Size-Dependent Structural Phase Transition Behaviors of CaF2 Nanocrystals

GONG Lei WANG Jingshu ZHANG Junkai CHEN Guangbo ZHANG Han WU Xiaoxin HU Tingjing CUI Hang

巩蕾, 王婧姝, 张俊凯, 陈广博, 张晗, 武晓鑫, 胡廷静, 崔航. CaF2纳米晶粒结构相变行为的尺寸依赖性[J]. 高压物理学报, 2022, 36(2): 021102. doi: 10.11858/gywlxb.20210842
引用本文: 巩蕾, 王婧姝, 张俊凯, 陈广博, 张晗, 武晓鑫, 胡廷静, 崔航. CaF2纳米晶粒结构相变行为的尺寸依赖性[J]. 高压物理学报, 2022, 36(2): 021102. doi: 10.11858/gywlxb.20210842
GONG Lei, WANG Jingshu, ZHANG Junkai, CHEN Guangbo, ZHANG Han, WU Xiaoxin, HU Tingjing, CUI Hang. Size-Dependent Structural Phase Transition Behaviors of CaF2 Nanocrystals[J]. Chinese Journal of High Pressure Physics, 2022, 36(2): 021102. doi: 10.11858/gywlxb.20210842
Citation: GONG Lei, WANG Jingshu, ZHANG Junkai, CHEN Guangbo, ZHANG Han, WU Xiaoxin, HU Tingjing, CUI Hang. Size-Dependent Structural Phase Transition Behaviors of CaF2 Nanocrystals[J]. Chinese Journal of High Pressure Physics, 2022, 36(2): 021102. doi: 10.11858/gywlxb.20210842

Size-Dependent Structural Phase Transition Behaviors of CaF2 Nanocrystals

doi: 10.11858/gywlxb.20210842
Funds: National Natural Science Foundation of China (11904128); Thirteenth Five-Year Program for Science and Technology of Education Department of Jilin Province (JJKH20200410KJ); Academic Graduate Students Scientific Research Innovation Fund of Jilin Normal University (202005)
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    Author Bio:

    GONG Lei (1998-), female, bachelor, major in high pressure structural phase transition of nanomaterials. E-mail: gl15734441063@126.com

    Corresponding author: WANG Jingshu (1982-), female, doctor, associate professor, major in high pressure behavior of nanomaterials. E-mail: wjs@jlnu.edu.cn
  • 摘要: 利用原位高压同步辐射X射线衍射方法,对尺寸为11 nm的CaF2纳米晶粒进行高压结构相变和压缩特性研究。当压力为12 GPa时,观察到由萤石结构向 α-PbCl2结构转变的一次相变,该相变压力点远高于体材料,但略低于粒径更小的 CaF2 纳米晶体。相比体材料,纳米尺寸的CaF2样品的体弹模量更大,说明其更难被压缩。当压力释放至常压时,11 nm的CaF2纳米晶粒的α-PbCl2型亚稳相结构被保留下来,相变不可逆。分析了影响11 nm CaF2纳米晶粒独特高压行为的原因,判定尺寸效应为主要因素,该尺寸下较高的表面能导致结构稳定性增强和体积模量增加。

     

  • Figure  1.  (a) TEM image of the as-synthesized CaF2 nanocrystals; (b) particle size distribution of the CaF2 nanocrystals

    Figure  2.  Rietveld refinement of the diffraction pattern of the synthesized CaF2 nanoparticles (Red dots, upper (blue), and lower (black) solid lines represent experimental, calculated, and residual patterns, respectively.)

    Figure  3.  High-pressure XRD patterns of the CaF2 nanocrystals, in which the peak (marked by asterisk) is derived from the gasket

    Figure  4.  Rietveld refinement of the diffraction pattern of the CaF2 nanocrystals at ambient conditions after decompression (Red dots, upper (blue), and lower (black) lines represent experimental, calculated, and residual patterns, respectively.)

    Figure  5.  Unit-cell volume as a function of pressure determined for the 11 nm-sized CaF2 nanocrystals (Solid curves are the Birch-Murnaghan EOS fits to the experimental data. Error bars are observed when they are large enough to exceed the sizes of the marked dots.)

    Figure  6.  HRTEM image of the as-synthesized 11 nm-sized CaF2 nanocrystals.

    Table  1.   Transition pressure (${p}{_{\rm T}}$), and EOS parameters (B0 and B0 ′) of the fluorite-type and the α-PbCl2-type CaF2

    MorphologySize$p{_{\rm T}} $/GPa${B{_0 } } $/GPa B0
    Fm3mPnmaFm3mPnma
    BulkMicro9.5[21]87(5) [21]74(5) [22] 54.7
    9[34]81(1) [34]5.22
    8.1[20]79.54[20]70.92[20]4.544.38
    Nanocrystals8 nm14[23]112(6)93(9) 54
    23 nm9.5[24]103(2) [24]78(2) [24]54
    11 nm12109(5)89(1)54
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  • 收稿日期:  2021-07-12
  • 修回日期:  2021-08-05
  • 录用日期:  2021-07-12

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