Cluster structure of fullerene-containing soot and C60 fullerene powder

Electron microscopy and electron diffraction methods were employed in a study of the structure of a fullerene-containing soot produced in gas discharge and of a C₆₀ fullerene powder. The data obtained were analyzed with the use of fractal geometry concepts. It has been shown that, in the structure of the objects studied, several spatial scales can be identified. The effective radius of the structure’s “elementary particles” calculated using scaling relationships is equal to 6 Å for the soot and 4.5 Å for the C₆₀ fullerene. The “elementary particles” combine into associates. The number of particles in an associate in both the soot and the C₆₀ powder is not large (about 10). The associates form fractal nanoclusters 30–80 nm in size having a fractal dimension of 1.60±0.05 in the soot and of 1.8±0.05 in the C₆₀ fullerene. The structure of the soot nanocluster is unstable and can be significantly modified by externally applied factors (e.g., as a result of treatment with toluene). The nanoclusters combine into aggregates having the form of branching cross-linked filaments. Eventually, these aggregates combine to form macroparticles of soot.     

Size effects in the exciton energy and first-order phase transitions in CuCl nanocrystals in glass

The absorption spectra and the melting and crystallization kinetics of CuCl nanocrystals in glass are investigated in the range of particle radii 1–30 nm. Three discontinuities are found on the curves representing the size dependence of the melting point T _m(R) and the crystallization point T _c(R). As the particle radius gradually decreases from 30 nm in the range R⩽12.4 nm there is a sudden 60° drop in the temperature T _c in connection with the radius of the critical CuCl nucleus in the melt. A 30° drop in T _m is observed at R=2.1 nm, and a second drop of 16° in the temperature T _c is observed for CuCl particles of radius 1.8 nm. The last two drops are associated with changes in the equilibrium shape of the nanoparticles. In the range of smaller particles, R⩽1.34 nm the T _c(R) curve is observed to merge with the T _m(R) curve, owing to the disappearance of the work of formation of the crystal surface during crystallization of the melt as a result of the zero surface tension of CuCl particles of radii commensurate with the thickness of the effective surface layer. An increase in the size shift of the exciton energy is observed in this same range of CuCl particle radii (1–1.8 nm). The size dependence of the melting and crystallization temperatures of the nanoparticles is attributed to variation of the free energy in the surface layer of a particle. Fiz. Tverd. Tela (St. Petersburg) 41, 310–318 (February 1999)     

On distribution over the cathode surface of the current due to positive ions in discharge with oscillating electrons

The mechanisms of processes determining distribution of positive ions on the cathode surface in a discharge with oscillating electrons are studied. At low pressures P≤5×10⁻⁵ torr over the entire range of anode length variation l _a=0.5–11 cm, the ion current distribution over the cathode radius J _i(r) features a single maximum in the center and drops steeply with distance from the axis. At pressures P=1–4×10⁻⁴ torr, the distribution J _i(r) for short anodes (l _a<6 cm) is similar to the previous one but, for long anodes (l _a=6–10 cm), new maxima at higher J _i values have been detected. A physical explanation for the obtained results is proposed.     

Formation of two distributions of nanoparticles of a new phase in a solid solution

Processes of the formation of the double distribution of CuCl nanoparticles in glass in two-stage annealing have been analyzed. The distribution of CuCl nanoparticles with the average radius R ₁ = 14 and 18 nm appears in 20 and 40 min at temperature T ₁ = 700°C in samples 1 and 2, respectively. By this time, the formation of new clusters ends, and only the growth of previously formed clusters occurs (the second stage of nucleation). Then, the formation of the CuCl phase continues at T ₂ = 500°C. A decrease in the temperature is accompanied by a decrease in the critical radius of particles of a new phase. For this reason, the formation and growth of new CuCl nuclei begin again and the second distribution with a mean radius of 1 nm or larger is formed. As a result, double distributions of CuCl nanoparticles with significantly different mean radii are formed in samples 1 and 2. The concentration and mean radius of CuCl particles in distributions have been determined from the optical absorption spectra of CuCl nanocrystals at 80 K in the wavelength range of 300–500 nm.     

