论文标题

由内部压力引起的玻璃长期腐蚀的热裂开机制:解聚,杂质迁移和在原子量表上破裂的过程

Thermal-fluctuation mechanism of long-term corrosion of glass caused by internal stress: processes of depolymerization, impurity migration and fracturing on an atomic scale

论文作者

Kadikova, Irina F., Yuryeva, Tatyana V., Morozova, Ekaterina A., Grigorieva, Irina A., Afanasyev, Ilya B., Karpenko, Vladimir Y., Yuryev, Vladimir A.

论文摘要

使用偏振光显微镜,FTIR和SEM(包括EDX和元素映射)研究了玻璃的长期腐蚀。 19世纪初由铅钾玻璃制成的珠子是研究的对象。在珠制造过程中,将非均匀分布的内部应力引入了研究的玻璃中。已经证明了19世纪珠玻璃的腐蚀,包括几个相互连接的过程,并平行和增强彼此。这些过程是玻璃的解聚,碱金属杂质和局部玻璃浸出的定向迁移,以及微不足的成核,然后是微裂纹的形成及其逐渐生长。随着时间的流逝,它们的累积且显然是协同作用会导致玻璃破裂终止,珠子碎成微小的变色颗粒。所有这些现象均由珠子生产过程源自内部应力控制。因此,应力的珠玻璃腐蚀的现象是通过裂缝的成核和生长在室温下持续数十年的玻璃内部应力松弛的过程。当珠子进行热处理时,它会大大加速。在300°C下退火15分钟。足以使最初完整珠的人工衰老。即使将珠子保存在控制良好的博物馆环境中,也观察到这种腐蚀发生在玻璃中。提出了局部的热裂开机制来解释原子量表的腐蚀现象。基于热裂开机制的方法适用于在应力下描述各种固体物质和复合材料中的降解和破坏过程;这种方法使理解纳米结构的形成和降解现象,e。 g。,具有量子井或量子点的异质结构。

Long-term corrosion of glass is studied using polarising light microscopy, FTIR and SEM including EDX and elemental mapping. Early 19th century beads made of lead-potassium glass are the object of the study. Non-uniformly distributed internal stresses were introduced into the studied glass during bead manufacturing. Corrosion of 19th century bead glass has been shown to comprise several mutually connected processes developing in parallel and intensifying one another. These processes are the depolymerization of glass, the directed migration of alkali-metal impurities and local glass leaching, and the nucleation of micro discontinuities followed by the formation of micro cracks and their gradual growth. In course of time, their cumulative and apparently synergistic effect results in glass fracturing terminated with bead crumbling into tiny discoloured particles. All these phenomena are controlled by the internal stress originated from the bead production process. Thus, the phenomenon of stressed bead glass corrosion is the process of the internal stress relaxation in glass through the nucleation and growth of cracks, which lasts for many decades at room temperature. It is dramatically accelerated when beads are heat treated. Annealing at 300°C for 15 min. is sufficient for artificial ageing of initially intact beads. The corrosion has been observed to occur in glass even if beads are kept in well-controlled museum environment. The local thermal-fluctuation mechanism is proposed to account for the corrosion phenomenon on an atomic scale. The approach based on the thermal-fluctuation mechanism is applicable to describe degradation and destruction processes in various solid substances and composite materials under stress; this approach enables understanding the phenomena of formation and degradation of nanostructures, e. g., heterostructures with quantum wells or quantum dots.

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