Gold Ruby Glass Research Articles

Gold nano-particles fixed on glass

A simple process for producing wear resistant gold nano-particle coatings on transparent substrates is proposed. Soda-lime-silica glasses were sputtered with gold and subsequently coated with SiO2 using a combustion chemical vapor deposition technique. Some samples were first coated with silica, sputtered with gold and then coated with a second layer of silica. The samples were annealed for 20min at either 550 or 600°C. This resulted in the formation of round, well separated gold nano-particles with sizes from 15 to 200nm. The color of the coated glass was equivalent to that of gold–ruby glasses. Silica/gold/silica coatings annealed at 600°C for 20min were strongly adherent and scratch resistant. X-ray diffraction and electron backscatter diffraction (EBSD) were used to describe the crystal orientations of the embedded particles. The gold particles are preferably oriented with their (111) planes perpendicular to the surface.

Optical properties of self assembled oriented island evolution of ultra-thin gold layers

Gold layers with a thickness of only 8 to 21nm were sputtered on soda–lime–silica glasses. Subsequent annealing at 300 and 400°C for 1 and 24h resulted in the formation of separated round gold particles with diameters from 8 to 200nm. Crystal orientations were described using X-ray diffraction and electron backscatter diffraction. The gold particles are oriented with their (111) planes perpendicular to the surface. Most gold nano particles are single crystalline, some particles are twinned. Thermal annealing of sputtered gold layers resulted in purple samples with a coloration comparable to that of gold ruby glasses. The color can be controlled by the thickness of the sputtered gold layer and the annealing conditions. The simple method of gold film preparation and the annealing temperature dependent properties of the layers make them appropriate for practical applications.

Kinetic Investigation on the Color Striking of Gold Ruby Glass

Gold ruby glass of recipes 71SiO2, 11CaO, 11Na2O, 1PbO, 6K2O (in wt. %) were melted in alumina crucibles at 1500°C for 2h with SeO2 (0-200ppm) and C (0.1-0.25wt %) as reducing agents and gold (in flaky form) at 200ppm as a colorant. Clear glass samples were annealed at 570°C for 30minutes. The kinetics of striking mechanism were studied by a UV-Vis spectrophotometer accompanied with a heating stage in order to determine a precise annealing and heat treatment schedule, and to increase the uniformity of the red colour in glass. The glass specimens were heated at 625°C, 650°C and 700°C for 5 – 300minutes respectively. The investigations on an absorption peak appeared close to the typical ruby colour absorption (530nm) presented the self-striking capability. Results showed that the potential self-striking glass contained 200ppm of Au0, 100ppm of SeO2, and 0.20 in wt % of C. The appropriate striking temperature was at 650°C, and the threshold of the soaking time was 270minutes.

Physical colors in cultural heritage: Surface plasmons in glass

Abstract Gold ruby glass and lustre ceramics are the almost unique examples of physical colors in the cultural heritage. The main physical effect at the origin of their color is the excitation of surface plasmon modes in metal nanoparticles. Moreover, in lustre, interference effects due a multilayer structure add a bright iridescence. The principle of plasmons is recalled in detail and applied to Gold ruby glass. The case of luster ceramics is treated in more detail due to the complexity of the effects involved: plasmon, scattering, interference between specular reflected light beams and also between scattered beams. To cite this article: J. Lafait et al., C. R. Physique 10 (2009).

Gold nanoparticles in ancient and contemporary ruby glass

Abstract Gold ruby glass was made by irradiating a soda-lime-silicate glass with ca. 0.2 weight % of gold with gamma rays and further heating instead of using a reducing agent such as stannous oxide. Different colours were obtained by controlling the temperature and heating times. A comparison of this process to develop ruby glass with the conventional ones is discussed. Ruby glass was also made by dissolving gold metal in soda-lime-silicate glass and using stannous oxide at 1500 °C. The colour of the gold ruby glass is due to the presence of gold nanoparticles. A small purple-red 17th century glass vase was also studied and it was found to contain only manganese as the colouring agent; in this case the colour is due to electronic d–d transitions. A tentative experiment to reproduce the colour of this vase showed that the oxidation conditions are critical.

Effects of Gold Nanoparticles on the Fabrication of Red Colored High Refractive Index Lead Glass

Red colored gold ruby glass used for decorations in ancient times was actually gold nanotechnology at work by the addition of gold particles into molten lead glass. Most of high refractive index glasses are based on lead-bearing silicate glass. High refractive index lead glasses (HRLG) made from local sands and lead oxide were successfully fabricated both in laboratory and larger scales. In this study, gold metal was doped into the lead glass mixtures. Morphology of the prepared lead glass was observed using SEM and compared with that of the red colored Ancient Thai Glass (ATG). It was found that the fabricated red colored HRLG yielded similar color and clarity to the red colored ATG. From electron micrographs, the presence of gold in lead glass was in the form of nanoparticles. The optical properties of the glasses were also examined.

