无机玻璃:21世纪前夕的新旧结构

J. Šesták, B. Hlaváček, N. Koga
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摘要

历史表明,玻璃是一种非凡的非晶体物质,通常由最简单的原料自然或人工制成。然而,模仿进化,人类创造了各种各样的眼镜的新家族,特别是在过去的一百年里,通过创造性思维逐渐出现。讨论最多的问题是玻璃态作为一种具有低维组织结构的特殊形式的物质的热力学稳定性,以及它在非结晶固体的层次水平中的分类。在这方面最重要的是熵。我们可以说,沃格尔温度下熵的主要部分T/下标v/来源于热熵的贡献W/下标th/。当温度高于T/下标v/时,熵的组态部分W/下标cf/开始起作用。W/sub cf/部分主要与粒子的微构型位移有关。在及以上玻璃化转变温度T/sub g/,熵的构象部分W/sub conf/,它与宏观样品中粒子通过扩散的位移有关。在T/sub g/跃迁以上的液体似乎是由两种机械上不同的“种类”形成的。在T/sub g/温度下,绝大多数矩阵体系是由被激发到非谐振子振幅较低水平的粒子形成的。在T/sub g/以上,第二个“种”开始出现,它是由热激粒子形成的,能够克服其附近矩阵的粘性和弹性力,并通过热激和其附近的相互作用将粒子带到非线性振荡器的较高振幅水平。热激发的粒子因此形成了活跃的和短暂的空缺空间。这些空位具有很高的膨胀系数,通常是造成液体膨胀系数高的原因。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Inorganic glasses: old and new structures on the eve of the 21/sup st/ century
History has shown that glass is a remarkable noncrystalline substance, usually made naturally or artificially from the simplest raw materials. Mimicking evolution however, mankind has been responsible for the creation of new families of a wide variety of glasses which gradually appeared through creative-thinking particularly during last hundred years. The most discussed issue is the thermodynamic stability of the glassy state as a special form of matter with its low-dimensional organisational structure, as well as its classification within the hierarchy level of noncrystalline solids. In this respect the most important is entropy. We can say that the major part of the entropy under Vogels temperature, T/sub v/, has its origin in the thermal entropy contribution, W/sub th/. When the temperature becomes higher than T/sub v/, the configurational part of the entropy, W/sub cf/, starts to play a role. This W/sub cf/ part is mainly connected to the micro-configurational displacements of particles. At, and above, the glass transition temperature, T/sub g/, the conformational part of entropy, W/sub conf/, which is connected to the displacements of particles through diffusion in the macro-sample is involved. It seems that liquids above the T/sub g/ transition are formed by two mechanically distinct "species". Under the T/sub g/ temperature, a matrix system is formed, in vast majority, by particles excited just to the lower level of the amplitude of an anharmonic oscillator. Above T/sub g/, the second "species" starts to appear which is formed by thermally-excited particles able to overcome viscous and elastic forces of the matrix in their vicinity and bring the particles, through thermal excitement and interactions within their vicinity, to the upper amplitude levels of a nonlinear oscillator. The thermally excited particles thus form the active and ephemeral vacancy spaces. These vacancies have very high expansion coefficient and are responsible for high expansion coefficient of liquids in general.
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