(铁离子)对ZrSiO4合成率的影响;采用XRD、SEM、激光粒度仪等分析了ZrSiO4的晶相组成、结晶形貌以及产物粒径大小。实验结果表明:未添加催化剂时,ZrSiO4的合成温度高达1500℃;引入催化剂铁离子之后,在1200℃合成率可达到91.20%,合成温度降低了300℃,得到的粉体颗粒发育完善,结晶性好。烧结机理分析表明,Si4+的扩散是影响硅酸锆形成的主要因素;加入的铁以Fe3+的形式进入到ZrSiO4结构中,取代部分Si4+,产生空位,加速Si4+的扩散,从而有效地促进ZrSiO4的结晶,降低ZrSiO4的合成温度。
ZrSiO4 has been synthesized by a sol-gel method.The effects of varying the sintering temperature,sintering duration and content of Fe3 +catalyst on the yield of ZrSiO4 were investigated.The compositions,microstructures and grain size of the products were studied by XRD,SEM and laser particle size analysis,respectively.The temperature required to synthesize ZrSiO4 without a catalyst is as high as 1500 ℃.However the sintering temperature can be reduced by 300 ℃ to 1200 ℃ by adding Fe3 +cations as a catalyst,giving a yield of 91.20%.The powder particles have a high degree of crystallinity.According to our analysis of the sintering mechanism,Fe3 +cations enter into the ZrSiO4 structure to replace part of the Si4 +and form a solid solution,resulting in the vacancies which accelerate the diffusion of Si4 +.This is the main factor affecting the formation of ZrSiO4,and by promoting crystallization in this way the synthesis temperature can be reduced.
ZrSiO4 has been synthesized by a sol-gel method.The effects of varying the sintering temperature,sintering duration and content of Fe3 +catalyst on the yield of ZrSiO4 were investigated.The compositions,microstructures and grain size of the products were studied by XRD,SEM and laser particle size analysis,respectively.The temperature required to synthesize ZrSiO4 without a catalyst is as high as 1500 ℃.However the sintering temperature can be reduced by 300 ℃ to 1200 ℃ by adding Fe3 +cations as a catalyst,giving a yield of 91.20%.The powder particles have a high degree of crystallinity.According to our analysis of the sintering mechanism,Fe3 +cations enter into the ZrSiO4 structure to replace part of the Si4 +and form a solid solution,resulting in the vacancies which accelerate the diffusion of Si4 +.This is the main factor affecting the formation of ZrSiO4,and by promoting crystallization in this way the synthesis temperature can be reduced.
引文
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[2]康厚军,王晓丽,卢喜瑞,等.锆英石微粉高温固相合成研究[J].成都理工大学学报:自然科学版,2010,37(3):332-335.Kang H J,Wang X L,Lu X R,et al.Technologic research on the synthesis of zircon powders by the high temperature solid state reaction[J].Journal of Chengdu University of Technology:Science and Technology,2010,37(3):332-335.(in Chinese)
[3]陆彩飞,王秀峰,苗红雁,等.纳米硅酸锆的水热合成[J].硅酸盐学报,2000,28(1):87-90.Lu C F,Wang X F,Miao H Y,et al.Hydrothermal synthesis of Zr Si O4nano-mater powder[J].Journal of the Chinese Ceramic Society,2000,28(1):87-90.(in Chinese)
[4]刘大为,王芬,朱建峰,等.纳米粉体的微波水热法合成及其合成机理[J].陕西科技大学学报,2011,29(1):43-46.Liu D W,Wang F,Zhu J F,et al.Preparation of NanoZr Si O4powders by microwave-hydrothermal method[J].Journal of Shanxi University of Science and Technology,2011,29(1):43-46.(in Chinese)
[5]Itoh T.Formation of polycrystalline zircon(Zr Si O4)from amorphous silica and amorphous zirconia[J].Journal of Cryst Growth,1992,125:223-228.
[6]杜春生,葛志平,杨正方,等.溶胶-凝胶法合成高纯锆英石粉[J].硅酸盐学报,1999,27(3):346-350.Du C S,Ge Z P,Yang Z F,et al.Study on the synthesis of zircon by sol-gel processing[J].Journal of the Chinese Ceramic Society,1999,27(3):346-350.(in Chinese)
[7]Parcianello G,Bernardo E,Colombo P.Low temperature synthesis of zircon from silicone resins and oxide nanosized particles[J].Journal of the European Ceramic Society,2012,32:2819-2824.
[8]董雪亮,滕元成,曾冲盛,等.溶胶-凝胶法合成硅酸锆[J].中国粉体技术,2010,16(6):4-7.Dong X L,Teng Y C,Zeng C S,et al.Synthesis of zircon by sol-gel method[J].China Powder Science and Technology,2010,16(6):4-7.(in Chinese)
[9]Alahakoon W P C M,Burrows S E,Howes A P,et al.Fully densified zircon co-doped with iron and aluminium prepared by sol-gel processing[J].Journal of the European Ceramic Society,2010,30:2515-2523.
[10]高栋,张跃,许春来,等.Zr B2-Si C超高温陶瓷氧化过程中Zr Si O4相形成机制研究[J].无机材料学报,2011,26(4):433-437.Gao D,Zhang Y,Xu C L,et al.Formation mechanism of zircon phase in Zr B2-Si C ceramic composites during oxidation[J].Journal of Inorganic Materials,2011,26(4):433-437.(in Chinese)
[11]Veytizou C,Quinson J F,Valfort O,et al.Zircon formation from amorphous silica and tetragonal zirconia:kinetic study and modelling[J].Solid State Ionics,2001,139:315-323.
[12]Herrera G,Montoya N,Alarcon J.Synthesis and characterization of iron-doped Zr Si O4solid solutions from gels[J].Journal of the American Ceramic Society,2011,94(12):4247-4255.
[13]Tartaj P,Gonzalez-Carreno T,Serna C J,et al.Iron zircon pigments prepared by pyrolysis of aerosols[J].Journal of Solid State Chemistry,1997,128:102-108.