Complexity of confined water vitrification and its glass transition temperature

• 成果类型: Article
• 署名作者: Melillo, Jorge H.; Cangialosi, Daniele; Di Lisio, Valerio; Steinruecken, Elisa; Vogel, Michael; Cerveny, Silvina
• 署名单位: Consejo Superior de Investigaciones Cientificas (CSIC); University of Basque Country; CSIC - UPV EHU - Centro de Fisica de Materiales (CFM); Technical University of Darmstadt
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-8819
• DOI: 10.1073/pnas.2407030121
• 发表日期: 2024-10-03
• 关键词: liquid transition; supercooled water; DYNAMICS; ice; relaxation; polymers; BEHAVIOR; phases; state

摘要

The ability of vitrification when crossing the glass transition temperature (T-g) of confined and bulk water is crucial for myriad phenomena in diverse fields, ranging from the cryopreservation of organs and food to the development of cryoenzymatic reactions, frost damage to buildings, and atmospheric water. However, determining water's Tg remains a major challenge. Here, we elucidate the glass transition of water by analyzing the calorimetric behavior of nano-confined water across various pore topologies (diameters: 0.3 to 2.5 nm). Our approach involves subjecting confined water to annealing protocols to identify the temperature and time evolution of nonequilibrium glass kinetics. Furthermore, we complement this calorimetric approach with the dynamics of confined water, as seen by broadband dielectric spectroscopy and linear calorimetric measurements, including the fast scanning technique. This study demonstrated that confined water undergoes a glass transition in the temperature range of 170 to 200 K, depending on the confinement size and the interaction with the confinement walls. Moreover, we also show that the thermal event observed at similar to 136 K must be interpreted as an annealing prepeak, also referred to as the shadow glass transition. Calorimetric measurements also allow the detection of a specific heat step above 200 K, which is insensitive to annealing and, thereby, interpreted as a true thermodynamic transition. Finally, by connecting our results to bulk water behavior, we offer a comprehensive understanding of confined water vitrification with potential implications for numerous applications.