晶须制备研究与镁资源开发
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摘要
晶须是已知固体形态中强度最大的形态之一,用作材料的增强,用途广泛,晶须的制备和应用处于世界的研究前沿。本文系统地探讨了制备MgO晶须常用的两种方法,助熔剂水解法和前体分解法,发明了新的晶须制备方法并成功应用于MgO晶须和ZnS晶须制备。本文还研究了碱式氯化镁晶须和Mg(OH)_2晶须的制备。这些制备方法亦可推广至其它晶须(包括纳米晶须)的制备过程。
本课题是国家“十一五”科技支撑计划项目“钾镁盐矿生态化开发系统工程研究”中的一部分,重点研究钾镁盐矿的镁资源开发利用问题。从该钾镁矿的实际出发,依据相平衡数据,提出了适合矿情的制备六水氯化镁的工艺,并在小试实验中制备了合格的工业级产品,研究了原料组成和蒸发终点对产品质量的影响。
在助熔剂水解法的研究中,系统地研究了实验原料、温度、助熔剂和气体流动状况对MgO晶须生长的影响,并对工艺进行了优化,显著提高了晶须产品的收率和质量。根据文献中热力学和熔盐性质的数据,研究了反应平衡,分析了反应过程,并结合实验中的系统研究,确定了助熔剂法中晶须的生长机理,并根据熔盐结构推测了助熔剂的作用。
根据上述机理,提出了制备晶须的绿色新工艺,成功制备了MgO晶须。对新工艺进行了热力学上的分析,在实验中研究了温度对晶须生长的影响。应用新工艺还成功制备了ZnS晶须,并对该反应进行了热力学分析,研究了助熔剂对晶须生长的影响。利用分子模拟软件Cerious2对ZnS晶须形貌进行了预测分析,根据晶体生长的理论模型探讨了ZnS晶须特殊形貌的成因。
在前体法中,系统地考察了碱式氯化镁晶须和Mg(OH)_2晶须作为MgO晶须前体的制备方法。借鉴镁水泥中碱式氯化镁的形成机理,对碱式氯化镁晶须的形成机理进行了详细分析。成功地利用Mg(OH)_2、Ca(OH)_2和MgCl2溶液为原料制备出了碱式氯化镁晶须,并对碱式氯化镁和Mg(OH)_2晶须的制备和转化工艺进行了优化。利用XRD、SEM和TEM研究了晶须转化前后的晶体结构和形貌。
率先采用XRD和化学滴定分别考察了以Mg(OH)_2和Ca(OH)_2为原料时碱式氯化镁晶须的生长动力学以及转化成Mg(OH)_2晶须的动力学,并结合晶体结构进行了理论分析。
以上研究内容国内外尚未见文献报导。
Crystal whisker is one of the strongest known forms of solid and has been widely employed as reinforcing additive of composite materials. At present, the preparation and application of whisker are in the frontier of research and development of materials around the world. Two conventional methods were systematically studied in the preparation of MgO whiskers: the method of hydrolysis of MgCl_2 with flux and the method of decomposition of precursor whiskers. A novel method was developed to prepare crystal whiskers and successfully applied in the preparation of MgO whiskers and ZnS whiskers. Besides, the investigation was also made on the preparation of magnesium hydroxychloride whiskers and Mg(OH)_2 whiskers. These methods can also be applied in the preparation of other crystal whiskers, including nanowhiskers.
The research project is one of the national eleventh five-year scientifical supporting and planning projects, named as systematical engineering study of ecological exploitation of KCl and MgCl_2·6H_2O minerals and focuses on deep exploitation of magnesium minerals. The crystallization process of MgCl_2·6H_2O was developed based on the fact of the minerals and phase equilibrium data from literature and qualified products of MgCl_2·6H_2O were prepared in laboratory. The effects of the composition of raw materials and the end-point of evaporation were investigated on the quality of product.
In the study of the method of hydrolysis with flux, the optimization of reaction conditions was performed and the effects of reactants, temperature and the nature of flux were systematically investigated. The yield and quality of crystal whiskers had been improved greatly after optimization.The reaction equilibrium and process were analyzed according to the thermodynamic data and the properties of molten salt reported in literature. The growth mechanism of MgO whiskers prepared by hydrolysis was brought forward based on experimental investigation and theoretical analysis. The role of flux was explained based on the structure of molten salt.
According to the crystal whisker growth mechanism, a novel green method was invented to prepare crystal whiskers and MgO whiskers were prepared successfully. The new process was thermodynamically analyzed and the effects of temperature and flux were investigated on the growth of MgO whiskers in experiments. ZnS whiskers were also prepared with the novel method. The preparation reaction was thermodynamically analyzed and the effects of flux and temperature were investigated on the growth of crystal whiskers. Theoretical prediction of ZnS morphology was performed with molecular simulation software Cerious2 and the special morphology of ZnS whiskers was analyzed based on crystal growth theories.
The method of decomposition of precursors has been researched, in which magnesium hydroxychloride whiskers and magnesium hydroxide whiskers were used as the precursors to prepare MgO whiskers. Learning from the formation mechanism of magnesium hydroxychloride in magnesium cement, a detailed analysis was made on the growth mechanism of magnesium hydroxychloride whiskers. Magnesium hydroxychloride whiskers were prepared successfully with Mg(OH)_2, Ca(OH)_2 and magnesium chloride solution and the process of the preparation and transformation of magnesium hydroxychloride whiskers is optimized. XRD, SEM and TEM studies were performed on the morphology and crystal structure of crystal whiskers before and after transformed to MgO whiskers.
