Abstract:
The appearance of a kind of synthetic beryl introduced into the market by Tairus Created Gems recently, is very similar to copper and manganese-bearing greenish blue elbaite tourmaline (referred to as “Paraíba” in the trade). Thus, the chemical compositions, spectrum characteristics and colouring mechanism of hydrothermal synthetic Paraíba-colour beryl samples were researched by using the conventional gemmological methods and modern analytical techniques including electron probe micro-analyzer (EPMA), Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible absorption spectrometry (UV-Vis). The results showed that the dominant wavelength, brightness and saturation (CIE 1931) of hydrothermal synthetic Paraíba-colour beryl samples are 487.7-490.2 nm, 17.1%-31.5% and 47.8%-93.7% respectively. The refractive index and birefringence are 1.584-1.589 and 0.005, and density is 2.771-2.789 g/cm
3, which are slightly higher than natural beryl. The gemmological microscope investigations revealed that hydrothermal synthetic Paraíba-colour beryl exhibits typical growth patterns such as micro-wave, stair-step, cross, disorder and subparallel ones. EPMA analysis showed that the hydrothermal synthetic Paraíba-colour beryl is characterized by poor alkali (the content of K
2O and Na
2O content is generally below 0.2%), rich copper (the content of CuO is higher than 5.00%) and iron (the content of FeO
T is 1.76%-3.00%), and nickel-bearing (the content of NiO is 0.03%-0.15%). The FT-MIR spectra defined the vibration areas of silica tetrahedron group in six-membered rings. The symmetry and asymmetry stretching modes of O—Si—O and Si—O—Si mainly appear at 970, 1 246 cm
-1 respectively. The FT-NIR analysis indicated that Type-Ⅰ and Type-Ⅱ water molecules are coexisting within the ring channel of hydrothermal synthetic Paraíba-colour beryl, and the absorption bands relating to the combination modes of type-Ⅰ and type-Ⅱ H
2O mainly appear at 5 450, 5 127 and 5 270 cm
-1. Besides, a certain amount of mineralizing agent used to synthetize beryl hydrothermally locates within the ring channel, and absorption bands appearing at 2 736 cm
-1 and 2 450 cm
-1 relating to chloridion are considered to be one of the identification characteristics of hydrothermal synthetic Paraíba-colour beryl. The UV-Vis spectra and EPMA results showed that the Paraíba-colour of hydrothermal synthetic beryl is mainly attributed to Cu
2+, Fe
2+, Fe
3+ and Ni
2+ in the crystal structure. The Fe
3+ with
6A1g→
4Eg(
4D) and
6A1g→
4Eg+
4A1g(
4D)
d—
d electron transition absorption bands appear at 370 nm and 426 nm. The Ni
2+ with
3A2g→
3T1g(
3P)
d—
d electron transition absorption band appears at 460 nm. A combination of the Cu
2+ with
2E→
2T2(
2D), the Fe
3+ with
6A1g→
4T2g(
4G), the Fe
2+ with
5T2g→
5Eg(
5D)
d—
d electron transition and Fe
2+—Fe
3+ charge transfer absorption bands result in the strong absorption between 613-638 nm and 1 500 nm.