The different degrees of freedom of a given system are usually independent of each other but can in some materials be strongly coupled, giving rise to phase equilibria sensitively susceptible to external perturbations. Such systems often exhibit unusual physical properties that are difficult to treat theoretically, as exemplified by strongly correlated electron systems such as intermediate-valence rare-earth heavy fermions and Kondo insulators, colossal magnetoresistive manganites and high-transition temperature (high-T(c)) copper oxide superconductors. Metal fulleride salts-metal intercalation compounds of C60--and materials based on rare-earth metals also exhibit strong electronic correlations. Rare-earth fullerides thus constitute a particularly intriguing system--they contain highly correlated cation (rare-earth) and anion (C60) sublattices. Here we show, using high-resolution synchrotron X-ray diffraction and magnetic susceptibility measurements, that cooling the rare-earth fulleride Sm2.75C60 induces an isosymmetric phase transition near 32 K, accompanied by a dramatic isotropic volume increase and a samarium valence transition from (2 + epsilon) + to nearly 2 +. The negative thermal expansion--heating from 4.2 to 32 K leads to contraction rather than expansion--occurs at a rate about 40 times larger than in ternary metal oxides typically exhibiting such behaviour. We attribute the large negative thermal expansion, unprecedented in fullerene or other molecular systems, to a quasi-continuous valence transition from Sm(2+) towards the smaller Sm((2+epsilon)+), analogous to the valence or configuration transitions encountered in intermediate-valence Kondo insulators like SmS (ref. 3).
Carbon multi-walled nanotubes (C-MWNTs) and alternatively carbon doublewalled nanotubes (C-DWNTs) were added in water, following our previous work, in order to enhance the thermal conductivity of this traditional heat transfer fluid. Hexadecyltrimethyl ammonium bromide (CTAB) and Nanosperse AQ were employed as dispersants. The transient hot-wire technique was used for the measurement of the thermal conductivity with an instrument built for this purpose. The absolute uncertainty is better than 2%. The maximum thermal conductivity enhancement obtained was 34% for a 0.6% volume C-MWNT suspension in water with CTAB. All measurements were made at ambient temperature. In an attempt to evaluate and explain the experimental results, information about the microstructure of the suspensions is needed. The findings of these investigations are presented here along with the analysis.
The pressure response of double-wall carbon nanotubes has been investigated by means of Raman spectroscopy up to 10 GPa. The intensity of the radial breathing modes of the outer tubes decreases rapidly but remain observable up to 9 GPa, exhibiting a behavior similar (but less pronounced) to that of single-wall carbon nanotubes, which undergo a shape distortion at higher pressures. In addition, the tangential band of the external tubes broadens and decreases in amplitude. The corresponding Raman features of the internal tubes appear to be considerably less sensitive to pressure. All findings lead to the conclusion that the outer tubes act as a protection shield for the inner tubes whereas the latter increase the structural stability of the outer tubes upon pressure application.
Optical detection of an individual single nano-object on an opaque substrate and direct determination of its absorption cross section is demonstrated using reflective spatial modulation spectroscopy. This method is applied to optical imaging and investigation of individual single-wall carbon nanotubes in the 1.6 nm diameter range on silicon substrates, which are also individually characterized by atomic force microscopy, scanning electron microscopy, and in situ micro-Raman spectroscopy. Absorption cross sections on the order of 10 −17 cm 2 per carbon atom are measured for the investigated semiconducting carbon nanotubes, with a light polarization absorption anisotropy of about 2.
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