硅酸盐学报

铁镁电气石Y位阳离子主导的构效关系

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周琳 ¹ , 张伟 ² , 周磊 ³ , 郭铭 ¹^,⁴ , 董发勤 ¹ , Elena Leonidovna Kotova ⁵ , Leonid Nafanailovichd Kotov ⁶

硅酸盐学报 | 环境矿物材料专题—研究论文 2024,52(10): 3192-3204

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硅酸盐学报 |环境矿物材料专题—研究论文 2024 , 52 (10) : 3192 -3204

铁镁电气石Y位阳离子主导的构效关系

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周琳¹, 张伟², 周磊³, 郭铭¹^,⁴, 董发勤¹, Elena Leonidovna Kotova⁵, Leonid Nafanailovichd Kotov⁶

作者信息

^1．西南科技大学固体废物处理与资源化教育部重点实验室，四川绵阳 621010，中国

^2．西南科技大学分析测试中心，四川绵阳 621010，中国

^3．西南科技大学核废物与环境安全国防重点学科实验室，四川绵阳 621000，中国

^4．西南科技大学环境与资源学院，四川绵阳 621010，中国

^5．Mining Museum, St. Petersburg Mining University, St Petersburg 199106, Russia

^6．Department of Radiophysics and Electronics, Syktyvkar State University, Syktyvkar 167001, Russia

通讯作者:

董发勤（1963—），男，博士，教授。

作者简介:

周琳（1994—），女，博士研究生。

Structure-Function Relationship of Fe-Mg Tourmaline Dominated by Positive Ion in Y Site

Lin ZHOU¹, Wei ZHANG², Lei ZHOU³, Ming GUO¹^,⁴, Faqin DONG¹, Elena Leonidovna KOTOVA⁵, Leonid Nafanailovichd KOTOV⁶

Affiliations

^1.Key Laboratory of Waste Solid Treatment and Resource Recycle of Ministry of Education, Mianyang 621010, Sichuan, China

^2.Analysis and Testing Center, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

^3.Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

^4.School of Environment and Resources, Southwest University of Science and Technology, Mianyang 621010, Sichuan, China

^5.Mining Museum, St. Petersburg Mining University, St Petersburg 199106, Russia

^6.Department of Radiophysics and Electronics, Syktyvkar State University, Syktyvkar 167001, Russia

Corresponding Author:

DONG Faqin (1963-), male, Ph.D., Professor. E-mail: fqdong@swust.edu.cn

ZHOU Lin (1994-), female, Doctoral candidate. E-mail: zhoulin_5189@163.com

出版时间: 2024-10-20 doi: 10.14062/j.issn.0454-5648.20240159

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摘要

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具有特异性对称结构的天然自发极化矿物—电气石被广泛应用于环保和医疗保健领域，厘清电气石成分-结构-性能之间的作用关系可为电气石行业提供性能最优的理想构型，为其他天然复杂矿物的构效分析和性能调控提供方法参考。通过对含铁电气石样品进行全成分、端元占位、晶体微结构和自发极化性能分析，揭示了铁镁电气石成分-微结构-自发极化性能的影响控制过程：在铁含量高于镁含量的电气石中，晶胞体积随镁含量升高而升高，Fe²⁺含量越高且Z位含铁时，电气石多面体扭曲增强，固有电偶极矩增大；在铁含量低于镁含量的电气石中，晶胞体积随铁含量升高而增大，结构扭曲和固有电偶极矩随铁含量的升高而减弱，随Fe²⁺含量增大而增大；自发极化性测试证明电气石的性能强弱与固有电偶极矩变化规律一致；整理过往文献数据，分析Y位阳离子主导下的电气石固有电偶极矩变化趋势，揭示以Fe元素为主要影响因素的构效关系：当Mg/Fe摩尔比小于1时，电气石性能随Fe含量的减小而减弱；当Mg/Fe摩尔比大于1时，电气石的性能随Fe含量减小而增强；而当Mg/Fe摩尔比大于2时，其自发极化性上升趋势则趋于平稳。

关键词

铁镁电气石 / Y位阳离子 / 自发极化性 / 构效关系

Abstract

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Introduction

Tourmaline is a kind of borosilicate mineral with complex structure and composition, which is used in the fields of functional materials, environmental protection and healthcare. Since the positive and negative charge centers of tourmaline do not coincide, tourmaline has a natural spontaneous polarization that is one of the most important properties, having its application in various fields. In previous studies, the changes of element occupancy, valence proportion of key elements and crystal structure parameters in tourmaline cause the lattice distortion, resulting in a change of spontaneous polarization intensity. It is thus of great significance to reveal the relationship among the composition, structure and property of tourmaline. In this paper, the control path along iron speciation-microstructure-spontaneous polarization of Fe-Mg tourmaline was investigated to clarify the structure-activity relationship dominated by cation occupancy in Y-site of tourmaline and propose the optimal configuration of tourmaline with the excellent performance.

Methods

Six single crystals of tourmaline samples with different Fe contents were collected from different locations in China (i.e., Hebei province, Xinjiang province, Yunnan province and Guangxi province), respectively. After digestion, the chemical compositions of the samples were determined by ICP. The natural tourmaline was crushed by a model RH-800 high-speed multifunctional pulverizer (Zhejiang Ronghao Industry and Trade, China), and ground by a model XPM-Φ100×4 planetary muller (Wuhan Prospecting Machinery Factory, China). The composition of tourmaline was determined by a model 7700x inductively coupled plasma optical emission spectrometry (ICP-OES, Agilent Co., USA). The crystallographic structure of tourmaline was examined by a model X'Pert PRO X-ray diffractometer (XRD, PANalytical B.V., the Netherlands) with Cu K_α radiation over a 2θ range between 3° and 80°. The occupancy of Fe²⁺ and Fe³⁺ at Y and Z sites of tourmaline was characterized by a model MVT-1000Mossbauer spectrometer (Wissel Co., Germany). The crystal structure of tourmaline was characterized by a model Smart APEX-CCD X-ray single-crystal diffractometer (Bruker Co., Germany) with Mo Kα radiation, and the structure refinement was completed by a crystallography software named SHELXS-97. The spontaneous polarization intensity was measured quantitatively and indirectly by an alkali solution method.