Gold-ruby glass in a new light: On the microstructuring of optical glasses with synchrotron radiation

We describe the microstructuring of gold-ruby glasses with synchrotron radiation. Plasmonic or luminescent microstructures with a lateral width of minimum 5 μm can be written directly into the glasses by implementing X-ray lithography. The technique involves two steps: First, gold containing glass samples are irradiated with synchrotron X-rays through a microstructured mask. And second, subsequent annealing at minimum 500°C induces the growth of gold nanoparticles. The patterned sites are ruby coloured due to the gold surface plasmon resonance of gold nanoparticles. Furthermore we investigated the photoluminescence of the microstructured glass. After synchrotron irradiation a red photoluminescence is observed under UV light excitation. Subsequent annealing for a few minutes at 300°C induces the quenching of the red luminescence. If the irradiated sample is annealed for 5 minutes at a higher temperature of 500°C a bright green light emission is detected. The green photoluminescence decreases after further annealing and finally vanishes. We assume that the origin of the luminescence are silicate hole centres. The technique of generating gold particles with synchrotron X-ray lithography has potential to produce micro-optical devices like optical storage units, photonic crystals, gratings or sensors.

Formation of gold nanoparticles in gold ruby glass: The influence of tin

197Au and 119Sn Mossbauer spectroscopy was used to study the effect of tin on the formation of gold nanoparticles in gold ruby glasses containing 200 ppm of gold and up to 2 wt.% of tin. The tin was found to speed up the formation of the metallic nanoparticles during annealing at temperatures around 600°C and to cause very small particles with sizes of only a few nanometres to be formed, whereas fewer but larger particles are formed in the absence of tin. This has consequences for the colour of the glasses, which changes from purple red for virtually tin-free to brown for tin-rich glasses.

Before striking gold in gold-ruby glass.

The chemistry of the magic ingredient in this ancient glass is no longer a mystery. The red colour of gold-ruby glass is caused by small particles of metallic gold that form when the gold-containing colourless glass is annealed. But the chemical state of the gold before striking red has been a mystery — is it dissolved in the glass as individual neutral gold atoms, like a frozen-in metal vapour that precipitates on annealing1, or as gold cations that must be reduced before the metallic clusters can grow and impart the lustrous colour2,3? Here we use Mossbauer spectroscopy to show that this gold is monovalent in the colourless glass, forming linear bonds to two neighbouring oxygen atoms.

Calculation of extinction and scattering spectra of large spheroidal gold particles embedded in a glass matrix

Glass samples containing elongated, uniformly oriented gold spheroids were produced by uniaxial tensile deformation of gold ruby glass. In this procedure the originally spherical Au particles were elongated to spheroids. The radius of the originally spherical gold particles in the glass was about R=45 nm. The extinction spectra of the stretched, dichroitic samples were measured using linearly polarized light. Additionally, the extinction and scattering spectra of these glasses were calculated by methods based on the Helmholtz vector wave equation. Hence, the methods of Asano and Yamamoto (AYM) and of Barber and Yeh (EBCM) were used. With the calculated data the shape and the size of the Au spheroids in the glass can be determined only from the measured extinction data.

Formation of oriented particles in an amorphous host: ZnS nanocrystals in silicon

Processes for incorporating randomly oriented crystalline precipitates in an amorphous host can be traced back to the 17th century when Cassius produced “gold ruby” glass. In this glass, octahedral colloidal precipitates of gold scatter light by the Mie process to produce a deep red color. In contrast to gold ruby glass, we describe a type of material in which the crystalline precipitates are crystallographically aligned in a coherent manner—even though they are dispersed in an amorphous matrix. Ion implantation and thermal processing are first used to form zinc sulfide nanocrystals that are coherently oriented with respect to a crystalline Si host. The Si is then amorphized by ion irradiation leaving the highly radiation-resistant ZnS precipitates in an aligned crystalline state. The process is anticipated to find applications in the creation of surfaces with unique optoelectronic properties.