C<Subscript>60</Subscript> fullerene as an η<Superscript>6</Superscript> ligand in π complexes of transition metals

The possible existence of complexes formed by the C₆₀ fullerene or its derivatives with transition metals interacting with the carbon cage via η⁶−π type bonding is discussed. The derivatives C₆₀ R ₆ of the C₆₀ fullerene (R = −, H, F, Cl, Br, CN) are analyzed using the density functional method within the Perdew-Burke-Ernzerhof approximation. In these molecules, the R groups are attached to carbon atoms located in the α positions with respect to the common hexagon of the C₆₀ fullerene. The structure and electron configuration of complexes formed by these molecules with Cr(C₆H₆), Cr(CO)₃, MoC₆H₆, and Mo(CO)₃ particles are modeled. The “dimer” systems C₆₀R₆-M-R ₆C₆₀ (M = Cr, Mo, R =-, H, F) are investigated in which two fullerene molecules interact via a transition-metal atom. It is found that the introduction of six R groups in the α sites with respect to the common hexagon of C₆₀ favors the formation of complexes of these derivatives of the C₆₀ fullerene with the Cr(C₆H₆), Cr(CO), Mo(C₆H₆), and Mo(CO)₃ particles in which η⁶-π type bonds arise between the metal and the atoms of the hexagon fringed with the R groups. It is also demonstrated that analogous complexes with a “bare” C₆₀ fullerene are possible, but they are significantly less stable. The (C₆H₆) M-R ₆C₆₀ R ₆-M (C₆H₆) complexes of particles M(C₆H₆) (M= Cr, Mo) and derivatives R ₆C₆₀ R ₆ (R =-, H, F, Cl, Br) are studied. In the R ₆C₆₀ R ₆ molecule, six R groups are located in the α sites with respect to the common hexagon of the C₆₀ fullerene and six other groups fringe the opposite hexagon. The obtained results can be applied to planning synthesis of new complexes that C₆₀ fullerene derivatives can form with transition metals. Original Russian Text ￠ E.G. Gal’pern, A.R. Sabirov, I.V. Stankevich, 2007, published in Fizika Tverdogo Tela, 2007, Vol. 49, No. 12, pp. 2220–2223.     

Photoionization of the outer electrons in noble gas endohedral atoms

We suggest a prominent modification of the outer shell photoionization cross section in noble gas (NG) endohedral atoms NG@C _n under the action of the electron shell of fullerene C _n . This shell leads to two important effects: a strong enhancement of the cross section due to fullerene shell polarization under the action of the incoming electromagnetic wave and to prominent oscillation of this cross section due to the reflection of a photoelectron from the NG by the fullerene shell. Both factors lead to powerful maxima in the outer shell ionization cross sections of NG@C _n , which we call giant endohedral resonances. The oscillator strength reaches a very large value in the atomic scale, 25. We consider atoms of all noble gases except He. The polarization of the fullerene shell is expressed in terms of the total photoabsorption cross section of the fullerene. The photoelectron reflection is taken into account in the framework of the so-called bubble potential, which is a spherical δ-type potential. It is assumed in the derivations that the NG is centrally located in the fullerene. It is also assumed, in accordance with the existing experimental data, that the fullerene radius R _C is much larger than the atomic radius r _A and the thickness Δ_C of the fullerene shell. As was demonstrated recently, these assumptions allow us to represent the NG@C _n photoionization cross section as a product of the NG cross section and two well-defined calculated factors. The text was submitted by the authors in English.     

Effect of C60 fullerene, fullerene-containing soot, and other carbon materials on the sliding edge friction of metals

A comparative study of different carbon materials (C₆₀ fullerene; soot, both with and without fullerenes; graphite; and industrial carbon black) as additives to industrial lubricating oils has been carried out for copper-steel and steel-steel sliding couples. The soot containing fullerene and the powder of pure fullerene produce a noticeable improvement in the antifriction and antiwear properties of steel-steel and steel-copper couples, especially under heavy loads and pressures at the contact. The greatest improvement was observed for the steel-steel couple. Structural-mechanical studies were carried out for copper riders and it has been demonstrated by several methods that the addition of the C₆₀ fullerene (pure fullerene or as a fullerene-containingsoot) creates a fullerene-polymer film on the frictional surface about 1000 Å thick, which has a protective effect.     

