ABSTRACT
Onion-like carbons (OLC) obtained by thermal transformation of nanodiamonds are agglomerates of multi-shell fullerenes, often covered by an external graphitic mantle. For the present work, elemental OLC units were constructed on the computer by coalescence of several two-layer fullerenes, in a structure similar to carbon peapods with a corrugated external wall. The electrical polarizability of such pod-of-peas fullerenes has been computed by a classical monopole-dipole atomistic theory. The description of pod-of-peas fullerenes was further simplified by representing them as linear arrays of point-like objects, whose polarizability matches that of the starting molecules. Calculations demonstrated that the static polarizability of spherically shaped assemblies of these arrays, modeling real OLC materials, is weakly dependent on the geometry of its constituent molecules and is chiefly proportional to the volume of the whole cluster. It increases with increasing filling fraction of the pod-of-peas fullerenes in the OLC aggregate. The polarizability so obtained can be used in Maxwell-Garnett theory to predict the permittivity of OLC-based composites, at least for static excitations. Experimental results obtained at GHz frequencies reveal a weak attenuation for OLC- and nanodiamond-based polydimethylsiloxane composites. In these silicone composites, we did not find long chains of coupled OLCs. Quite separated clusters were found instead, which contribute little to the polarizability and to the dielectric properties, in good agreement with our theoretical predictions.
ABSTRACT
A semicontinuum approach on the basis of an effective polarizability tensor per length and radius units is used to describe the dielectric response of a long single wall nanotube to the adsorption of an extended molecule. Changes in the permittivity ratio of the nanotube+molecule over the nanotube alone, which are directly connected to frequency shifts of the nanotube in a resonator configuration due to the presence of the molecule, provide a test of sensitivity of the system. The behavior of this ratio is analyzed for linear and circular geometries of the molecule, as a function of the tube characteristics (length and radius) and of the molecular size and polarizability distribution. Extension to three dimensional systems with a large set of polarizable centers is discussed in terms of self-polarization of the centers and morphology of the surface of the sensed system.
Subject(s)
Electrons , Nanotubes/chemistryABSTRACT
Recent measurements of the resonance frequency of a copper disk covered with carbon nanotube bundles have shown characteristic resonance shifts during exposure with various gas molecules. The shifts were interpreted as the change of the dielectric permittivity of the system forming the sensor due to the electric properties of the adsorbed molecules. Starting from a simplified sensor model formed by one single wall nanotube, we develop a self-consistent approach to describe the variation of the linear dielectric susceptibility of the tube at the atomic scale when molecules are adsorbed at its external surface. The sensitivity of this model sensor is tested as a function of the apolar or polar nature of the admolecules, their adsorption geometry, their concentration, and the characteristics of the tube (length, diameter,...). The comparison with data on dielectric constant changes vs adsorption, coming from measurements of the resonance frequency shifts, displays striking agreement for most of the molecular species considered.
