Control of selective silicate glass coloration by gold metallic nanoparticles: structural investigation, growth mechanisms, and plasmon resonance modelization

N. Pellerin,M. Allix,S. Ory,J-P. Blondeau,D. Massiot,S. Noui,D. De Sousa Meneses,O. Veron

doi:10.1007/s13404-013-0121-x

Abstract

Soda lime silicate oxide glasses are studied to perform coloration thanks to gold nanoparticles’ crystallization. This precipitation is conducted by chemical reduction of gold ions with stannous or antimony oxides as reducing agents. A control of the rendered coloration between blank to red shades has been obtained using Sb2O3 agent and appropriate thermal treatments. The glasses remain colorless while heating up to 450 °C. Structural glasses evolution is studied by MAS NMR spectroscopy of 29Si and 23Na nuclei to investigate the silicate network polymerization change and the modification of sodium/oxygen bond length versus nucleation state and growth of Au nanoparticles. A clear decrease of the Q2 species part is observed with nanoparticles growth confirmed by the evolution of chemical shift for 23Na resonance. A slight network polymerization is then showed independently of the only thermal treatment. This structural change could be induced by the antimony oxidation and change towards higher coordinations. Finally, the glasses chemical durability has been studied by leaching tests and shows lower alteration for colored glass. The optical spectroscopy applied to colored glasses has given rise to plasmon resonance phenomena at around 600 nm which is the typical surface plasmon resonance of gold for a refractive medium index of 1.5, with a shift of the resonance towards the higher wavelengths with increasing thermal treatment temperature. This shift is modelized by Drude and MIE approaches and confirms the trend observed by UV-visible measurement with an increasing absorption at the SPR correlated to a typical Ostwald growth mechanism according to the increase of the annealing temperature.

Highlights

IntroductionAccording to the cadmium toxicity, another common way to elaborate ruby glasses is the addition of gold (or cupper) and reducing agents as stannous oxide or antimony oxides to promote the gold reduction, according to the method delivered by the cultural heritage whose first historical trace is at the fourth century [1, 3, 4]
Cadmium sulfoselenide is currently used as pigment for red glass making [1, 2]
The base glass composition 70 %SiO2–10 %CaO–20 %Na2O has allowed to test the red color appearance according to the reducing agents choice and to the thermal treatments performed

Summary

Introduction

According to the cadmium toxicity, another common way to elaborate ruby glasses is the addition of gold (or cupper) and reducing agents as stannous oxide or antimony oxides to promote the gold reduction, according to the method delivered by the cultural heritage whose first historical trace is at the fourth century [1, 3, 4]. The peculiar optical properties observed in the visible spectral range are explained by the surface plasmon resonance originating an absorption band usually around 530 nm (for gold) produced by these metal particles in the nanometer size range. The colors are variable, depending in part on the concentration and sizes of the gold particles dispersed throughout the glass and in another part of the processing parameters like thermal treatments. About 0.001– 0.1 wt% gold is required to provide coloration in silicate

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