超临界水热合成制备超细金属氧化物的实验研究
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摘要
超临界水热合成技术(Supercritical Hydrothermal Synthesis)在制备超细金属氧化物微粒研究领域取得快速发展。该技术是将超临界流体引入到传统的水热合成微粒制备技术中,其特点是制备的粒子纯度高、分散性好、晶形好且可控制、反应时间短、环境友好,是对微粒制备技术的有效拓展。
首先对原有超临界水氧化装置进行了一系列改造和调整。除对所需的管路和阀门进行了调整外,还添加了小型反应釜和循环水冷却系统,以使设备在能够满足实验过程要求的前提下,提高自身的灵活性、安全性及节省能源等。同时,实验的过程参数更容易被测量和控制,设备更便于操作。
实验以乙酸锌、乙酸钴、氧氯化锆和乙酸锰为典型材料,进行了超临界水热合成制备金属氧化物微粒的研究。考察了各过程参数(实验温度、实验压力、反应物浓度和进水速率)对产品微粒粒径的影响;利用XRD、SEM和Zetasizer对实验制备的微粒进行了表征;并对微粒的成核机理进行了初步的热力学分析。本论文的主要研究工作及所形成的主要结果与结论如下:
实验温度、压力和反应物浓度是影响制备微粒的最为关键的因素。制备的金属氧化物微粒粒径随实验温度的升高而减小;实验压力增大,微粒粒径随之增大;应物浓度增加,微粒粒径也增大;但进水速率对制备微粒粒径的影响不是很明显,随进水速率的增大粒径略有减小。
由表征结果可知,实验成功制备出最小平均粒径为9.55nm的ZnO球形微粒、最小平均粒径为138nm的CoO六面体微粒、最小平均粒径为170nm的ZrO_2球形微粒和最小平均粒径为305nm的Mn_3O_4球形微粒,粒径分布范围较窄。
对水热合成过程溶质微粒的晶化趋势以及晶核的形成与生长过程进行了初步的热力学分析,推导出水热合成的成核速率公式以及核生长速率公式,成功解释了本文的部分实验现象,为今后更深入的热力学及动力学理论分析提供了一定的理论参考。
通过本文的实验研究,对用超临界水热合成制备金属氧化物超细微粒过程有了较深入的认识,掌握了各过程参数对氧化物微粒粒径影响的基本规律,为该工艺的进一步工业应用与理论分析提供了必要的实验数据和理论基础。
The preparation technology of metal oxide particles by supercritical hydrothermal synthesis has been rapidly developed. The technology introduces supercritical fluid into the traditional hydrothermal synthesis method. The advantage of the partiles obtained is characterized by high purity, good dispersion, highly crystalline which can be well controlled, short reaction time and environment-friendly.
The experimental setup is build upon the reconstruction of Supercritical Water Oxidation. A series of pipes and valves are reasonable modified, a small autoclave reactor and the circulating water cooling system are added, which can not only meet the equipment requirements of the experiment, but also enhance the experimental flexibility, equipment safety, and save energy required. At the same time, the equipment and the experimental process parameters are more easily to operate, measure and control.
Zinc acetate, cobaltous Acetate, zirconium oxychloride and manganese acetate are used as typical experimental materials. The effects of four process parameters, like temperature, pressure, material concentration and water flowrate, on the particles size and distribution of the metal oxides are well investigated. The as-prepared powders are fully characterized by complementary experiments: X-ray diffraction(XRD), scanning electron microscope (SEM) and Zetasizer Analysis Apparatus(Zetasizer). The nucleation mechanism is preliminary analyzed by thermodynamics. The main experimental research results and conclusions are as follows:
The experimental pressure, temperature and material concentration are the most important factors to effect particle size. Both the increasing operating pressure and decreasing operating temperature lead to an increase in the particle size. Besides, the increasing concentration of reactants also results in the particle with larger diameter. The strong influence of increasing water flowrate on the particle size is not obviously observed. It is just a little decrease in the particle size with the increasing water flowrate.
The high-purity ZnO spherical particles with minimal average particle size of 9.55nm. CoO hexahedral particles with minimal average particle size of 138nm, ZrO_2 spherical particles with minimal average particle size of 170nm, and Mn_3O_4 spherical particles with minimal average particle size of 305nm are successfully obtained. The narrow particle size distribution is found as well.
The solute particles crystallization trends and the formation and growth process of nucleation in hydrothermal synthesis are analyzed using preliminary thermodynamic theory. The rate formula for nuclear formation and its growth are educed, which explaine some experiments phenomena successfully and provide a certain theoretical reference for the future more in-depth thermodynamic and dynamical analysis.
