CNRS, Université d'Orléans, UPR 3079 CEMHTI, 45071 Orléans, France.
Inorg Chem. 2009 Dec 7;48(23):10972-5. doi: 10.1021/ic9010086.
Self-diffusion is a fundamental property of liquid dynamics that also provides important structural information. To explore the dynamics in inorganic melts with high liquidus temperature, we propose a new setup based on pulsed field gradient NMR combined with laser heating that makes possible in situ self-diffusion coefficient measurements up to 1500 K. Applied to several corrosive molten fluorides in a wide range of compositions and temperature, we have evidenced the different key parameters of their motion along with their structural characteristics. In alkali fluorides, the self-diffusion coefficient of fluorine depends slightly on the composition compared to the temperature, displaying these systems as an ideal bath of polarizable hard spheres. In contrast, self-diffusion in rare earth and alkali fluorides mixtures presents a complicated balance between temperature and the network-forming process of the ionic long-lived units. These results open wide perspectives in the study of high temperature liquids.
自扩散是液体动力学的基本属性,它也提供了重要的结构信息。为了探索高液相温度的无机熔体的动力学,我们提出了一种新的基于脉冲场梯度 NMR 与激光加热相结合的装置,该装置使得在 1500 K 下原位自扩散系数的测量成为可能。将其应用于多种腐蚀性熔融氟化物,这些氟化物具有广泛的组成和温度范围,我们已经证明了它们在运动方面的不同关键参数及其结构特征。在碱金属氟化物中,氟的自扩散系数与温度相比,其组成依赖性较小,表明这些体系为可极化硬球的理想浴。相比之下,在稀土和碱金属氟化物混合物中的自扩散呈现出温度与离子长寿命单元的网络形成过程之间复杂的平衡。这些结果为高温液体的研究开辟了广阔的前景。