Phase transformations in amorphous fullerite C60 under high pressure and high temperature

First phase transformations of amorphous fullerite C₆₀ at high temperatures (up to 1800 K) and high pressures (up to 8 GPa) have been investigated and compared with the previous studies on the crystalline fullerite. The study was conducted using neutron diffraction and Raman spectroscopy. The amorphous fullerite was obtained by ball-milling. We have shown that under thermobaric treatment no crystallization of amorphous fullerite into С₆₀ molecular modification is observed, and it transforms into amorphous-like or crystalline graphite. A kinetic diagram of phase transformation of amorphous fullerite in temperature–pressure coordinates was constructed for the first time. Unlike in crystalline fullerite, no crystalline polymerized phases were formed under thermobaric treatment on amorphous fullerite. We found that amorphous fullerite turned out to be less resistant to thermobaric treatment, and amorphous-like or crystalline graphite were formed at lower temperatures than in crystalline fullerite.     

Phase Transitions in a Mixture of Amorphous C<Subscript>60</Subscript> and C<Subscript>70</Subscript> Fullerene Phases at High Temperatures and Pressures

Phase transitions in two types of amorphous fullerene phases (C₆₀–C₇₀ (50/50) mixtures and an amorpous C₇₀ fullerene phase) are studied via neutron diffraction at pressures of 2–8 GPa and temperatures of 200–1100°C. Fullerenes are amorphized by grinding in a ball mill and sintered under quasi-hydrostatic pressure in a toroidal-type chamber. Diffraction studies are performed ex situ. It is shown that the amorphous phase of fullerenes retains its structure at temperatures of 200–500°C, and amorphous graphite is formed at 800–1100°C with a subsequent transition to crystalline graphite. This process is slow in a mixture of fullerenes, compared to C₇₀ fullerene. According to neutron diffraction data, the amorphous graphite formed from amorphous fullerene phases has anisotropy that is much weaker in a fullerene mixture.     

Copper-oxygen substructures in carbon allotropes (graphite and fullerites)

A comparative study of crystalline graphite and copper-doped fullerite membranes is reported. It is assumed that C₆₀ clusters form complexes with oxygen and copper similar to those known to exist in graphite. Above room temperature, these complexes, first, change the symmetry of the fullerite lattice and, second, are responsible for the nonmonotonic temperature dependence of the electrical resistance. Fiz. Tverd. Tela (St. Petersburg) 41, 748–750 (April 1999) Deceased.     

Electroconductivity and pressure–temperature states of step shocked C60 fullerite

A study of electrophysical and thermodynamic properties of C₆₀ single crystals under step shock loading has been carried out. The increase and the following reduction in specific electroconductivity of C₆₀ fullerite single crystals at step shock compression up to pressure 30 GPa have been measured. The equations of state for face centred cubic (fcc) C₆₀ fullerite as well as for two-dimensional polymer C₆₀ and for three-dimensional polymer C₆₀ (3D-C₆₀) were constructed. The pressure–temperature states of C₆₀ fullerite were calculated at step shock compression up to pressure 30 GPa and temperature 550 K. The X-ray diffraction studies of shock-recovered samples reveal a mixture of fcc C₆₀ and a X-ray amorphous component of fullerite C₆₀. The start of the formation of the X-ray amorphous component occurs at a pressure P _m≈ 19.8 GPa and a temperature T _m≈ 520 K. At pressures exceeding P _m and temperatures exceeding T _m, the shock compressed fullerite consist of a two-phase mixture of fcc C₆₀ fullerite and an X-ray amorphous component presumably consisting of the nucleators of polymer 3D-C₆₀ fullerite. The decrease in electroconductivity of fullerite can be explained by the percolation effect caused by the change of pressure, size and number of polymeric phase nuclei.     

Effect of deuterium on phase transformations in fullerenes at high temperatures and high pressures

The effect deuterium has on phase transformations is studied for amorphous and crystalline fullerenes C₆₀ and C₇₀ at high temperatures of up to 1300°C and high pressures (2–8 GPa). Amorphous fullerene phases are obtained via long grinding in a planetary mill. Structure is studied by means of neutron diffraction. In all cases, amorphous graphite (nanographite) forms in the temperature range of 800–1100°C. This material has different diffraction spectra distinguished by the heights of the halos observed on the graphite diffraction maxima and their relative intensities. These spectra (the structure of nanographite) are affected by preliminary amorphization, the number of carbon atoms in the fullerenes (C60 or C70), and the introduction of deuterium atoms. The different spectra of amorphous (disordered) graphite testify to its varying structure.     