Structure of aluminum alloys irradiated with reactor neutrons

Samples of the CAB-1 alloy in the initial state and irradiated with fast neutrons at an fluence of 2 × 10²¹ neutrons/cm² have been studied by small-angle neutron scattering. It has been demonstrated that the observed large scattering cross sections are associated with the presence of nanosized pores with radii R ∼ 5–50 nm in the alloy, whereas for possible inclusions of the Mg₂Si and Si phases, the contrast factors and limiting volume fractions lead to the estimated cross sections that are two orders of magnitude smaller than those observed in the experiment. As a result of the irradiation, the volume fraction of scattering objects (pores) 40–50 nm in radius decreases by a factor of more than two. This is compensated, to a large extent, by an increase in the total fraction of particles with radii of 5–8 and 20–25 nm as the total surface area of the scattering objects increases by 40%.     

Electron-induced radiation from C60 fullerene in the gas phase

The formation of radiating particles in the excitation of C₆₀ fullerene molecules by electrons with energies E _e<100 eV is investigated by the method of crossed molecular and electron beams. A quasicontinuous (with a spectral resolution of 3 nm) emission spectrum, close to the Planck emission spectrum of a heated body, is recorded in the wavelength range 300–800 nm. The temperature of the radiation corresponds to an internal energy of the C₆₀ molecule of approximately 40 eV. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 12, 915–919 (25 June 1996)     

Phase behaviour of colloid-polymer mixtures

Summary We review the phase behaviour of mixtures of colloids and non-adsorbing polymers. The exclusion of polymer molecules from overlapping ?depletion zones? between two neighbouring colloidal particles results in an unbalanced osmotic pressure pushing the particles together. This depletion potential is separately tunable in range and depth. Theory predicts that the resulting phase behaviour is sensitive to ξ=r _g/R, the ratio of the radius of gyration of a polymer molecule, to the radius of the colloid. At large ξ, a stable colloidalliquid phase becomes possible. This has been confirmed by recent experiments. The formation of non-equilibrium ?transient gel? states when the size ratio is small (≈0.08) is also introduced briefly. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Negative ions in liquid helium: Existence of new bound states

It is shown that fundamentally new bound states can be formed when a foreign negative ion is embedded in liquid helium. For such states the excess electron forms a bubble with a radius R ₀≃17–18 Å, and a foreign neutral atom is trapped inside this bubble because of the polarization interaction with the electric field of the excess electron, which has a maximum at a point r≃R ₀/2. The main properties of such structures are considered. Pis’ma Zh. éksp. Teor. Fiz. 65, No. 6, 454–458 (25 March 1997) Published in English in the original Russian journal. Edited by James Anderson and Steve Torstveit.     

Pulsed-periodic discharge in cesium as an effective source of light

The spectrum of visible radiation from an inhomogeneous cesium-plasma column is evaluated in the approximation of locally thermodynamically equilibrium plasma. The plasma parameters correspond to a pulsed-periodic low-power discharge at pressures of 0.1–1.0 atm and the axial temperature T=5500 K. Under these conditions, the visible spectrum of the cesium plasma changes from discrete (line) to continuous as the pressure varies from 0.1 to 1.0 atm. This is associated largely with an increase in the intensity of the 6P and 5D recombination continua and an appreciable shift of the thresholds of the continua toward larger wavelengths (by ≈100 nm for 6P and by ≈150 nm for 5D) when the plasma density rises to ≈4×10¹⁷ cm⁻³. In this case, the optical thickness of the plasma column approaches unity and the average luminous flux per unit length of the arc column is close to 6500 lm/cm at the column radius R=2 mm and a duty ratio of 0.1.     

