绿色氟羟磷灰石热处理及颜色成因探究

doi:10.3964/j.issn.1000-0593(2025)07-1961-07

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摘要：磷灰石标准化学式为[Ca₁₀(PO₄)₆ (F, Cl, OH)₂]，是一种应用广泛的无机非金属材料和重要的地质指示矿物，也是常见的宝石品种。磷灰石中Ca²⁺可被二价过渡族金属阳离子（Fe²⁺、Mn²⁺等）、稀土元素离子（La³⁺、Ce³⁺、Gd³⁺等）或碱金属和碱土金属离子（K⁺、Na⁺、Sr²⁺等）类质同象替代，从而呈现黄色、绿色、蓝色、紫色及变色效应。绿色氟羟磷灰石经650 ℃–700℃热处理转变为鲜艳的蓝色，具有较高的观赏性和商业价值。运用电子探针（EPMA）、傅里叶变换中红外光谱（Mid FT-IR）、紫外-可见光光谱（UV-Vis）和电子顺磁波谱（EPR），测试与观察热处理前后氟羟磷灰石的化学组成以及不同温度下颜色变化。结果显示，样品化学成分主要由Ca²⁺和P⁵⁺及少量的N⁵⁺组成，N⁵⁺主要以—NH₂形式少量替代[PO₃]，表明样品形成与生物化学作用密切相关。样品热处理前后的UV-Vis特征显示，垂直于c轴方向的吸收带主要位于264～402和584～804 nm区域，其颜色主要由Ce³⁺和Mn²⁺类质同象替代畸变八面体中的Ca²⁺形成蓝绿区透过窗所致。热处理前绿色磷灰石样品中的缺陷主要为离子心F^--O^--F^-，以及由Ce³⁺类质同象替代CaⅠ位所致的空穴心O^2--O^--V和OH^--O^--V，热处理后由于空穴心的恢复则主要表现为Mn²⁺替代CaⅠ和CaⅡ位畸变八面体引起的离子心缺陷。结合EPR波谱表征可知，Mn²⁺在CaⅠ和CaⅡ位置均有分布，是样品呈现蓝色直接原因；Ce³⁺在CaⅠ位置类质同象替代程度较高时，样品颜色以绿色为主，反之呈现蓝色。

关键词：绿色磷灰石；热处理；颜色成因；EPR谱

Abstract：Apatite is widely used as an inorganic non-metallic material, a geological indicator mineral, and a common gemstone variety. The chemical formula for apatite is [Ca₁₀(PO₄)₆(F, Cl, OH)₂], Ca²⁺sites can be isomorphously substituted by divalent transition metal cations (Fe²⁺, Mn²⁺, etc. ), rare earth element ions (La³⁺, Ce³⁺, Gd³⁺, etc. ), or alkali and alkaline earth metal ions (K⁺, Na⁺, Sr²⁺, etc. ), resulting in various colors such as yellow, green, blue, purple, and photochromic effects. Green fluor-hydroxyapatite turns into a bright blue hue after heat treatment at 650～700 ℃, possessing high ornamental and commercial value. The results show that the samplesare mainly composed of Ca²⁺ and P⁵⁺ with a small amount of N⁵⁺, which is mainly substituted [PO₃] in the form of —NH₂, indicating biochemical behavior correlated in formation. UV-Vis results show that the sample's color is mainly caused by the isomorphic substitution of Ce³⁺ and Mn²⁺ in the distorted octahedron of Ca²⁺, forming a blue-green transmission window. The defects in the green apatite sample before heat treatment are mainly ionic centers F^--O^--F^-, combining with O^2--O^--V and OH^--O^--V, caused by the isomorphic substitution of Ce³⁺ at the CaⅠ site. After heat treatment, the recovery of hole centers is mainly manifested as ionic center defects caused by Mn²⁺ substituting the distorted octahedron at CaⅠ and CaⅡ sites. Combining EPR spectra shows that Mn²⁺ can be distributed at both CaⅠ and CaⅡ positions, causing a blue hue in the samples; otherwise, when Ce³⁺ is highly substituted at the CaⅠ position, the samples turn green.

Key words：Green apatite; Heat treatment; Color mechanism; EPR spectra

收稿日期: 2024-06-09 修订日期: 2025-02-25

中图分类号:

P575.4

基金资助: 国家自然科学基金项目(41403032)，广东省教育厅普通高校特色创新项目（2022KTSCX184），青年创新人才项目（2022KQNCX144），广州市创新团队科研项目（202235328），广州番禺职业技术学院科技类重大项目（2024KJ01）资助

通讯作者: 岳素伟，剡晓旭 E-mail: yuesw@gzpyp.edu.cn；yanxiaoxu@gcu.edu.cn

作者简介: 岳素伟，1985年生，广州职业技术大学珠宝学院教授 e-mail: yuesw@gzpyp.edu.cn

引用本文:

岳素伟，剡晓旭，陈思敏，罗洁. 绿色氟羟磷灰石热处理及颜色成因探究[J]. 光谱学与光谱分析, 2025, 45(07): 1961-1967.
YUE Su-wei, YAN Xiao-xu, CHEN Si-min, LUO Jie. The Heat Treatment Process and Color Mechanism of Green Fluor-Hydroxyapatite. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(07): 1961-1967.

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