Selective laser sintering of amorphous metal powder

For the first time, selective sintering of amorphous PtCuNiP powder with a pulsed Nd:YAG laser has been studied. Upon pulsed interaction, the grains melt only superficially to build necks between the grains. Depending on the laser parameters, the sintered material can be crystallized or retained amorphous. By contrast with crystalline powder, laser sintering of amorphous powder is achieved at substantially lower pulse energies due to its low melting point. The obtained results are compared with previous results from selective laser sintering of titanium powder. PACS 61.43.Dq; 81.20.Ev, 81.05.Rm     

Formation of graphite encapsulated iron nanoparticles during mechanical activation and annealing analyzed by Mössbauer spectroscopy

The investigation performed by means of Mössbauer spectroscopy, X-ray diffraction and transmission electron microscopy demonstrated that the interaction in the system iron-amorphous carbon proceeds via the formation of nano-sized iron particles (10–40 nm) and the carbide nano- phases distributed over amorphous carbon matrix. The annealing of these samples causes a crystallization of the amorphous carbon, decomposition of nano-sized carbide phases and formation of iron nanoparticles (50–100 nm) encapsulated by graphite.     

The performance of iron-containing catalysts prepared at low temperature for carbon monoxide hydrogenation

The performance for carbon monoxide hydrogenation of amorphous- and crystalline-unsupported iron oxides following low temperature pretreatment in nitrogen, carbon monoxide and hydrogen has been examined. The phase compositions of the catalysts before and after catalytic evaluation have been determined by⁵⁷Fe Mössbauer spectroscopy. Pretreatment of amorphous non-potassium doped precipitates gave the formation of metallic iron catalysts which were catalytically active at low temperatures and which were shown by Mössbauer spectroscopy to be converted during evaluation to iron carbide and the iron oxide Fe₃O₄. Catalysts which were not pretreated were reduced during catalytic evaluation to Fe₃O₄. Pretreated potassium-doped catalysts composed of either iron carbide or a mixture of iron carbide and metallic iron gave hydrocarbon product distributions which showed a higher Schulz-Flory alpha value and a lower selectivity towards methane when the catalyst reached steady state as a result of an increase in carbon monoxide adsorption and/or a decrease in hydrogen adsorption. The used catalysts were shown by Mössbauer spectroscopy to contain iron carbide together with various proportions of metallic iron and the iron oxide Fe₃O₄. The activities of the pretreated amorphous and crystalline catalysts were comparable and may be related to the disintegration of the crystalline catalysts during pretreatment in carbon monoxide which induces the formation of particles with surface areas similar to those observed in the amorphous catalysts.     

Enhanced multiple exciton generation in amorphous silicon nanowires and films

ABSTRACT

Multiple exciton generation (MEG) in nanometer-sized hydrogen-passivated silicon nanowires (NWs), and quasi two-dimensional nanofilms depends strongly on the degree of the core structural disorder as shown by the perturbative many-body quantum mechanics calculations based on the density functional theory simulations. Working to the second order in the electron–photon coupling and in the screened Coulomb interaction, we calculate quantum efficiency (QE), the average number of excitons created by a single absorbed photon, in the Si₂₉H₃₆ quantum dots (QDs) with crystalline and amorphous core structures, simple cubic three-dimensional arrays constructed from these QDs, crystalline and amorphous NWs, and quasi two-dimensional silicon nanofilms, also both crystalline and amorphous. Efficient MEG with QE ranging from 1.3 up to 1.8 at the photon energy of about 3E_g, where E_g is the electronic gap, is predicted in these nanoparticles except for the crystalline NW and crystalline film where QE ? 1. MEG in the amorphous nanoparticles is enhanced by the electron localisation due to structural disorder. Combined with the lower gaps, the nanometer-sized amorphous silicon NWs and films are predicted to have effective carrier multiplication within the solar spectrum range.     

Ferromagnetismus von amorphem Eisen

In a previous paper a method has been described to produce thin films of amorphous iron by simultaneous condensation of iron and small additions of oxygen, silicon, or germanium onto a substrate at 20 °K. During annealing the amorphous films crystallize within a narrow range of temperature. In this paper the magnetic properties of these films are investigated. By a new lowtemperature ?gnetometer the magnetization curves can be registered for the different states of annealing. It results that even in the amorphous state iron is ferromagnetic. Below a critical concentration of the oxygen, silicon, or germanium admixtures the magnetic moment of the iron atoms is smaller and the coercive force is greater in the amorphous than in the crystalline structure. Above that concentration the magnetic moments in the two structures are equal, whereas the coercive force of the amorphous films is smaller than that of the crystalline ones. The results are explained by a concentration depending short range order in the amorphous films.     

Preferential substitution of 57Fe in Co1−χBχ glasses

The substitution of iron for cobalt in crystalline Co₃B and Co₇₈B₂₂ and Co₇₂Si₂B₂₆ glasses has been studied by Mössbauer spectroscopy. In both crystalline and amorphous states, iron preferentially replaces those cobalt atoms which have two boron nearest neighbours.     

