27Al NMR study of the structure of lanthanum- and yttrium-based aluminosilicate glasses and melts.

We have investigated by (27)Al nuclear magnetic resonance spectroscopy some compositions in the Ln(2)O(3)-Al(2)O(3)-SiO2 (Ln = Y or La) ternary phase diagram containing more than 60 mol % of SiO2. One- and two-dimensional high-field (17.6 T) high-speed (30 kHz) magic angle spinning experiments have been performed along with simulations of the spectra to quantify the amount of penta-coordinated aluminum present in those glasses as a function of composition. Very high-temperature experiments have allowed to follow selected samples from 2200 degrees C down to 1700 degrees C and hence to characterize the aluminum coordination state and dynamics in those liquids. The present study re-enforces the current view that "minor" species such as penta-coordinated aluminum are actually present in a considerable amount in aluminosilicate glasses, and high-temperature liquids at and above the charge compensation join. The high-field strength of Y3+ and La3+ reveal, for the first time in glasses, a different mean electric field gradient perceived by the tetra- and penta-coordinated aluminum environments. The movements responsible for the NMR relaxation of aluminum in the high-temperature liquid are shown to be uncorrelated with the movements responsible for the macroscopic shear viscosity. Results obtained both on glasses and in situ at high-temperature suggest a preferential localization of Ln3+ nearby tetra-coordinated aluminum species, with possible formation of tricluster and/or Ln3+ coordination changes.

Liquid alumina: detailed atomic coordination determined from neutron diffraction data using empirical potential structure refinement.

The neutron scattering structure factor S(N)(Q) for a 40 mg drop of molten alumina (Al2O3) held at 2500 K, using a laser-heated aerodynamic levitation furnace, is measured for the first time. A 1700 atom model of liquid alumina is generated from these data using the technique of empirical potential structural refinement. About 62% of the aluminum sites are 4-fold coordinated, matching the mostly triply coordinated oxygen sites, but some 24% of the aluminum sites are 5-fold coordinated. The octahedral aluminum sites found in crystalline alpha-Al2O3 occur only at the 2% level in liquid alumina.

14N NMR in AlN and BN.

A characterisation by 14N NMR of the binary nitrides AlN and BN is presented. Both the static and magic angle spinning (MAS) lineshapes have been investigated in order to determine, or set upper limits on, the nuclear quadrupole coupling (Cq) at the nitrogen site. Additional data are given for the Cq values at the Al and B sites. A comparison is made with other similar (mainly wurtzite) binary compounds for which Cq is known at each atomic site.

Two-dimensional magic-angle spinning isotropic reconstruction sequences for quadrupolar nuclei.

Two-dimensional magic-angle spinning (triple quantum, single quantum) correlation pulse sequences and phase cycles based on the technique of Frydman and Harwood for the reconstruction of the isotropic spectrum of half-integer spin quadrupolar nuclei broadened to second-order are described. These sequences provide pure absorption mode two-dimensional lineshapes and increased sensitivity. Experimental examples on spin I = 3/2 (87Rb in RbNO3) and I = 5/2 (27Al in NaSi3AlO8) are presented. The isotropic chemical shift and quadrupolar coupling parameters could be obtained from a simple analysis of the triple quantum filtered single quantum magic-angle spinning cross-sections.

A time resolved 27Al NMR study of the cooling process of liquid alumina from 2450 degrees C to crystallisation.

Nuclear magnetic resonance is able to give insight into the structure and dynamics of liquids at very high temperature (T > 2000 degrees C). 27Al NMR spectra have been recorded every 25 ms during the cooling of an aerodynamically levitated liquid alumina droplet from 2450 degrees C to crystallisation in less than 3 s. The temperature is measured jointly by pyrometry and NMR, and this time resolved experiment provides a unique way of exploring the temperature dependence of both the structure (shift) and the dynamics (relaxation time of 27Al of the liquid and the supercooled liquid alumina until the crystallisation of alpha-Al2O3. The apparent Arrhenian activation energy of 130 kJ mol-1, derived from T1 measurement, is understood as the signature of the macroscopic viscosity in this high temperature liquid.

Double rotation and magic-angle spinning nuclear magnetic resonance study of 27Al: reexamination of the aluminium borate 9Al2O3.2B2O3.

27Al nuclear magnetic resonance spectra of polycrystalline aluminium borate 9Al2O3.2B2O3 have been measured in double rotation at 11.7 and 7.0 T and high-speed magic-angle spinning at 7.0, 9.4, 11.7, 14.1 and 17.6 T. Spinning sidebands from the satellite transitions were observed at 7.0 and 14.1 T. Each of the four structural aluminium sites [Al(IV), Al(V)(1), Al(V)(2) and Al(VI)] are observed, characterised and assigned in the spectra. The obtained parameter set gives a fully consistent interpretation in agreement with the crystal structure of the compound.

71Ga and 69Ga nuclear magnetic resonance study of beta-Ga2O3: resolution of four- and six-fold coordinated Ga sites in static conditions.

71Ga and 69Ga nuclear magnetic resonance (NMR) spectra have been obtained for beta-Ga2O3 at magnetic fields of 11.7 and 7.0 T with a combination of static and spinning samples and using echo techniques. Isotropic chemical shifts and well constrained electric field gradient (EFG) tensors were measured for the GaIV and GaVI sites in beta-Ga2O3 and are reported for the first time. Due to its high quadrupolar coupling constant the GaIV site in beta-Ga2O3 is only resolved in static conditions. Analysis of spectral discontinuities obtained for different isotopes and magnetic field strengths and a method of readily obtaining very broad spectra without point by point acquisition demonstrate an approach that should be very useful in constraining the chemical shifts and quadrupole parameters involved in solid-state gallium NMR spectra.

Magnesium and Calcium Aluminate Liquids: In Situ High-Temperature 27Al NMR Spectroscopy.

The use of high-temperature nuclear magnetic resonance (NMR) spectroscopy provides a means of investigating the structure of refractory aluminate liquids at temperatures up to 2500 K. Time-averaged structural information indicates that the average aluminum coordination for magnesium aluminate (MgAl(2)O(4)) liquid is slightly greater than for calcium aluminate (CaAl(2)O(4)) liquid and that in both liquids it is close to four. Ion dynamics simulations for these liquids suggest the presence of four-, five-, and six-coordinated aluminate species, in agreement with NMR experiments on fast-quenched glasses. These species undergo rapid chemical exchange in the high-temperature liquids, which is evidenced by a single Lorentzian NMR line.