Optical properties of gold in acetate glasses

Colors of gold ruby glasses are variable, depending in part on the sizes of the gold particles dispersed in the colloidal state throughout the silicate glass. Gold has been incorporated into analogous low-melting acetate liquids and glasses. The resulting colors imparted to lead–lithium acetate glasses and sodium–potassium–calcium acetate glasses vary from pink to purple, as the colloidal dispersion is affected by the structure of the acetate system. The structural dependence of the color of gold in these acetate systems is unlike that for the dependence of the color of Co 2+ in the same acetates.

Special Issue on Nonlinear-Optic Waveguide Materials and Devices. Metal Fine Particle Doped Glass and Its Application to Nonlinear Optical Devices.

Nonlinear optical properties of metal fine particle doped glasses and their application to waveguide device are reviewed. Emphasis is made on cubic nonlinear optical properties of gold fine particle doped glasses. Early pioneering studies of commercially available gold ruby glass were followed by the review of investigations of tailor-made gold fine particle glasses. In those studies, degenerate four-wave mixing (DFWM) was employed to study cubic optical nonlinearity of gold fine particle doped glasses. The measurement of cubic nonlinear suscepti-bility and time response of these glasses are discussed. An application of gold fine particle sys-tem to waveguide phase conjugation iss ummarized.

Studies on the development process of gold ruby glasses

The relationship between the size of Au crystallites and the temperature of heat treatment in the development process of gold ruby glasses has been studied by small-angle X-ray scattering and transmission electron microscope. Glasses were heat-treated at temperatures from 550°C to 900°C. But the color can only be developed at temperatures higher than 600°C. The particle size of gold crystallites is about 340 Å at this moment and increases with temperature, the final particle size of Au crystallites being about 550 Å, the size at 900°C is almost identical with that at 700 °C. The particle size distribution of Au crystallites in gold ruby glasses will be more concentrated with the increase of temperature. Once the ruby color emerges, change in color induced by further heat treatment will be extremely small.

Colloidal gold. Part I

Colloidal gold has a long history (1). Gold’s lustre, chemical stability and high price fascinated many ancients. Its preparation to give beautiful ruby red ‘solution’ intrigued the alchemists. Unusual medical properties were ascribed to this ‘potable gold’ and hope was expressed that this may be the ‘elixir of life’. This hope found a modest realization in the ‘Danziger Gold’, an alcoholic concoction containing finely-divided gold. Still available, its exhilarating effects are due not to the gold but to its alcoholic content. Gold ruby glass was manufactured at the end of the 16th century and the ‘Purple of Cassius’, prepared by the reduction of soluble gold salts by tin chloride, has been known since the 17th century.

ChemInform Abstract: NUCLEATION IN PHOTOSENSITIVE GOLD RUBY GLASS

AbstractDie Anzahl der Au‐Partikel in einem Au‐Rubinglas wird als Funktion der Bestrahlungsdauer, der Keimbildungs‐ und Bestrahlungstemp. und der Ce‐Konzentration berechnet.

Nucleation in Photosensitive Gold Ruby Glass

The numbers of gold particles in a gold ruby glass were calculated as a function of irradiation time, nucleation and irradiation temperature, and cerium concentration. Photonucleation in Ce‐containing glasses and nucleation by X rays in glasses without cerium were similar, suggesting that cerium was not directly involved in nucleating the gold particles. The results were consistent with nucleation by trapped photoelectrons. Temperature of irradiation and cerium concentration influenced production and recombination of the trapped electrons. A decreased number of nuclei as the nucleation temperature increased probably resulted from recombination of the trapped electrons.

Self-setting gold ruby glass

Self-setting gold ruby glass

XII. Colours in metal glasses and in metallic films

The present paper contains a discussion of some optical properties of a medium containing minute metal spheres. The discussion is divided into two Parts: the first Part dealing with colours in metal glasses, in which the proportion of volume occupied by metal is small; the second Part dealing with metal films, in which this proportion may have any value from zero to unity. In Part I. the observations of Siedentopf and Zsigmondy beyond the limit of microscopic vision (‘Ann. der Phys.,’ January, 1903) are discussed. It is shown that the particles seen in a gold ruby glass are particles of gold which, when their diameters are less than 0.1μ, are accurately spherical. I have endeavoured to show that the presence of many of these minute spheres to a wave-length of light in the glass will account for all the optical properties of “regular” gold ruby glass, and that the irregularities in colour and in polarisation effects sometimes exhibited by gold glass are due to excessive distance between consecutive gold particles or to excessive size of such particles, the latter, however, involving the former. It is also shown that the radiation from radium is capable of producing in gold glass the ruby colour which is generally produced by re-heating. The method adopted enables us to predict from a knowledge of the metal present in metallic form in a glass what colour that glass will be in its “regular” state.