Zhu Junhao, Wang Zhongyi, Dai Zheng, Wang Yanhua, Wang Meng
College of Power and Energy Engineering, Harbin Engineering University, Harbin 150000, China.
J Colloid Interface Sci. 2025 Dec;699(Pt 2):138227. doi: 10.1016/j.jcis.2025.138227. Epub 2025 Jun 18.
The underlying segregative freezing mechanism of saltwater is widely relevant to metallurgy, materials processing, environmental systems, and biomaterials. Under the effect of ion exclusion, the freezing process of saltwater may significantly differ from that of pure water due to variations in dendritic growth. Moreover, differences in droplet supercooling significantly influence dendrite formation at the freezing front, thereby affecting heat transfer during crystallization.
We prepared NaCl solutions covering the salinity range of marine conditions and utilized hydrophobically microstructured surfaces. Under controlled temperature and humidity, we conducted experiments on the impact freezing of saltwater droplets and observed the morphology and growth of the freezing front.
The freezing interface displayed distinct burr-like structures-irregular, short, and sharp protrusions-which evolved into more typical dendritic patterns under enhanced supercooling. Based on these observations, we proposed a new heat transfer calculation method using the Lattice Boltzmann Method, incorporating the effect of ion exclusion. Simulation results confirmed that the presence of burr-like structures enhances thermal conduction, and the model is also applicable to pure water freezing. Furthermore, we found that thickened phase change regions, slowed freezing at the droplet top, and reduced freezing depth lead to a blurred interface in later stages and disappearance of the freezing tip (singularity). Finally, we quantified the influence of salinity on freezing time, showing that salinity governs freezing depth and plays a critical role in the reduced mechanical hardness of saltwater ice.
盐水的潜在分离冻结机制与冶金、材料加工、环境系统和生物材料广泛相关。在离子排斥作用下,由于枝晶生长的变化,盐水的冻结过程可能与纯水有显著差异。此外,液滴过冷度的差异会显著影响冻结前沿的枝晶形成,从而影响结晶过程中的热传递。
我们制备了涵盖海洋条件盐度范围的氯化钠溶液,并使用了疏水微结构表面。在控制温度和湿度的条件下,我们对盐水液滴的冲击冻结进行了实验,并观察了冻结前沿的形态和生长情况。
冻结界面呈现出明显的毛刺状结构——不规则、短而尖锐的突起——在增强过冷度的情况下演变成更典型的枝晶模式。基于这些观察结果,我们提出了一种使用格子玻尔兹曼方法的新的热传递计算方法,该方法纳入了离子排斥的影响。模拟结果证实,毛刺状结构的存在增强了热传导,并且该模型也适用于纯水冻结。此外,我们发现相变区域增厚、液滴顶部冻结减缓以及冻结深度减小会导致后期界面模糊和冻结尖端(奇点)消失。最后,我们量化了盐度对冻结时间的影响,表明盐度控制冻结深度,并在降低盐水冰的机械硬度方面起着关键作用。