4.6 Article

Synthesis of the Zn1.9Cu0.1SiO4 pigment via the sol-gel and coprecipitation methods

Journal

JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY
Volume 100, Issue 3, Pages 404-413

Publisher

SPRINGER
DOI: 10.1007/s10971-021-05648-1

Keywords

Willemite; Pigment; Sol-gel method; Coprecipitation method; Simultaneous thermal analyses; Scanning electron microscopy

Funding

  1. State Contract of the Institute of Solid State Chemistry of the Ural Branch of the Russian Academy of Sciences [AAAA-A19-119031890026-6, AAAA-A19119031890025-9]
  2. Russian Fond of Basic Research [19-03-00189]

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Two soft chemistry methods were used to obtain Zn1.9Cu0.1SiO4 pigment, showing that the sequence of phase formation is influenced by the initial solutions characteristics. The sol-gel method involves structural transformations due to the removal of organic components and destruction of the polymer network, while in coprecipitation method crystallization occurs after removal of organic components and structurally bound water. Well-crystallized single-phase Zn1.9Cu0.1SiO4 samples can be obtained by annealing at 800 degrees C for 10 h. UV-Vis-NIR spectra show broad band electronic d-d transitions in the samples.
The Zn1.9Cu0.1SiO4 pigment was obtained by two variants of soft chemistry methods: using sol-gel synthesis in ethanol from TEOS and zinc and copper acetates and by coprecipitation of hydroxosilicate from an aqueous solution of zinc acetate and copper formate with sodium silicate. Thermal behavior of precursors, characterization of intermediate and final synthesis products were carried out by DSC, XRD, electron microscopy, colorimetry, IR, and UV-Vis-NIR spectroscopy. It is shown that the sequence of the phase formation of the synthesis product is determined by the characteristics of the initial solutions. It was established for the first time that when using the sol-gel method, the sequence of structural transformations is caused by the removal of the organic components and the destruction of the three-dimensional polymer network equivalent to Si-O-Si equivalent to. In the coprecipitation method, crystallization occurs after the removal of the organic components and structurally bound water. It is shown that a feature of this method is the simultaneous crystallization of two structural modifications Zn1.9Cu0.1SiO4, the metastable phase transforms into the willemite structure with a further increase in the temperature. It was found that well-crystallized single-phase Zn1.9Cu0.1SiO4 samples synthesized by these methods can be obtained by annealing at 800 degrees C for 10 h. The differences in the shape of the samples depend on the morphological and dimensional variations of the particles. UV-Vis-NIR spectra show the broad band with a maximum at about 760 nm corresponding to two electronic d-d transitions: B-2(1g) -> E-2(g) and B-2(1g) -> B-2(2g).

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