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亚稳准晶诱导大块非晶形成液体中的成核。

Metastable quasicrystal-induced nucleation in a bulk glass-forming liquid.

机构信息

Laboratory of Metal Physics and Technology, Department of Materials, ETH Zurich, 8093 Zurich, Switzerland

Laboratory of Metal Physics and Technology, Department of Materials, ETH Zurich, 8093 Zurich, Switzerland.

出版信息

Proc Natl Acad Sci U S A. 2018 Jun 12;115(24):6123-6128. doi: 10.1073/pnas.1717941115. Epub 2018 May 23.

Abstract

This study presents a unique Mg-based alloy composition in the Mg-Zn-Yb system which exhibits bulk metallic glass, metastable icosahedral quasicrystals (iQCs), and crystalline approximant phases in the as-cast condition. Microscopy revealed a smooth gradual transition from glass to QC. We also report the complete melting of a metastable eutectic phase mixture (including a QC phase), generated via suppression of the metastable-to-stable phase transition at high heating rates using fast differential scanning calorimetry (FDSC). The melting temperature and enthalpy of fusion of this phase mixture could be measured directly, which unambiguously proves its metastability in any temperature range. The kinetic pathway from liquid state to stable solid state (an approximant phase) minimizes the free-energy barrier for nucleation through an intermediate state (metastable QC phase) because of its low solid-liquid interfacial energy. At high undercooling of the liquid, where diffusion is limited, another approximant phase with near-liquid composition forms just above the glass-transition temperature. These experimental results shed light on the competition between metastable and stable crystals, and on glass formation via system frustration associated with the presence of several free-energy minima.

摘要

本研究提出了一种独特的 Mg-Zn-Yb 系 Mg 基合金成分,该合金在铸态下具有块状金属玻璃、亚稳二十面体准晶(iQCs)和晶态近似相。显微镜揭示了从玻璃到 QC 的平滑渐变过渡。我们还报告了通过在高速率下使用快速差示扫描量热法(FDSC)抑制亚稳到稳定的相转变,完全熔化亚稳共晶相混合物(包括 QC 相)。可以直接测量该相混合物的熔化温度和熔化焓,这明确证明了其在任何温度范围内的亚稳性。从液态到稳定固态(近似相)的动力学途径通过中间状态(亚稳 QC 相)最小化了形核的自由能垒,因为其具有低的固液界面能。在液态过冷度高、扩散受限的情况下,另一种具有近液态成分的近似相在玻璃转变温度以上形成。这些实验结果揭示了亚稳和稳定晶体之间的竞争,以及与多个自由能最小值相关的系统受挫导致的玻璃形成。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/2042/6004477/a48f3fd8c0ad/pnas.1717941115fig01.jpg

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