Open Access

Low melting Li2O-PbO-B2O3, Me2O-ZnO-B2O3, Me = Li, Na, K, Rb and CaO-ZnO-B2O3 glasses were studied with Raman and infrared spectroscopies to advance the structural understanding of zinc borate glasses as potential candidates for substitution of lead containing glasses. Although the effect of type of alkali ions on the number (N4) of fourfold coordinated boron (B4) in the glasses is small, the alkali ions direct the type of borate groups, i.e., pentaborate in lithium, sodium, and calcium zinc borate glasses, as well as diborate in potassium and rubidium containing ones. Both groups were simultaneously found in Li2O-PbO-B2O3. Alkali ions are mainly responsible for the formation of B4-units and metaborate. Zinc ions favorably compensate non-bridging oxygen and partially form ZnO4. With decreasing N4 and field strength of the alkali ions the atomic packing density, glass transition temper ature and Young’s Modulus also decrease. The coefficient of thermal expansion increases with decreasing N4.

Zn-K transmission EXAFS measurements were performed on vitrified ashes from municipal waste incinerator facilities, which contain low amounts of Zn (up to 3 wt%) and sulphur (up to 0.5 wt%) in a ZnS phase. From the Fourier transform it can be concluded that the zinc ions are fourfold co-ordinated by oxygen or sulphur ions. The amount of zinc ions of sulphur environment, e.g. the concentration of ZnS, was determined by Fourier filtering and subsequent parameter fitting. A quantitative analysis of low ZnS concentrations up to 1 wt% has been performed for samples with a molar ratio Zn/S < 5.

The fate of doped iron species during various mechanically and thermally initiated redox reactions and aggregation processes in crystalline and amorphous AlO(OH) or Al2O3 matrices was investigated. The amorphization of the matrix was performed by chemical (i.e., via sol-gel processes) or mechanochemical treatment (high-energy ball milling). Thermal analysis, coupled with mass spectrometry (TA-MS), Mössbauer spectroscopy, and electron spin resonance (ESR), was used. The TA under various gas atmospheres allowed preparing samples under a controlled temperature regime, together with a controlled gas influence. Both the effect of mechanical activation and the influence of the iron doping could be followed macroscopically via the down-shift of the peak temperature of the corundum formation. The ESR data characterize the Fe3+ ions and their interaction with the magnetic surrounding based on the fine structure parameters. The Mössbauer data allowed the characterization of the Fe(0), Fe2+, and Fe3+ species, together with providing information about their coordinative surrounding. Both methods provided general complementary spectroscopical information. Unexpectedly, (FeOx)n and (FexAl1-x)2O3 aggregates could also be detected in the range of low Fe concentrations. It was demonstrated that even in the low-level doped systems [(FexAl1-x)2O3 with x ≥ 0.01], all the essential spectroscopic phenomena occur. At higher Fe concentrations, they were discovered to be caused by magnetic and spin exchange interactions as well as by solid-state reactions during and after the mechanical activation.

Alumina coatings are a promising candidate for the protection of metals prone to high temperature corrosion. If applied via sol–gel process, especially by using so called aqueous modified Yoldas-sols, the deposition is hardened by differences in surface free energy of substrate and sol. In this paper the apparent surface properties of samples to be coated and sols were examined by contact angle measurements, IR-spectroscopy and tensiometry. The results imply, after consideration of possible uncertainties, the use of surface tension reducing 2-butanol already present during hydrolysis of the sols to obtain an easy and successful coating process.