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    磷酸二氢钾在乙二醇-水体系中的成核机制及结晶动力学

    Nucleation mechanism and crystallization kinetics of potassium dihydrogen phosphate in ethylene glycol-water system

    • 摘要: 磷酸二氢钾(KDP)是一种泛化性应用于工业、农业和医学中的重要化学成分。工业上KDP的生产已经较为纯熟,但纯水体系中易出现包裹体、裂纹、枝晶生长,导致光学均匀性差、激光损伤阈值低等问题。针对这一问题,文中探讨了KDP在一定比例乙二醇-水体系中的生长成核动力学,并通过控制溶液的过饱和比和温度,分析了诱导期与成核速率之间的关系。研究结果表明:在过饱和比S > 1.08时,均质成核占主导地位,而在S < 1.06时,异质成核占主导。在成核参数方面,随着过饱和比的增加,成核自由能阻碍,临界成核半径与临界成核分子数均显著降低,初级成核速率增加,印证了温度和过饱和比在成核过程中的重要作用;通过对表面熵因子的分析,证明了KDP的结晶主要采用连续生长机制。此外,探究了转速、过饱和比、悬浮密度对粒径、生长速率及成核速率的影响,使用二参数C-R模型和三参数ASL模型对KDP的线性生长速率进行拟合及计算,确定了生长与成核过程的动力学方程。研究结论为解决工业合成KDP的晶体缺陷、能耗高、工艺不稳定等核心问题提供参考。

       

      Abstract: Potassium dihydrogen phosphate (KH2PO4) is a crucial chemical component widely applied in industry, agriculture, and medicine. Although its industrial production has been relatively mature, issues such as inclusions, cracks, and dendritic crystal growth often occur in pure water systems, leading to poor optical uniformity and a low laser damage threshold. To address this problem, this study explored the growth and nucleation kinetics of KH2PO4 in an ethylene glycol-water system at a specific ratio.First, by controlling the solution’s supersaturation ratio (S) and temperature, the relationship between the induction period and nucleation rate was analyzed. The results showed that homogeneous nucleation dominated when S>1.08, while heterogeneous nucleation dominated when S<1.06. Regarding nucleation parameters, an increase in the supersaturation ratio significantly reduced the nucleation free energy barrier, critical nucleation radius, and critical number of nucleation molecules, while increasing the primary nucleation rate, which confirmed the important roles of temperature and supersaturation ratio in the nucleation process. Analysis of the surface entropy factor demonstrated that the crystallization of KH2PO4 primarily followed a continuous growth mechanism.Second, the effects of rotation speed, supersaturation ratio, and suspension density on particle size, growth rate, and nucleation rate were investigated. The linear growth rate of KDP was fitted and calculated using the two-parameter C-R model and three-parameter ASL model, and the kinetic equations for the growth and nucleation processes were determined. This study provides a reference for solving core issues in industrial KDP synthesis, such as crystal defects, high energy consumption, and unstable processes.

       

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