Local structural distortions in SnTe investigated by EXAFS.

Extended x-ray absorption fine structure (EXAFS) has been measured at theKedge of Sn in SnTe in the temperature range from 5 to 480 K. EXAFS results are consistent with the presence of a local rhombohedral distortion in the full temperature range from 5 to 300 K, even well above the ferroelectric transition temperature, suggesting a partial order-disorder character of the transition. At and above 300 K, the anomalous behaviour of the third and fourth EXAFS cumulants reveals a modification of the anharmonicity of the effective pair potential, possibly connected with the softening of high frequency modes or to the presence of multiple phases.

Nearest-neighbour distribution of distances in crystals from extended X-ray absorption fine structure.

Extended X-ray absorption fine structure (EXAFS) is a powerful probe of the distribution of nearest-neighbour distances around selected atomic species. We consider here the effect of vibrational disorder in crystals. The potential of EXAFS for the accurate evaluation of the coefficient of bond thermal expansion and its temperature dependence is discussed, with the aim of stimulating and facilitating the comparison with the results from total scattering experiments. The meaning of the distribution asymmetry in crystals and its connection with the effective potential anharmonicity and the bond expansion is quantitatively explored by comparing the results for a number of different systems. The extent of the relative atomic vibrations perpendicular to the bond direction and the perpendicular to parallel anisotropy are correlated with the extent of lattice negative thermal expansion as well as with the ionic mobility in superionic crystals.

Strain heterogeneity and magnetoelastic behaviour of nanocrystalline half-doped La, Ca manganite, La0.5Ca0.5MnO3.

Elastic and anelastic properties of La0.5Ca0.5MnO3 determined by resonant ultrasound spectroscopy in the frequency range ∼100-1200 kHz have been used to evaluate the role of grain size in determining the competition between ferromagnetism and Jahn-Teller/charge order of manganites which show colossal magneto resistance. At crystallite sizes of ∼75 and ∼135 nm the dominant feature is softening of the shear modulus as the charge order transition point, Tco (∼225 K), is approached from above and below, matching the form of softening seen previously in samples with 'bulk' properties. This is consistent with a bilinear dominant strain/order parameter coupling, which occurs between the tetragonal shear strain and the Jahn-Teller (Γ3(+)) order parameter. At crystallite sizes of ∼34 and ∼42 nm the charge ordered phase is suppressed but there is still softening of the shear modulus, with a minimum near Tco. This indicates that some degree of pseudoproper ferroelastic behaviour is retained. The primary cause of the suppresion of the charge ordered structure in nanocrystalline samples is therefore considered to be due to suppression of macroscopic strain, even though MnO6 octahedra must develop some Jahn-Teller distortions on a local length scale. This mechanism for stabilizing ferromagnetism differs from imposition of either an external magnetic field or a homogeneous external strain field (from a substrate), and is likely to lead both to local strain heterogeneity within the nanocrystallites and to different tilting of octahedra within the orthorhombic structure. An additional first order transition occurs near 40 K in all samples and appears to involve some very small strain contrast between two ferromagnetic structures.

Reliability and accuracy of environmental analytical data on moss samples: an interlaboratory comparison.

An inter-comparison exercise was performed between two laboratories on mineralised moss samples. Ten samples, together with three certified reference materials (CRM 61, CRM 62 and CRM 482) and five blanks were mineralised independently in the two laboratories and then analysed by both with different techniques (AAS, ICP-MS, and INAA). The elements analysed were: Cd, Cr, Cu, Fe, Ni, and Pb. Accuracy tests showed that, for AAS, the relative standard deviations for five repetitions of the same sample were between 0.2% for Cd and 2.9 % for Cr and that the concentration values found reference materials were withn one standard deviation from the certified values, with the exception of Cr and Cd for CRM 482. The statistical analysis was performed first with a simple linear regression and a Student t-test taking into account the possible influence of the mineralisation procedure and of the analytical technique, in order to evaluate their reliability. The results showed that more than 78% of the regressions had a correlation coefficient higher than 0.750, and that 83% of the slopes were not different from one with a level of significance of 0.01. Afterwards, the precision of the measurements were evaluated using maximum likelihood; the normalised errors showed that ICP-MS had a better performance on most of the elements analysed (with the exception of Fe) and that both the mineralisation procedures gave satisfactory results. The two laboratories were then found to produce reliable results.