Weidendorfer Daniel, Hess Kai-Uwe, Ruhekenya Ruben M, Schawe Jürgen E K, Wilding Martin C, Dingwell Donald B
Department of Earth and Environmental Sciences, LMU Munich, Theresienstrasse 41, 80333 Munich, Germany.
Analytical, Mettler-Toledo GmbH, Heuwinkelstrasse 3,8603 Nänikon, Switzerland.
Philos Trans A Math Phys Eng Sci. 2023 Oct 16;381(2258):20220355. doi: 10.1098/rsta.2022.0355. Epub 2023 Aug 28.
Calorimetric measurements of the glass transition temperatures () of hydrous carbonate melts are reported on a near-eutectic composition of 55 mol% KCO - 45 mol% MgCO with up to 42 mol% bulk HO dissolved in the carbonate melt. Hydrous melts were quenched from 750°C to transparent and crystal-free glasses and were subsequently analysed for water content before and after measuring by high-sensitivity differential scanning calorimetry. The glass transition and limited fictive temperatures as a function of the water content were determined at 10 K/min cooling/heating rates resulting in ranging from 245°C at nominally anhydrous conditions to 83°C in the presence of 42 mol% HO in the glass. Through a generalized Gordon-Taylor analysis, the factors (7.27), (3.2) and the interaction parameter (0.49) were derived. The limited fictive temperature of a hypothetically, zero water containing 55 mol% KCO - 45 mol% MgCO glass is 232 ± 5°C (505 K). The high value of the interaction parameter indicates strong specific molecular interactions between water and the carbonates in the glassy state and a large decrease in the excess enthalpy of mixing during the conversion of the glassy into the liquid state at the glass transition. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.
报道了对含碳酸盐水合物熔体玻璃化转变温度()的量热测量结果,该熔体的近共晶组成为55摩尔%KCO - 45摩尔%MgCO,其中高达42摩尔%的总HO溶解在碳酸盐熔体中。含水熔体从750°C淬火成透明且无晶体的玻璃,随后在通过高灵敏度差示扫描量热法测量之前和之后分析其含水量。在10 K/min的冷却/加热速率下测定了玻璃化转变温度和有限的虚构温度随含水量的变化,结果表明,在名义上无水的条件下为245°C,在玻璃中存在42摩尔%HO时为83°C。通过广义的戈登 - 泰勒分析,得出了因子(7.27)、(3.2)和相互作用参数(0.49)。假设的含55摩尔%KCO - 45摩尔%MgCO且含水量为零的玻璃的有限虚构温度为232±5°C(505 K)。相互作用参数的高值表明在玻璃态下,水与碳酸盐之间存在强烈的特定分子相互作用,并且在玻璃转变时从玻璃态转变为液态的过程中,混合过剩焓大幅降低。本文是主题为“探索具有挑战性材料的长度尺度、时间尺度和化学性质(第1部分)”的一部分。