The growth and transformation kinetics of magnesium hydroxychloride whiskers were investigated with chemical titration and XRD for the first time and the transformation was analyzed based on crystal structures of crystal whiskers.
All the contents above have never been reported at present.
本课题是国家“十一五”科技支撑计划项目“钾镁盐矿生态化开发系统工程研究”中的一部分,重点研究钾镁盐矿的镁资源开发利用问题。从该钾镁矿的实际出发,依据相平衡数据,提出了适合矿情的制备六水氯化镁的工艺,并在小试实验中制备了合格的工业级产品,研究了原料组成和蒸发终点对产品质量的影响。
在助熔剂水解法的研究中,系统地研究了实验原料、温度、助熔剂和气体流动状况对MgO晶须生长的影响,并对工艺进行了优化,显著提高了晶须产品的收率和质量。根据文献中热力学和熔盐性质的数据,研究了反应平衡,分析了反应过程,并结合实验中的系统研究,确定了助熔剂法中晶须的生长机理,并根据熔盐结构推测了助熔剂的作用。
根据上述机理,提出了制备晶须的绿色新工艺,成功制备了MgO晶须。对新工艺进行了热力学上的分析,在实验中研究了温度对晶须生长的影响。应用新工艺还成功制备了ZnS晶须,并对该反应进行了热力学分析,研究了助熔剂对晶须生长的影响。利用分子模拟软件Cerious2对ZnS晶须形貌进行了预测分析,根据晶体生长的理论模型探讨了ZnS晶须特殊形貌的成因。
在前体法中,系统地考察了碱式氯化镁晶须和Mg(OH)_2晶须作为MgO晶须前体的制备方法。借鉴镁水泥中碱式氯化镁的形成机理,对碱式氯化镁晶须的形成机理进行了详细分析。成功地利用Mg(OH)_2、Ca(OH)_2和MgCl2溶液为原料制备出了碱式氯化镁晶须,并对碱式氯化镁和Mg(OH)_2晶须的制备和转化工艺进行了优化。利用XRD、SEM和TEM研究了晶须转化前后的晶体结构和形貌。
率先采用XRD和化学滴定分别考察了以Mg(OH)_2和Ca(OH)_2为原料时碱式氯化镁晶须的生长动力学以及转化成Mg(OH)_2晶须的动力学,并结合晶体结构进行了理论分析。
以上研究内容国内外尚未见文献报导。
Crystal whisker is one of the strongest known forms of solid and has been widely employed as reinforcing additive of composite materials. At present, the preparation and application of whisker are in the frontier of research and development of materials around the world. Two conventional methods were systematically studied in the preparation of MgO whiskers: the method of hydrolysis of MgCl_2 with flux and the method of decomposition of precursor whiskers. A novel method was developed to prepare crystal whiskers and successfully applied in the preparation of MgO whiskers and ZnS whiskers. Besides, the investigation was also made on the preparation of magnesium hydroxychloride whiskers and Mg(OH)_2 whiskers. These methods can also be applied in the preparation of other crystal whiskers, including nanowhiskers.
The research project is one of the national eleventh five-year scientifical supporting and planning projects, named as systematical engineering study of ecological exploitation of KCl and MgCl_2·6H_2O minerals and focuses on deep exploitation of magnesium minerals. The crystallization process of MgCl_2·6H_2O was developed based on the fact of the minerals and phase equilibrium data from literature and qualified products of MgCl_2·6H_2O were prepared in laboratory. The effects of the composition of raw materials and the end-point of evaporation were investigated on the quality of product.
In the study of the method of hydrolysis with flux, the optimization of reaction conditions was performed and the effects of reactants, temperature and the nature of flux were systematically investigated. The yield and quality of crystal whiskers had been improved greatly after optimization.The reaction equilibrium and process were analyzed according to the thermodynamic data and the properties of molten salt reported in literature. The growth mechanism of MgO whiskers prepared by hydrolysis was brought forward based on experimental investigation and theoretical analysis. The role of flux was explained based on the structure of molten salt.
According to the crystal whisker growth mechanism, a novel green method was invented to prepare crystal whiskers and MgO whiskers were prepared successfully. The new process was thermodynamically analyzed and the effects of temperature and flux were investigated on the growth of MgO whiskers in experiments. ZnS whiskers were also prepared with the novel method. The preparation reaction was thermodynamically analyzed and the effects of flux and temperature were investigated on the growth of crystal whiskers. Theoretical prediction of ZnS morphology was performed with molecular simulation software Cerious2 and the special morphology of ZnS whiskers was analyzed based on crystal growth theories.
The method of decomposition of precursors has been researched, in which magnesium hydroxychloride whiskers and magnesium hydroxide whiskers were used as the precursors to prepare MgO whiskers. Learning from the formation mechanism of magnesium hydroxychloride in magnesium cement, a detailed analysis was made on the growth mechanism of magnesium hydroxychloride whiskers. Magnesium hydroxychloride whiskers were prepared successfully with Mg(OH)_2, Ca(OH)_2 and magnesium chloride solution and the process of the preparation and transformation of magnesium hydroxychloride whiskers is optimized. XRD, SEM and TEM studies were performed on the morphology and crystal structure of crystal whiskers before and after transformed to MgO whiskers.
The growth and transformation kinetics of magnesium hydroxychloride whiskers were investigated with chemical titration and XRD for the first time and the transformation was analyzed based on crystal structures of crystal whiskers.
All the contents above have never been reported at present.
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