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| The Heat Treatment Process and Color Mechanism of Green
Fluor-Hydroxyapatite |
| YUE Su-wei1*, YAN Xiao-xu2*, CHEN Si-min2, LUO Jie2 |
1. Jewelry Institute, Guangzhou Polytechnic University, Guangzhou 511483, China
2. School of Jewelry, Guangzhou City University of Technology, Guangzhou 510800, China
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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 O2--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.
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Received: 2024-06-09
Accepted: 2025-02-25
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Corresponding Authors:
YUE Su-wei, YAN Xiao-xu
E-mail: yuesw@gzpyp.edu.cn；yanxiaoxu@gcu.edu.cn
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