Structure,Chirality, and Formation of Giant Icosahedral Fullerenes and Spherical Graphitic Onions

We describe the topology, structure, and stability of giant fullerenes exhibiting various symmetries (I, I _h , D _2h , T). Our results demonstrate that it is possible to create two new families of nested chiral icosahedral (I) fullerenes namely C₂₆₀@C₅₆₀@C₉₈₀@C₁₅₂₀@, ...,and C₁₄₀@C₃₈₀@C₇₄₀@C₁₂₂₀@ ..., which exhibit interlayer separations of ca. 3.4 Å. These chiral fullerenes are thought to possess metalliclike conduction properties. We discuss in detail the transformation of polyhedral graphitic particles into quasispherical nested giant fullerenes by reorganization of carbon atoms, which result in the formation of additional pentagonal and heptagonal carbon rings. These spherical structures are metastable and we believe they could be formed under extreme conditions, such as those produced by high-energy electron irradiation. There is circumstantial experimental evidence for the presence of heptagonal rings within these spherical fullerenes.     

Molecular junctions by joining single-walled carbon nanotubes

Crossing single-walled carbon nanotubes can be joined by electron beam welding to form molecular junctions. Stable junctions of various geometries are created in situ in a transmission electron microscope. Electron beam exposure at high temperatures induces structural defects which promote the joining of tubes via cross-linking of dangling bonds. The observations are supported by molecular dynamics simulations which show that the creation of vacancies and interstitials induces the formation of junctions involving seven- or eight-membered carbon rings at the surface between the tubes.     

Creation of helical vortices during magnetization of aligned carbon nanotubes filled with Fe: theory and experiment

We report a novel magnetic phenomenon consisting of the formation of helical spin configurations during the magnetization of densely packed ferromagnetic nanowires encapsulated inside carbon nanotubes. We studied the hysteresis loops when the magnetic fields are applied parallel and perpendicular to the nanotubes axes. We also performed theoretical calculations on aligned nanowire arrays that clearly indicate the creation of helical spin vortices in the hysteresis loops. The latter are caused by the presence of strong dipolar interactions among neighboring wires.     

Structure,transport and field-emission properties of compound nanotubes: CN<Subscript>x</Subscript> vs. BNC<Subscript>x</Subscript> (<Emphasis Type="Italic">x</Emphasis><0.1)

Transport and field-emission properties of as-synthesized CN_x and BNC_x (x<0.1) multi-walled nanotubes were compared in detail. Individual ropes made of these nanotubes and macrofilms of those were tested. Before measurements, the nanotubes were thoroughly characterized using high-resolution and energy-filtered electron microscopy, electron diffraction and electron-energy-loss spectroscopy. Individual ropes composed of dozens of CN_x nanotubes displayed well-defined metallic behavior and low resistivities of ∼10–100 kΩ or less at room temperature, whereas those made of BNC_x nanotubes exhibited semiconducting properties and high resistivities of ∼50–300 MΩ. Both types of ropes revealed good field-emission properties with emitting currents per rope reaching ∼4 μA(CN_x) and ∼2 μA (BNC_x), albeit the latter ropes se- verely deteriorated during the field emission. Macrofilms made of randomly oriented CN_x or BNC_x nanotubes displayed low and similar turn-on fields of ∼2–3 V/μm. 3 mA/cm² (BNC_x) and 5.5 mA/cm² (CN_x) current densities were reached at 5.5 V/μm macroscopic fields. At a current density of 0.2–0.4 mA/cm² both types of compound nanotubes exhibited equally good emission stability over tens of minutes; by contrast, on increasing the current density to 0.2–0.4 A/cm², only CN_x films continued to emit steadily, while the field emission from BNC_x nanotube films was prone to fast degradation within several tens of seconds, likely due to arcing and/or resistive heating. Received: 29 October 2002 / Accepted: 1 November 2002 / Published online: 10 March 2003 RID="*" ID="*"Corresponding author. Fax: +81-298/51-6280, E-mail: golberg.dmitri@nims.go.jp     

