Negative Thermal Expansion in Fluoroapatite Pb5(VO4)3F Enhanced by the Steric Effect of Pb2+

被引：2

作者：

Oka, Kengo ^{[1
]}

Takasu, Miho ^{[1
]}

Nishiki, Wataru ^{[1
]}

Nishikubo, Takumi ^{[2
,3
]}

Azuma, Masaki ^{[2
]}

Noma, Naoki ^{[1
]}

Iwasaki, Mitsunobu ^{[1
]}

机构：

[1] Kindai Univ, Fac Sci & Engn, Dept Appl Chem, Higashiosaka, Osaka 5778502, Japan

[2] Kanagawa Inst Ind Sci & Technol, Ebina, Kanagawa 2430435, Japan

[3] Tokyo Inst Technol, Lab Mat & Struct, Midori Ku, Yokohama, Kanagawa 2268503, Japan

来源：

INORGANIC CHEMISTRY | 2022年 / 61卷 / 32期

关键词：

DIFFERENTIAL SCANNING CALORIMETER; CRYSTAL-STRUCTURE; 3-DIMENSIONAL VISUALIZATION; PHASE-TRANSITION; PERFORMANCE; ORIGIN;

D O I：

10.1021/acs.inorgchem.2c01300

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Negative thermal expansion (NTE) is an unusual thermophysical phenomenon and has gained attention as a way of controlling thermal expansion. Here, we report a substantial NTE in fluoroapatite Pb-5(VO4)(3)F in a limited temperature range. The dilatometric study revealed volume shrinkage below 150 K, giving a linear thermal expansion coefficient of alpha(L) = -44 ppm/K in the temperature range from 140 to 120 K upon heating. The NTE behavior is associated with a structural transition from the hexagonal (P6(3)/m) phase to the monoclinic (P2(1)/b) phase. Such a structural transition has been found in other apatite-type compounds, but the magnitude of the volume change in Pb-5(VO4)(3)F is remarkable. Our structural analysis revealed that the structural transition is classified as an antiferroelectric-to-paraelectric transition and the volume change during the transition is enhanced by the steric effect of 6s(2) lone-pair electrons of Pb2+.

引用

页码：12552 / 12558

页数：7

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