Neutron studies of structural changes in amorphous C60 fullerite under temperature, pressure, and thermobaric effects

The structural behavior of amorphous fullerites obtained as a result of mechanical activation and thermal, baric, and thermobaric effects is studied via neutron diffraction. It is shown that the phase transition between the molecular crystal (fullerite) and atomic crystal (graphite) phases in the nanoscale state occurs through intermediate amorphous phases.     

Photoemission and band structure of crystalline and amorphous iron phosphoborides

The electronic structure of some crystalline and amorphous iron phosphobirdes is investigated by the photoemission technique : XPS and UPS. For the crystalline compounds the experimental results, compared to those of pure iron, show a rearrangement of iron d states ; such results can be interpreted in a qualitative model where the low energy levels are related to the iron-metalloid bondïng levels meanwhile the upper levels are related to d iron states. For the amorphous alloys our results suggest that the electronic structure is similar to that of crystalline counterpart ; from U.V. spectra there is some hint that the slight variation of the electronic structure from crystalline Fe₃B to Fe₃P is reproduced in the amorphous alloys when the relative phosphorus concentration is increased. However, in the amorphous state the Fermi edge can be sharper and the effect of the structural disorder seems to be a broadening of the low lying states of the valence band.     

Mössbauer study of Fe powder mechanically alloyed by power ultrasonics

The Mössbauer and transmission electron microscopy (TEM) analysis of Fe-powder and Fe₄₆C₅₄-powder blend, mechanically milled by high power ultrasonics (USM) in He environment for 20–75 hours, have been carried out. As shown, the USM results in effective grinding of initial polycrystalline iron particles up to formation of single crystalline state, dissolution of carbon in iron particles, synthesis of carbides and possibly penetration of Fe atoms into graphite. Annealing of processed Fe₄₆C₅₄ powder causes carbide reaction.     

高温高压下非晶Co80B20合金的相稳定性

本文研究常压至770kbar压力范围内,非晶Co₈₀B₂₀合金所形成的结晶相的结构,并与Fc-B非晶合金进行比较。 关键词：     

On the determination of the volume fraction of the crystalline phase in amorphous-crystalline alloys

The possibility of determining volume fractions of crystalline and amorphous phases of partially crystalline alloys from X-ray diffraction data has been discussed. The crystallization of an amorphous microwire of the Fe_73.9B_13.2Si_10.9C₂ composition has been investigated. The crystallization leads to the formation of α-Fe and Fe(Si). An analysis has been made of the X-ray diffraction patterns recorded for a series of samples with different contents of the crystalline and amorphous phases. The angular range has been determined and the calibration graph has been constructed, which can be used to determine the volume fractions of the amorphous and crystalline components in amorphous-crystalline samples.     

Deposition of fullerene films from the ablation plasma generated by high-power ion beams on graphite targets

A possibility of deposing carbon films with a high content of C₆₀ and C₇₀ fullerenes from an ablation plasma generated as a result of irradiation of graphite targets by pulsed high-power ion beams is shown. The relative contents of the crystalline diamond-like carbon phase, crystalline fullerene phase, and amorphous carbon phase have been determined by X-ray diffraction analysis for different deposition conditions. The nanohardness and Young’s modulus of the deposited films and their adhesion to the single-crystal silicon substrate have been measured.     

Superparamagnetism of magnetite particles in C<Subscript>60</Subscript> fullerite powder

A new magnetic material, C₆₀ fullerite powder doped by magnetite (Fe₃O₄) nanoparticles, is obtained by heating a mixture of fullerite and iron(III) acetylacetonate. It is shown that the material offers superparamagnetic properties. Surface bonding between the nanoparticles and the fullerite is established.     

Influence of electromagnetic radiation on the phase composition of clustered CN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> films

The effect of white and UV radiation on the phase composition of amorphous CN _x films are studied by X-ray diffraction analysis and visible-range spectroscopy. The films have variable-range atomic order and consist of amorphous graphite clusters (30 Å) crystalline clusters (50–100 Å) of graphite, diamond, and carbon nitride phases; and intercluster medium with long-range (1–2 Å) atomic order. It is shown that irradiation of the films by white light facilitates the growth of fine graphite clusters. Irradiation by UV light suppresses the growth of the graphite and carbon nitride phases, favoring the growth of the diamond phase (1.5%). It is demonstrated that a change in the mesoscopic phase composition of the CN _x films causes a change in the energy gap width in the visible range from E _g = 0.75 eV for the films irradiated by white light to E _g = 1.75 eV for those exposed to UV radiation.