Effect of an edge field on the acceptance of a quadrupole mass filter operating at the bottom vertex of the stability rectangle

A quadrupole mass filter (QMF) can operate with a large acceptance and high transmission at the bottom vertex S (a=2.5210, q=2.8153) of the stability quadrilateral. The combined acceptance at a level of 50% transmission and a resolving power of 100 equals 2.0×10⁻³ r ₀ ⁴ f ², which is comparable to the acceptance (5.1×10⁻³ r ₀ ⁴ f ²) of the standard operating regime of a QMF in the first stability region under the same computational conditions and optimal on-axis ion velocity. The acceptance is approximately three times higher in the presence of edge fields than in their absence. The optimal on-axis ion energy equals 1.15r ₀ f, where r ₀ is the radius of the field (the radius of the inscribed circle between the vertices of the electrodes) and f is the working frequency. In the gas-analysis regime a sensitivity of 10⁻⁵ A/Pa is achieved on a mass filter with rod length and rod diameter of 15 cm and 8 mm, respectively, frequency f=1 MHz, and field radius r ₀=0.35 cm. Zh. Tekh. Fiz. 67, 121–124 (October 1997)     

A new approach to diffusion-limited reaction rate theory

A new approach to the diffusion-limited reaction rate theory is developed on the base of a similar approach to consideration of Brownian coagulation, recently proposed by the author. The traditional diffusion approach to calculation of the reaction rate is critically analyzed. In particular, it is shown that the traditional approach is applicable only to the special case of reactions with a large reaction radius, [`(r)]<sub>A</sub> << R<sub>AB</sub> << [`(r)]_B\bar r_A \ll R_{AB} \ll \bar r_B (where [`(r)]<sub>A</sub>\bar r_A, [`(r)]_B\bar r_B are the mean interparticle distances), and becomes inappropriate to calculation of the reaction rate in the case of a relatively small reaction radius, R_AB << [`(r)]<sub>A</sub>R_{AB} \ll \bar r_A, [`(r)]_B\bar r_B. In the latter, most general case particles collisions occurmainly in the kinetic regime (rather than in the diffusion one) characterized by a homogeneous (at random) spatial distribution of particles. Homogenization of particles distribution occurs owing to particles diffusion mixing on the length scale of the mean interparticle distance with the characteristic diffusion time being small in comparison with the characteristic reaction time. The calculated reaction rate for a small reaction radius in 3D formally (and casually) coincides with the expression derived in the traditional approach for reactions with a large reaction radius, however, notably deviates at large times from the traditional result in the plane (2D) geometry.     

Approximate solution of the Percus-Yevick equation for a binary mixture of hard spheres with non-additive diameters

We present an approximate solution of the Percus-Yevick integral equation for a binary mixture of hard spheres with non-additive diameters. Defining R_ij the distance of closest approach between particles of species i and j by R ₁₂ = ½(R ₁₁ + R ₂₂) + α, we obtain a closed set of equations for the direct correlation functions c_ij (r) when 0 < α ? min [½(R ₂₂ - R ₁₁), ½R ₁₁]. Our expressions for c_ii (r), and for c ₁₂(r) in the range 0 < r ? ½[R ₂₂ - R ₁₁] - α, agree with those previously obtained by Lebowitz and Zomick.     

Spectroscopy of the regenerative soot

The mechanisms and processes of the formation of the regenerative soot in a graphite hollow cathode discharge that produces and emits carbon clusters are presented. Mass spectrometry with a specially designed E×B velocity filter analyzes the entire range of the charged clusters from C ₁ to ∼C ₄₃₀₀. The state of the carbon vapour within the source is evaluated by using the characteristic line emissions from the carbonaceous discharge whose formative mechanisms depend upon the kinetic and potential sputtering of the sooted cathode. The carbonaceous discharge generates atomic and ionic C and its clusters C _m (m≥ 2), noble gas metastable atoms and ions, energetic electrons and photons in the cavity of the graphite hollow cathode. The parameters of soot formation and its recycling depend critically on the discharge parameters, the geometry of the hollow cathode and 3D profile of the cusp magnetic field contours. Received 2nd July 2001 and Received in final form 10 September 2001     

