Abstract Increased knowledge on fluid-solid phase transitions is needed, both when they are undesired and can impair process operations, and when strict control is required in fields such as food technology, the pharmaceutical industry and cryogenic CO2 capture. We present experimental results and theoretical predictions for the solid-formation and melting temperatures of ice in four binary water–alcohol mixtures containing methanol, ethanol, 1-propanol and 1-butanol. A dual fiber sensor set-up with a fiber Bragg grating sensor and a thin-core interferometer is used to detect the solid-formation. The predictions of melting temperatures with the cubic plus association equation of state combined with an ice model are in good agreement with experiments, but deviations are observed at higher alcohol concentrations. The measured degree of supercooling displays a highly non-linear dependence on the alcohol concentration. A heterogeneous nucleation model is developed to predict the solid-formation temperatures of the binary alcohol–water mixtures. The predictions from this model are in reasonable agreement with the measurements, but follow a qualitatively different trend that results in systematic deviations. In particular, the predicted degree of supercooling is found to be an essentially colligative property that increases smoothly with alcohol concentration. Experimental results are also presented for the growth rate of ice crystals in water–ethanol mixtures. For pure water, the measured crystal growth rate is 10.2 cm/s at 16 K supercooling. This is in excellent agreement with previous results from the literature. The crystal growth rate observed in ethanol–water mixtures however, can be orders of magnitude lower, where a mixture with 2% mole fraction ethanol has a growth rate of 2 mm/s. Further work is required to explain the large reduction in crystal growth rate with increasing alcohol concentration and to reproduce the behavior of the solid-formation temperatures with heterogeneous nucleation theory.

中文翻译：

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过冷水-酒精混合物中的冰形成和生长：双光纤传感器的理论和实验

摘要 需要增加关于流固相变的知识，无论是当它们是不希望的并且会损害过程操作时，以及在食品技术、制药工业和低温 CO2 捕获等领域需要严格控制时。我们展示了四种含有甲醇、乙醇、1-丙醇和 1-丁醇的二元水-醇混合物中冰的固体形成和熔化温度的实验结果和理论预测。带有光纤布拉格光栅传感器和薄芯干涉仪的双光纤传感器设置用于检测固体形成。用立方加关联状态方程结合冰模型预测的融化温度与实验非常吻合，但在较高的酒精浓度下观察到偏差。测得的过冷度与酒精浓度呈高度非线性相关。开发了一种异质成核模型来预测二元醇-水混合物的固体形成温度。该模型的预测与测量结果相当一致，但遵循导致系统偏差的性质不同的趋势。特别是，发现预测的过冷度基本上是一个依数属性，随着酒精浓度的增加而平滑地增加。还提供了水-乙醇混合物中冰晶生长速率的实验结果。对于纯水，测得的晶体生长速率在 16 K 过冷下为 10.2 cm/s。这与文献中先前的结果非常一致。然而，在乙醇-水混合物中观察到的晶体生长速率可能要低几个数量级，其中含有 2% 摩尔分数的乙醇混合物的生长速率为 2 mm/s。需要进一步的工作来解释随着醇浓度的增加晶体生长速率的大幅降低，并用异相成核理论重现固体形成温度的行为。