Shi Kaiyuan, Dong Xiao, Zhao Zhisheng, Su Lei, Ji Cheng, Li Bing, Zhang Jiaqing, Dong Xingbang, Qiao Pu, Zhang Xin, Yang Haotian, Yang Guoqiang, Gregoryanz Eugene, Mao Ho-Kwang
Key Laboratory of Photochemistry, Institute of Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Beijing, 100190, China.
Center for High Pressure Science and Technology Advanced Research, Beijing, 100093, China.
Nat Commun. 2025 Jan 3;16(1):357. doi: 10.1038/s41467-024-55028-w.
Due to the sulfur's atoms' propensity to form molecules and/or polymeric chains of various sizes and configuration, elemental sulfur possesses more allotropes and polymorphs than any other element at ambient conditions. This variability of the starting building blocks is partially responsible for its rich and fascinating phase diagram, with pressure and temperature changing the states of sulfur from insulating molecular rings and chains to semiconducting low- and high-density amorphous configurations to incommensurate superconducting metallic atomic phase. Here, using a fast compression technique, we demonstrate that the rapid pressurisation of liquid sulfur can effectively break the molecular ring structure, forming a glassy polymeric state of pure-chain molecules (Am-S). This solid disordered chain state appears to be (meta)stable in the P-T region usually associated with phase I made up of S. The elemental sulfur glass, made up from one of the simplest building blocks, offers a unique prospect to study the structure and property relationships of various other phases of sulfur and their interactions. More importantly, the fast compression technique performed at any temperature effectively like thermal quenching, opening up possibilities in high pressure synthesis by providing an effective and fast way of changing the fundamental thermodynamical parameter.
由于硫原子倾向于形成各种尺寸和构型的分子和/或聚合物链,在环境条件下,元素硫比任何其他元素拥有更多的同素异形体和多晶型物。起始结构单元的这种多变性部分归因于其丰富而迷人的相图,压力和温度会使硫的状态从绝缘的分子环和链转变为半导体的低密度和高密度非晶态构型,再到不相称的超导金属原子相。在此,我们使用快速压缩技术证明,液态硫的快速加压能够有效打破分子环结构,形成纯链分子的玻璃态聚合物状态(Am-S)。这种固体无序链状态在通常与由S组成的相I相关的P-T区域似乎是(亚)稳定的。由最简单的结构单元之一构成的元素硫玻璃,为研究硫的各种其他相的结构与性质关系及其相互作用提供了独特的前景。更重要的是,在任何温度下进行的快速压缩技术都像热淬火一样有效,通过提供一种有效且快速改变基本热力学参数的方法,为高压合成开辟了可能性。