Spectroscopic Characteristics and Coloring Mechanism of Greenish-Yellow Beryl Under Heating Treatment
YAN Xiao-xu1, 2, WANG Pei-lian1, YUE Su-wei1, 2*
1. School of Jewelry, Guangzhou College South China University of Technology, Guangzhou 510800, China
2. Institute of Jewelry, Guangzhou College South China University of Technology, Guangzhou 510800, China
Abstract:Beryl group belongs to the hexagonal system and contains a series of beryllium-aluminosilicate minerals. Beryl gems normally show various colors, due to the occurrence of different trace elements. Greenish-yellow beryl and aquamarine are usually colored by iron ions in different valence states. Fe3+ and Fe2+ may occupy tetrahedral position (Fe2+4), octahedral position (Fe3+6) and crystalline channel([Fe2(OH)4]2+). Light blue aquamarine can be obtained by heating treatment of greenish-yellow beryl: (1) in 300~550 ℃ step heating-treatment experiments, the color of samples changes successively from light green, pale yellowish-green, through light yellow, pale blue to light blue; (2) the color turns into pale blue in 550~600 ℃; (3) desirable color modification occurs in 500~550 ℃. Mid FT-IR, UV-Vis and EPR spectroscopic analyses were conducted on beryl samples before and after heating treatment. The mid-FT-IR spectra of heated and unheated samples show similar molecular vibration spectroscopy characteristics. The absorption peaks in the region of 1 250~600 cm-1 which correlate to the typical vibration of [Si6O18] group shift to the direction of low wave number, along with the reduction of absorption intensity, indicating changes in Fe3+-O2- charge transfer and the bending vibration of the structural water during heating: (1) the weakening of Fe3+-O2- charge transfer was caused by the reduction of Fe3+ in the structural channel; (2) the weakening of bending vibration of structural water was caused by the water loss in heating treatment. The UV-Vis spectra show that same characteristics in both reductive and oxidative environment. However, there are some changes indicating the weakening of Fe3+ forbidden transition which leads to the disappearance of yellow color compared to unheated samples: (1) the absorption peak which attributed to O2-→Fe3+ charge transfer shifts towards the ultraviolet-light region and forms 322 nm absorption; (2) 6A1g→4T2g transfer shifts towards violet-light region and form 370 nm absorption; (3) 6A1g→4Eg+4A1g transfer shifts towards red-light region and form 427 nm absorption. Also, a wide absorption band near 823 nm was enhanced and shifted towards the visible-light region indicating a content increase of Fe2+ in structural channels which led the appearance of blue color. The ESR spectrum of natural greenish yellow beryl shows that Fe3+, Mn2+ and OH radical exist both in Al—O octahedron and structural channels. Following conclusions can be drawn from combined UV-Vis spectra: (1) Fe3+ in structural channels has been reduced to Fe2+ in heating treatment; (2) the forbidden transition of Fe3+ in Al—O octahedron is weakened during heating treatment; (3) the blue color acquired from heating treatment is caused by a combination of the above two changes in beryl crystals.
剡晓旭,王沛炼,岳素伟. 热处理绿黄色绿柱石光谱特征与颜色成因探究[J]. 光谱学与光谱分析, 2020, 40(12): 3795-3800.
YAN Xiao-xu, WANG Pei-lian, YUE Su-wei. Spectroscopic Characteristics and Coloring Mechanism of Greenish-Yellow Beryl Under Heating Treatment. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2020, 40(12): 3795-3800.
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