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Radical species like CO-2,CO-3, SO-2, and SO-3 can be created by exposing natural and synthetic calcium carbonates to sunlight or to the light of a Hg(Xe) lamp. This poses as a risk for ESR dating of these materials, because the radicals formed by light exposure cannot be distinguished from those generated by radioactivity. Furthermore, paramagnetic centers like SO-2, electrons trapped near Zn2+ or Cd2+ ions, surface defects, and radicals with g?=2.0040, can be bleached in ?-irradiated samples by light and show conversion effects.
Radiation defects in alkaline earth silicate glasses are studied by means of ESR and optical spectroscopies. Previously undiscovered relations between findings of both methods are deduced using four different experimental tools: (i) variation of chemical glass composition; (ii) isochronal annealing of ggr-irradiated samples; (iii) optical bleaching of ggr-irradiated samples; (iv) variation of the ggr-dose. Oxygen hole centres are mainly responsible for the radiation induced absorption in the visible part of the optical spectrum. Previously undescribed electron centres with broad and asymmetric ESR resonances (gprime=1·955) contribute to the optical spectra (2002000 nm) in a small way. It is suggested they are electrons trapped on small aggregates of alkaline earth ions. The radiation induced recharging of incorporated Fe3+ ions is also evidenced by optical and ESR spectroscopies. Fe3+ ions react as electron traps forming not only Fe2+ but also {Fe3+}- species which might be responsible for an absorption band at 300 nm. A correlation was found between the changes of intensity with those of the ESR spectroscopically detected Fe3+ content of the samples.
Direct coupling of an excimer laser to the cavity of an X-band ESR spectrometer enabled in situ observation of ultraviolet irradiation (248 nm) induced effects in aluminosilicate glasses. Under these conditions the radiation was absorbed by iron traces present in the glasses and finally electron/hole pairs were formed. The trapping and detrapping of electrons and holes, e.g. generation and decay of paramagnetic defects, could be followed in dependence on repetition rate of the laser (120 Hz), temperature during irradiations (4·2300 K) and composition of the glasses. The holes were trapped at SiO and AlOSi sites. Zn2+ and Cd2+ ions (likely as parts of ZnO or CdO aggregates) as well as Fe3+ ions served as effective electron traps. Additionally, changes of the dielectric properties of the samples during and after ultraviolet irradiations could be monitored directly. These are large if relatively mobile ions (e.g. Na+) are present in the sample. Comparison of ultraviolet to -irradiated samples shows that the type of traps present in the samples mainly depends on the glass composition. However, the relative amounts of stabilised holes and electrons essentially depend on the conditions and parameters of irradiation.
Glasses in the systems Li2OB2O3V2O5 and ZnOB2O3V2O5 as well as crystalline reference substances were investigated by V-K-EXAFS. The glasses have a high modifier content ([Li2O, ZnO]/[B2O3] ratio>1) and contain 1050 mol% V2O5. The VO interatomic distance, coordination number and DebyeWaller factor were determined from the analysis of the measured absorption spectra. In the glasses investigated (and in binary lithium or zinc vanadate glasses too) VO4 tetrahedra are the predominant coordination polyhedra for the vanadium ions. The symmetry of the tetrahedra is more or less distorted in comparison to crystalline substances. The VO4 tetrahedra can be either directly connected to each other or incorporated into borate BO3/BO4 groupings. Structural elements which are comparable to those in crystalline substances can be discussed. In glasses of the metaborate composition, vanadium can be incorporated in chain or ring [BØ2O-]n metaborate groupings. With increasing V2O5 content the vanadium ions can extensively replace boron ions and form distorted tetrahedra in VØ2O2- metavanadate groups. In glasses of high modifier content and low vanadium amount the vanadium ions create nearly regular tetrahedra of isolated VO43- ortho- or V2ØO64- pyrovanadate groups in the presence of B2ØO44- pyroborate, BO33- orthoborate and BØ4- groups.
Electron paramagnetic resonance (EPR) of Fe3+ ions in Al2O3 is studied in powder samples prepared by different routes and/or modified by thermal or mechanical treatments, with different doping levels and grain sizes. The measurements are performed in various frequency bands (S, X, K, Q and W) and with bimodal detection in X-band. Simulations of the spectra are achieved with a code designed for computing EPR powder spectra described by any spin Hamiltonian including second-, fourth-and sixth-order ZFS terms (S ? 7/2). The linewidths, intensities and lineshapes are accounted for. The lineshape is Gaussian at low Fe3+ concentration whereas it is Lorentzian for higher concentration. The linewidths are interpreted as the superimposition of three main contributions: intrinsic linewidth, dipolar broadening and broadening due to lattice imperfections. The latter is tentatively interpreted in terms of quadrupolar spin Hamiltonian parameter distributions treated using first-order perturbation theory. Whatever the sample, only the b22 spin Hamiltonian parameter is found to be distributed around a mean zero value which corresponds to rhombic distortions. Angle and bond length distributions are tentatively extracted from the b22 distributions which gives some insight into the local order around the spin probe in relation to the preparation and treatment of the samples.
We have carried out some laboratory experiments to establish possibilities to melt 16Na2O*10CaO*74SiO2 glasses from consisting of mainly quarz sands of Buir nuur lake. When the sands used directly, the formed glasses had slight blue colour, the origin of which may be connected with aluminium and iron impurities in the sands. Presence of these impurities is confirmed by chemical analyse and ESR study data. Allso have been studied liquid gas extraction phenomena in the sands and melted glass samples and determined some physical properties of them.