Through this work, the experiment technique of ultrafine metal oxide particles synthesis is investigated deeply. The basic influence rules of the process parameters working on the particle size and morphology are understood detailed. It provides experimental basis for the thermodynamic analysis behind, necessary basic data for future industrialization.
首先对原有超临界水氧化装置进行了一系列改造和调整。除对所需的管路和阀门进行了调整外,还添加了小型反应釜和循环水冷却系统,以使设备在能够满足实验过程要求的前提下,提高自身的灵活性、安全性及节省能源等。同时,实验的过程参数更容易被测量和控制,设备更便于操作。
实验以乙酸锌、乙酸钴、氧氯化锆和乙酸锰为典型材料,进行了超临界水热合成制备金属氧化物微粒的研究。考察了各过程参数(实验温度、实验压力、反应物浓度和进水速率)对产品微粒粒径的影响;利用XRD、SEM和Zetasizer对实验制备的微粒进行了表征;并对微粒的成核机理进行了初步的热力学分析。本论文的主要研究工作及所形成的主要结果与结论如下:
实验温度、压力和反应物浓度是影响制备微粒的最为关键的因素。制备的金属氧化物微粒粒径随实验温度的升高而减小;实验压力增大,微粒粒径随之增大;应物浓度增加,微粒粒径也增大;但进水速率对制备微粒粒径的影响不是很明显,随进水速率的增大粒径略有减小。
由表征结果可知,实验成功制备出最小平均粒径为9.55nm的ZnO球形微粒、最小平均粒径为138nm的CoO六面体微粒、最小平均粒径为170nm的ZrO_2球形微粒和最小平均粒径为305nm的Mn_3O_4球形微粒,粒径分布范围较窄。
对水热合成过程溶质微粒的晶化趋势以及晶核的形成与生长过程进行了初步的热力学分析,推导出水热合成的成核速率公式以及核生长速率公式,成功解释了本文的部分实验现象,为今后更深入的热力学及动力学理论分析提供了一定的理论参考。
通过本文的实验研究,对用超临界水热合成制备金属氧化物超细微粒过程有了较深入的认识,掌握了各过程参数对氧化物微粒粒径影响的基本规律,为该工艺的进一步工业应用与理论分析提供了必要的实验数据和理论基础。
The preparation technology of metal oxide particles by supercritical hydrothermal synthesis has been rapidly developed. The technology introduces supercritical fluid into the traditional hydrothermal synthesis method. The advantage of the partiles obtained is characterized by high purity, good dispersion, highly crystalline which can be well controlled, short reaction time and environment-friendly.
The experimental setup is build upon the reconstruction of Supercritical Water Oxidation. A series of pipes and valves are reasonable modified, a small autoclave reactor and the circulating water cooling system are added, which can not only meet the equipment requirements of the experiment, but also enhance the experimental flexibility, equipment safety, and save energy required. At the same time, the equipment and the experimental process parameters are more easily to operate, measure and control.
Zinc acetate, cobaltous Acetate, zirconium oxychloride and manganese acetate are used as typical experimental materials. The effects of four process parameters, like temperature, pressure, material concentration and water flowrate, on the particles size and distribution of the metal oxides are well investigated. The as-prepared powders are fully characterized by complementary experiments: X-ray diffraction(XRD), scanning electron microscope (SEM) and Zetasizer Analysis Apparatus(Zetasizer). The nucleation mechanism is preliminary analyzed by thermodynamics. The main experimental research results and conclusions are as follows:
The experimental pressure, temperature and material concentration are the most important factors to effect particle size. Both the increasing operating pressure and decreasing operating temperature lead to an increase in the particle size. Besides, the increasing concentration of reactants also results in the particle with larger diameter. The strong influence of increasing water flowrate on the particle size is not obviously observed. It is just a little decrease in the particle size with the increasing water flowrate.
The high-purity ZnO spherical particles with minimal average particle size of 9.55nm. CoO hexahedral particles with minimal average particle size of 138nm, ZrO_2 spherical particles with minimal average particle size of 170nm, and Mn_3O_4 spherical particles with minimal average particle size of 305nm are successfully obtained. The narrow particle size distribution is found as well.
The solute particles crystallization trends and the formation and growth process of nucleation in hydrothermal synthesis are analyzed using preliminary thermodynamic theory. The rate formula for nuclear formation and its growth are educed, which explaine some experiments phenomena successfully and provide a certain theoretical reference for the future more in-depth thermodynamic and dynamical analysis.
Through this work, the experiment technique of ultrafine metal oxide particles synthesis is investigated deeply. The basic influence rules of the process parameters working on the particle size and morphology are understood detailed. It provides experimental basis for the thermodynamic analysis behind, necessary basic data for future industrialization.
引文
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