Effect of post-growth anneals in oxygen-containing atmosphere on the microhardness of single crystal calcium molybdate CaMoO4

E. V. Zabelina, N. Kozlova, O. Buzanov, Elena D. Krupnova
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Abstract

Single crystal calcium molybdate CaMoO4 is a well-known material. However the interest to CaMoO4 has recently grown due to a number of its important applications including as a working material in cryogenic scintillation bolometers. CaMoO4 single crystals acquire blue color during growth due to the presence of color-center type defect centers which are unacceptable for optical applications. Color can be eliminated through annealing in an oxygen containing atmosphere, following which required optical components can be produced from the single crystals by mechanical treatment (cutting, polishing etc.). Therefore assessment of the mechanical properties of these single crystal materials is an important task for the optimal solution of issues occurring in the fabrication of optical components and their further practical application. There are but scarce data on the mechanical properties of CaMoO4, and the available ones have been reported without allowance for anisotropy. There is a significant scatter of data on the Mohs hardness of the single crystals, ranging from 3.3 to 6 in different publications. In this work we present data on calcium molybdate single crystals in the initial state and after high-temperature anneals of different durations in an oxygen containing atmosphere. We show that long-term annealing leads to decolorization of the crystals. Calcium molybdate single crystals prove to be quite brittle: the brittleness index Zp of the crystals in the initial state is the highest and equals 5, while annealing reduces the brittleness index to 4. The Palmqvist toughness factors S have been calculated The limit indentation destruction loads Flim have been determined and annealing in an oxygen containing atmosphere has been shown to increase Flim by 2.5 times for the Z cut and by 10 times for the X cut. The microhardness of the crystals has been shown to exhibit a II type anisotropy: the microhardness of all the specimens was higher for the Z cut than for the X cut. The microhardness anisotropy coefficients KH of the specimens have been evaluated. The bond ionicity degree I has been calculated on the basis of the experimentally measured microhardness.
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含氧气氛中长大后退火对钼酸钙单晶CaMoO4显微硬度的影响
单晶钼酸钙CaMoO4是一种众所周知的材料。然而,由于CaMoO4的一些重要应用,包括作为低温闪烁测热计的工作材料,对CaMoO4的兴趣最近有所增长。由于存在色中心型缺陷中心,CaMoO4单晶在生长过程中获得蓝色,这在光学应用中是不可接受的。可以通过在含氧气氛中退火来消除颜色,随后可以通过机械处理(切割,抛光等)从单晶中生产所需的光学元件。因此,评估这些单晶材料的力学性能对于优化解决光学元件制造中出现的问题及其进一步的实际应用是一项重要的任务。关于CaMoO4力学性能的数据很少,而且现有的数据都是在没有考虑各向异性的情况下报道的。在不同的出版物中,单晶的莫氏硬度数据有明显的分散,从3.3到6不等。在这项工作中,我们介绍了钼酸钙单晶在初始状态和在含氧气氛中经过不同持续时间的高温退火后的数据。我们表明,长期退火导致晶体脱色。钼酸钙单晶具有较强的脆性,初始状态下晶体的脆性指数Zp最高,为5,退火后晶体的脆性指数降至4。测定了薄膜的极限压痕破坏载荷,结果表明,在含氧气氛中退火可使Z形切割的薄膜增加2.5倍,X形切割的薄膜增加10倍。晶体的显微硬度表现出II型各向异性:所有样品的显微硬度在Z切割比X切割高。测定了试样的显微硬度各向异性系数KH。根据实验测得的显微硬度计算了键离子度I。
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