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The effect of silicate network modifiers on colour and electron spectra of transition metal ions

机译：硅酸盐网络改性剂对过渡金属离子颜色和电子光谱的影响

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摘要

Coloured silicate glasses of Li_2O-SiO_2, Na_2O-SiO_2 and K_2O-SiO_2 systems were produced by melting at 1400 ℃. As dyes, compounds of cobalt, nickel, chromium and manganese were used. The aim of this study was to determine the effect of glass matrix modifiers on colour and d-d electron spectra of chosen transition metal ions. From the analysis of colour and electron spectra of the obtained glasses it follows that the chemical composition of the glass matrix influences the coordination state as well as the oxidation state of the transition metal. Cobalt and nickel occur in examined glasses as divalent ions (Co~(2+), Ni~(2+)) in both coordinations - octahedral and tetrahedral. A decrease of the electronegativity of modifiers (Li → Na → K) and an increase of the glass matrix basicity promotes the tetrahedral coordination of cobalt and nickel. Chromium and manganese occur in silicate glasses in various oxidation state, though Cr~(3+) and Mn~(3+) ions in octahedral coordination are dominant. The decrease of the electronegativity of the modifiers causes a shift of oxidation/reduction equilibrium towards higher valence of the transition metals (Cr~(6+), Mn~(3+)).
机译：Li_2O-SiO_2，Na_2O-SiO_2和K_2O-SiO_2体系的有色硅酸盐玻璃是在1400℃下熔融制得的。作为染料，使用钴，镍，铬和锰的化合物。这项研究的目的是确定玻璃基质改性剂对所选过渡金属离子的颜色和d-d电子光谱的影响。从获得的玻璃的颜色和电子光谱的分析可以得出，玻璃基质的化学组成影响过渡金属的配位态和氧化态。钴和镍在被检查的玻璃中以八面体和四面体两种配位形式的二价离子（Co〜（2 +），Ni〜（2+））出现。改性剂（Li→Na→K）的电负性的降低和玻璃基质碱度的提高会促进钴和镍的四面体配位。铬和锰以各种氧化态存在于硅酸盐玻璃中，尽管八面体配位的Cr〜（3+）和Mn〜（3+）离子占主导地位。改性剂电负性的降低导致氧化/还原平衡向过渡金属（Cr〜（6 +），Mn〜（3+））的更高价态转移。

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