On the influence of wavelength-dependent light scattering on the UV-VIS absorption spectra of oxygen-based minerals: a study on silicate glass ceramics as model substances

• Published in: Physics and chemistry of minerals Vol. 30; no. 2; pp. 98 - 107
• Main Authors: Khomenko, V. M., Langer, K., Wirth, R.
• Format: Journal Article
• Language: English
• Published: Heidelberg Springer Nature B.V 01.03.2003
• Subjects: Absorption; Absorption spectra; Ceramics; Charge transfer; Color; Composition; Crystals; Depletion; Garnets; Glass ceramics; Heat treatment; Inclusions; Light scattering; Microcrystals; Mie scattering; Minerals; Nucleation; Ordination; Parameters; Phase separation; Refractivity; Size distribution; Spectrometry; Titanium; Transition metals; Transmission electron microscopy; Zirconium oxides
• ISSN: 0342-1791; 1432-2021
• DOI: 10.1007/s00269-002-0292-0

The Mie scattering theory shows that the presence of randomly distributed submicroscopic inclusions with narrow size distribution and a refractive index ni in a matrix with different refractive index nm may give rise to a λ-dependent, band-like scattering (e.g., Kortüm 1969). Intensity and spectral position of this scattering depend on a combination of several independent parameters, such as size and number of inclusions, their form and ni/nm ratio (Kortüm 1969). Recently, it was confirmed that at a certain inclusion size and ni/nm ratio the scattering bands can contribute to the UV-edge in the electronic absorption spectra of garnets, influencing their colour (Khomenko et al. 2001). In natural minerals, however, it is impossible to differentiate between individual influence on scattering of the above mentioned parameters because of complex and interconnected variations in number, size and type of inclusions. Additionally, in most natural minerals variable amounts of transition metal ions are present. They may cause UV-VIS absorption due to ligand to metal charge transfer (LMCT) in the same region where band-like scattering may occur (Khomenko et al. 2001). At least some of these difficulties may be avoided in the case of some glass ceramics where number and size of crystalline microinclusions can be controlled by varying ceramization conditions such that fine-grained homogeneous microstructures are formed (e.g., James 1982; Petzoldt and Pannhorst 1991). Thus, glass ceramics of known composition, containing different amounts of microcrystals of specified size, may serve as unique patterns for the experimental study of effects caused by submicrocrystals on bulk properties of transparent solid materials, such as scattering, UV-VIS transparency and colour. Four types of parent glasses and a series of glass ceramic materials produced from them by heat treatment were investigated using transmission electron microscopy (TEM). These materials were also studied by transmission spectrometry in the range 35 000–20 000 cm−1. Different inclusions, from five to several hundred nm in size, were observed in the glass matrices depending on their compositions and heating history. These inclusions represent two groups: early very small crystals of Ti, Zr oxides and relatively large crystals of stuffed high-quartz type or keatite. The absorption spectra of the glass ceramics show largely varying long-wavelength slopes of the UV absorption. UV-edge intensity correlates mostly with the size of the inclusions and changes drastically when larger keatite-type microcrystals are growing. Small variations in the UV edges also follow the early process of Ti-phase separation and nucleation. This may be explained by Ti depletion from the glass matrix and, thus, by reducing the measured intensity of LMCT in the first co-ordination sphere of Ti4+ ions. The different yellowish colourations of unheated glasses studied here are caused by this effect, whereas developing several hundred-nm-large keatite crystals leads to a strong scattering effect and a milky colour in glass ceramics.