Measurement of soot morphology by integrated LII and elastic light scattering

A compact experimental setup that integrates laser-induced incandescence (LII) and one-angle elastic light scattering (1A-ELS) to measure the size of polydisperse soot aggregates is described. A 532 nm laser and a detection angle of 35 degrees were employed, which provided sensitivity for aggregate radius of gyrations (R _g) of R _g≤200 nm. Both lognormal and self-preserving distribution functions are compared with width parameters derived from both aggregation theory and transmission electron microscopy (TEM) measurements. Using these distributions, mean aggregate sizes derived from the scattering measurements are compared. The LII+1A-ELS technique is validated with a two-angle elastic light scattering (2A-ELS) approach with an additional detection angle at 145 deg. Unlike LII+1A-ELS, the 2A-ELS technique has the advantage of not requiring knowledge of soot optical properties. Good agreement is found between the two techniques for a given distribution. A fundamental discrepancy exists between distributions derived from TEM and those according to aggregation theory, limiting the accuracy of both 2A-ELS and LII+1A-ELS. The dependence of both techniques on laser fluence and hence soot temperature is examined and discussed.     

Subnormal glow discharge in a Xe/Cl2 mixture in a narrow discharge tube

Electrical and optical characteristics of a subnormal glow discharge in a short (L=10 cm) discharge tube with an inner diameter of 5 mm are investigated. The dependences of the discharge current-voltage characteristic, the energy deposition in the discharge, the plasma spectral characteristics in the 130-to 350-nm wavelength range, the emission intensities of the XeCl(D-X) 236-nm and XeCl(B-X) 308-nm bands, and the total emission intensity in the range 180–340 nm on the pressure and composition of the Xe/Cl₂ mixture are studied. Two modes of glow discharge are shown to exist: the low-current mode at a discharge current of I _ch ≤2 mA and the high-current mode at I _ch >2 mA. The transition from one mode to another occurs in a stepwise manner. The increase in the chlorine content causes the discharge voltage and the energy deposition in the plasma to increase. At low pressures of the Xe/Cl₂ mixture (P≤0.7 kPa), stationary strata form in the cathode region. The lower the discharge current, the greater the volume occupied by the strata. This longitudinal discharge acts as a powerful source of continuous broadband emission in the range 180–340 nm, which forms due to overlapping the XeCl(D, B-X) and Cl ₂ ^* bands with edges at λ=236, 308, and 258 nm. The intensity of the 236-nm band is at most 20% of the total intensity of UV radiation. The maximum power of UV radiation (3 W at an efficiency of 8%) is attained at a xenon partial pressure of 250–320 Pa and a total pressure of the mixture of 2 kPa.     

Size dependence of complex refractive index function of growing nanoparticles

The evidence of the change of the complex refractive index function E(m) of carbon and iron nanoparticles as a function of their size was found from two-color time-resolved laser-induced incandescence (TiRe-LII) measurements. Growing carbon particles were observed from acetylene pyrolysis behind a shock wave and iron particles were synthesized by pulse Kr–F excimer laser photo-dissociation of Fe(CO)₅. The magnitudes of refractive index function were found through the fitting of two independently measured values of particle heat up temperature, determined by two-color pyrometry and from the known energy of the laser pulse and the E(m) variation. Small carbon particles of about 1–14 nm in diameter had a low value of E(m)∼0.05–0.07, which tends to increase up to a value of 0.2–0.25 during particle growth up to 20 nm. Similar behavior for iron particles resulted in E(m) rise from ∼0.1 for particles 1–3 nm in diameter up to ∼0.2 for particles >12 nm in diameter.     

Synthesis of nanoparticles in an atmospheric pressure glow discharge

Nanopowders are produced in a low temperature, non-equilibrium plasma jet (APPJ), which produces a glow discharge at atmospheric pressure, for the first time. Amorphous carbon and iron nanoparticles have been synthesized from Acetylene and Ferrocene/H₂, respectively. High generation rates are achieved from the glow discharge at near-ambient temperature (40–80°C), and rise with increasing plasma power and precursor concentration. Fairly narrow particle size distributions are measured with a differential mobility analyzer (DMA) and an aerosol electrometer (AEM), and are centered around 30–35 nm for carbon and 20–25 nm for iron. Particle characteristics analyzed by TEM and EDX reveal amorphous carbon and iron nanoparticles. The Fe particles are highly oxidized on exposure to air. Comparison of the mobility and micrograph diameters reveal that the particles are hardly agglomerated or unagglomerated. This is ascribed to the unipolar charge on particles in the plasma. The generated particle distributions are examined as a function of process parameters.