ZrO_2溶胶的稳定性及溶胶-凝胶材料转变的物相-化学结构分析
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摘要
以Zr(NO_3)_4·5H_2O为前驱体,采用溶胶-凝胶法制备ZrO_2溶胶.通过测定ZrO_2溶胶的密度、黏度,计算ZrO_2溶胶体系的黏滞性活化吉布斯自由能,采用红外光谱、粒径分析、X射线衍射(XRD)和扫描电镜(SEM)对ZrO_2溶胶及其凝胶材料进行分析表征.结果表明,所形成的ZrO_2溶胶粒径小且分布窄,平均粒径为2.89nm.在25℃陈化的前60d内,ZrO_2溶胶的密度、黏度、粒径以及黏滞性活化吉布斯自由能略有增大,表明溶胶体系内部颗粒间有较大的摩擦力,溶胶稳定性和分散性良好.ZrO_2溶胶及其凝胶材料中均没有Zr-O键,Zr元素是以无定型ZrOC2O4·2H2O的形式存在,400℃焙烧后出现的是四方相ZrO_2晶体.
ZrO_2 sol was prepared by sol-gel method using Zr(NO_3)_4·5 H_2O as precursor.The Gibbs free energy of ZrO_2 sol system was calculated by measuring the density and viscosity of ZrO_2 sol.Infrared spectra(IR),particle size analysis,X-ray diffraction(XRD)and scanning electron microscopy(SEM)were used to characterize the properties of ZrO_2 sol and its gel material.The results show that the freshly prepared ZrO_2 sol has a narrow particle size distribution with an average particle size of 2.89 nm.Within the first 60 days aged at 25℃,the density,viscosity,particle size and viscosity-activated Gibbs free energy of ZrO_2 sol slightly increase,indicating that the great friction exists among the particles of the system and ZrO_2 sol has good stability and dispersibility.There is no Zr—O bond in the ZrO_2 sol and its gel material,and Zr element exists in the form of amorphous ZrOC_2O_4·2 H_2O.Tetragonal ZrO_2 crystal appears in the sample calcined at 400℃.
ZrO_2 sol was prepared by sol-gel method using Zr(NO_3)_4·5 H_2O as precursor.The Gibbs free energy of ZrO_2 sol system was calculated by measuring the density and viscosity of ZrO_2 sol.Infrared spectra(IR),particle size analysis,X-ray diffraction(XRD)and scanning electron microscopy(SEM)were used to characterize the properties of ZrO_2 sol and its gel material.The results show that the freshly prepared ZrO_2 sol has a narrow particle size distribution with an average particle size of 2.89 nm.Within the first 60 days aged at 25℃,the density,viscosity,particle size and viscosity-activated Gibbs free energy of ZrO_2 sol slightly increase,indicating that the great friction exists among the particles of the system and ZrO_2 sol has good stability and dispersibility.There is no Zr—O bond in the ZrO_2 sol and its gel material,and Zr element exists in the form of amorphous ZrOC_2O_4·2 H_2O.Tetragonal ZrO_2 crystal appears in the sample calcined at 400℃.
引文
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[3]宋大雷,刘思奇,李丰,等.硅烷改性纳米ZrO2对镁锂合金表面环氧树脂涂层耐蚀性能的影响[J].高等学校化学学报,2017,38(1):77-84.
[4]郭攀,常弈,王毅,等.模板剂对合成氧化锆晶体性质的影响研究[J].人工晶体学报,2014,43(10):2687-2692.
[5]李慧.负载型ZrO2催化剂的制备、表征及氨氧化反应性能研究[D].长春:吉林大学,2017.
[6]高悝,叶春,李春华.纳米材料用于改性水处理中的有机-无机杂化膜的研究进展[J].应用化工,2017,46(10):1999-2004.
[7]同帜,霍乐乐,董旭娟,等.溶胶-凝胶法制备氧化锆薄膜的工艺与表征[J].粉末冶金材料科学与工程,2016,21(1):174-179.
[8]Nagaprabha P,Bhattacharya S.Rheological characterisation of sol-gel phenomenon and stability of green gram and foxtail millet flour gels[J].LWT-Food Sci Technol,2016,65:917-923.
[9]Li L,Qi H.Gas separation using sol-gel derived microporous zirconia membranes with high hydrothermal stability[J].Chinese J Chem Eng,2015,23(8):1300-1306.
[10]Soo M T,Prastomo N,Matduda A,et al.Elaboration and characterization of sol-gel derived ZrO2thin films treated with hot water[J].Appl Surf Sci,2012,258(13):5250-5258.
[11]Hassein-bey-Larouci A,Igoujilen O,Aitkaci A,et al.Dynamic and kinematic viscosities,excess volumes and excess Gibbs energies of activation for viscous flow in the ternary mixture{1-propanol+N,N-dimethylformamide+chloroform at temperatures between293.15Kand 323.15K[J].Thermochim Acta,2014,589(10):90-99.
[12]Li D,Fang W J,Liu L,et al.Volumetric and viscous properties for binary mixtures of N-methyl piperazine with ethyl acette or butyl acetate from 298.15 Kto313.15K[J].Chem J Chinese Universities,2013,34(8):1924-1928.
[13]Xu Q,Sun S,Lan G,et al.Excess properties and spectral investigation for the binary system diethylene glycol dimethyl ether+water at T=(293.15,298.15,303.15,308.15and 313.15)K[J].Chem Eng Data,2015,60(1):2-10.
[14]杨凤军,郭永胜,魏会,等.正构烷烃/JP-10二元体系的体积性质[J].高等学校化学学报,2010,31(6):1222-1226.
[15]王大志,罗毅,杨兰,等.非晶氧化锆水合物红外研究[J].化学物理学报,2000,13(4):481-486.
[16]刘宇尘,陈卫平,聂东红,等.铈稳定钪掺杂氧化锆的水热合成与结构表征[J].粉末冶金材料科学与工程,2014,19(5):715-720.
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