Vibration sample magnetometry, a good tool for the study of nanomagnetic inclusions

The accurate determination of the ferromagnetic contribution in a composite in which the ratio of the ferromagnetic part vs. the total of composite is 10⁻⁴–10⁻⁵ is a problem of great importance in relation to the development of new materials in our days. In this work, the potential of Vibration Sample Magnetometry (VSM) in the identification and quantification of nanomagnetic inclusions is illustrated and discussed in three different cases: PbFe₁₂O₁₉/ Al₂O₃ thin films, nanopowders of magnetite in a polymeric matrix, and carbon nanotubes with iron inside in a silica matrix (Fe/ CN_x/ SiO₂). In all cases, the determination of the existence of preferential orientation, the correct quantification of the magnetic part, and the dependence of the coercive field with on synthesis conditions were revealed using this technique.     

N-doping and coalescence of carbon nanotubes: synthesis and electronic properties

Self-assembly pyrolytic routes to large arrays (<2.5 cm²) of aligned CN_x nanotubes (15–80 nm OD and <100 μm in length) are presented. The method involves the thermolysis of ferrocene/melamine mixtures (5:95) at 900–1000 °C in the presence of Ar. Electron energy loss spectroscopy (EELS) reveals that the N content varies from 2–10%, and can be bonded to C in two different fashions (double-bonded and triple-bonded nitrogen). The electronic densities of states (DOS) of these CN_x nanotubes, using scanning tunneling spectroscopy (STS), are presented. The doped nanotubes exhibit strong features in the conduction band close to the Fermi level (0.18 eV). Using tight-binding and ab initio calculations, we confirm that pyridine-like (double-bonded) N is responsible for introducing donor states close to the Fermi Level. These electron-rich structures are the first example of n-type nanotubes. Finally, it will be shown that moderate electron irradiation at 700–800 °C is capable of coalescing single-walled nanotubes (SWNTs). The process has also been studied using tight-binding molecular dynamics (TBMD). Vacancies induce the coalescence via a zipper-like mechanism, which has also been observed experimentally. These vacancies trigger the organization of atoms on the tube lattices within adjacent tubes. These results pave the way to the fabrication of nanotube heterojunctions, robust composites, contacts, nanocircuits and strong 3D composites using N-doped tubes as well as SWNTs. Received: 10 October 2001 / Accepted: 3 December 2001 / Published online: 4 March 2002     

Curved graphite and its mathematical transformations

Mathematical transformations for graphite with positive, negative and zero Gaussian curvatures are presented. When the Gaussian curvatureK is zero, we analyse a bending transformation from a planar sheet into a cone. The Bonnet, the Goursat and a mixed transformation are studied for graphitic structures with the same topologies as triply periodic minimal surfaces (K < 0). We have found that using the Kenmotsu equations for surfaces of constant mean curvature it is possible to invert spherical and cylindrical graphite. A bending transformation for surfaces of revolution is also studied; during this transformation the helical arrangement of cylinders changes. All these transformations can give an insight into kinematic processes of curved graphite and into new shapes.     

The characterisation of coordination polyhedra by invariants

We have extended the use of the invariants of spherical harmonics for the characterisation of the angular distribution of coordinating atoms about a central atom. These invariants are suitable indices for use in clustering algorithms for automatic crystal chemistry. Invariants for coordination polyhedra in intermetallic compounds and Ca-O silicates are considered. A study of invariants in coordination polyhedra distorted by the Jahn-Teller effect is presented. In addition, Invariants from small clusters and the cuboctahedron-icosahedron transition are analyzed.     

Nanotube brushes: polystyrene grafted covalently on CNx nanotubes by nitroxide-mediated radical polymerization

Polymer brushes consisting of polystyrene (PS) chains bonded covalently to N-doped multiwalled carbon nanotubes (CNx) were synthesized by a "grafting from" route using nitroxide mediated radical polymerization (NMRP).