Results and discussion

The structure difference due to different composition of tourmaline is mainly caused by the element change in Y site, in which Fe element plays a crucial role. Based on the calculation of intrinsic electric dipole moment, the spontaneous polarization intensity of tourmaline along the c-axis is more intense than that in other directions (cylinder), and the T polyhedron is the largest contributor to the intrinsic electric dipole moment of tourmaline. The intrinsic electric dipole moments generated by each polyhedron along the a and b axes cancel each other due to the toroidal symmetrical structure of tourmaline, resulting in a small total intrinsic electric dipole moment.

The intrinsic electric dipole moment and the spontaneous polarization intensity of the six tourmaline samples are in the order GX-1>YN-1>XJ-1>HB-1>XJ-2>HB-2. The more intense the polyhedral distortion is, and the larger the intrinsic electric dipole moment and the more intense the spontaneous polarization will be. For tourmalines with Fe content that is higher than Mg content, the polyhedron distortion of tourmaline and the intrinsic electric dipole moment increase with the increase of Fe²⁺ content and iron atom in Z site. For tourmalines with Fe content that is lower than Mg content, the structure distortion and the intrinsic electric dipole moment decrease with the increase of Fe content, and increases with the increase of Fe²⁺ content.

For the Fe-Mg tourmalines, the Y site is mainly occupied by Fe atoms and Mg atoms, and the change of Mg/Fe molar ratio directly affects the expansion and deformation of Y polyhedron, resulting in the change of tourmaline structure. After the intrinsic electric dipole moment of tourmaline is analyzed at different Mg/Fe ratios, the intrinsic electric dipole moment of tourmaline decreases with the decrease of Fe content when the molar ratio of Mg/Fe is less than 1. This is due to the decrease of Fe²⁺ content, leading to the weakening of structural distortion. The intrinsic electric dipole moment of tourmaline increases with the decrease of Fe content when the Mg/Fe molar ratio is greater than 1, which is consistent with the previous results. For tourmaline with Fe content that is lower than Mg content, the lower the Fe content is, and the more intense the structural distortion and the greater the inherent electric dipole moment will be. When the Mg/Fe molar ratio is greater than 2, the intrinsic electric dipole moment and the spontaneous polarization intensity of tourmaline at different Mg/Fe molar ratios become stable.

Conclusions

For tourmalines with Fe content that was higher than Mg content, the cell volume increased with the increase of magnesium content, and the polyhedron distortion of tourmaline and the intrinsic electric dipole moment increased with the increase of Fe²⁺ content and iron atom in Z site. For tourmalines with Fe content that was lower than Mg content, the cell volume increased with the increase of Fe content, the structural distortion and the intrinsic electric dipole moment decreased with the increase of Fe content, and increased with the increase of Fe²⁺ content. The results of spontaneous polarization test showed that the characteristic properties of tourmaline were consistent with the intrinsic electric dipole moment. The configuration structure-function relationship of tourmaline with Fe as a main factor was revealed via analyzing the variation trend of intrinsic electric dipole moment under the dominance of Y-end positive ion. The performance of tourmaline decreased with the decrease of Fe content when the Mg/Fe molar ratio was less than 1. The performance of tourmaline increased with the decrease of Fe content when the Mg/Fe molar ratio was greater than 1. The spontaneous polarization increased when the Mg/Fe molar ratio was greater than 2.

Key words

iron-magnesium tourmaline / positive ion in Y site / spontaneous polarization / structure-function relationship

引用本文

周琳, 张伟, 周磊, 郭铭, 董发勤, Elena Leonidovna Kotova, Leonid Nafanailovichd Kotov. 铁镁电气石Y位阳离子主导的构效关系. 硅酸盐学报, 2024 , 52 (10) : 3192 -3204 . DOI: 10.14062/j.issn.0454-5648.20240159

Lin ZHOU, Wei ZHANG, Lei ZHOU, Ming GUO, Faqin DONG, Elena Leonidovna KOTOVA, Leonid Nafanailovichd KOTOV. Structure-Function Relationship of Fe-Mg Tourmaline Dominated by Positive Ion in Y Site[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (10) : 3192 -3204 . DOI: 10.14062/j.issn.0454-5648.20240159

基金

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国家自然科学基金项目(51974261)

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2024年第52卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240159

接收时间：2024-02-28
首发时间：2026-10-22
出版时间：2024-10-20

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收稿日期：2024-02-28
修回日期：2024-04-22

基金

国家自然科学基金项目(51974261)

作者信息

^1．西南科技大学固体废物处理与资源化教育部重点实验室，四川绵阳 621010，中国

^2．西南科技大学分析测试中心，四川绵阳 621010，中国

^3．西南科技大学核废物与环境安全国防重点学科实验室，四川绵阳 621000，中国

^4．西南科技大学环境与资源学院，四川绵阳 621010，中国

^5．Mining Museum, St. Petersburg Mining University, St Petersburg 199106, Russia

^6．Department of Radiophysics and Electronics, Syktyvkar State University, Syktyvkar 167001, Russia

通讯作者:

董发勤（1963—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240159

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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