Changes in the chemical state and concentration of iron in carbon nanotubes obtained by the CVD method and exposed to pulsed ion irradiation

Data on the distribution of iron in nitrogen-containing multiwall carbon nanotubes (N-MWCNTs) and changes in its chemical state and concentration under different parameters of irradiation by a pulsed ion beam are obtained by methods of transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersion analysis. It is shown that the irradiation of N-MWCNTs with an energy density of 0.5 J/cm² lead to the formation, on their lateral surfaces, of structures with a size of 2–10 nm, consisting of metallic iron encapsulated in a carbon shell. An increase in the energy density to 1–1.5 J/cm² leads to a substantial removal of iron clusters from the tips of carbon nanotubes and a reduction in the amount of iron in the bulk of the N-MWCNT layer.

     

C36团簇自组装的分子动力学研究

提出了利用C36团簇在气相条件下自组装制备新纳米团簇的设想，并利用分子动力学方法模 拟了包括真实氦气氛作用的碳团簇生长过程，发现环境气体温度是影响最后所生成的团簇结 构的关键因素：C36团簇在1000?K到2000?K的温度范围内，自组装形成保持C36线径特征的 蚕茧状新纳米团簇；在高于2000?K的温度下，最后形成的团簇趋于球状. 关键词： 分子动力学模拟 纳米碳团簇     

Modelling non-equilibrium self-assembly from dissipation

Non-equilibrium self-assembly is ubiquitous in physico-chemical and biological systems, and manifests itself at different scales, ranging from the molecular to the cosmological. The formation of microtubules, gels, cells and living beings among many others takes place through self-assembly under nonequilibrium conditions. We propose a general thermodynamic non-equilibrium model to understand the formation of assembled structures such as gels and Liesegang patterns and at the same time able to describe the kinetics and the energetics of the structure formation process. The model is supported for a global mechanism to obtain self-assembled structures from building blocks via activation, deactivation, assembly, and disassembly processes. It is proposed that the resulting structures can be characterised by a structural parameter. Our model may contribute to a better understanding of non-equilibrium self-assembly processes and give deeper insight as to how to obtain a specific structural architecture to materials, such as hydrogels which are of great importance in the design of advanced devices and novel materials.     

Carbon-supported iron catalysts: Iron-57 Mössbauer spectroscopic studies of phase formation and dispersion properties which influence catalytic performance

The treatment of carbon-supported iron in hydrogen and carbon monoxide gives the formation of iron carbide phases, the nature of which depends on the degree of dispersion of the supported iron phase. The carbon-supported iron catalysts show high activity, low conversion to methane, and good selectivities for the formation of gaseous olefins and liquid hydrocarbons. The catalytic performance is associated with strong interactions between the carbon support and the metallic iron particles as revealed by⁵⁷Fe Mössbauer spectroscopy. The results imply that the carbon may not only function as a support for the dispersion of iron, but that electron movement to the iron/carbon interface influences catalytic performance.     

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.     

Multiple patterns of diblock copolymer confined in irregular geometries with soft surface

The different confinement shapes can induce the formation of various interesting and novel morphologies, which might inspire potential applications of materials. In this paper, we study the directed self-assembly of diblock copolymer confined in irregular geometries with a soft surface by using self-consistent field theory. Two types of confinement geometries are considered, namely, one is the concave pore with one groove and the other is the concave pore with two grooves. We obtain more novel and different structures which could not be produced in other two-dimensional(2D) confinements. Comparing these new structures with those obtained in regular square confinement, we find that the range of ordered lamellae is enlarged and the range of disordered structure is narrowed down under the concave pore confinement.We also compare the different structures obtained under the two types of confinement geometries, the results show that the effect of confinement would increase, which might induce the diblock copolymer to form novel structures. We construct the phase diagram as a function of the fraction of B block and the ratio of h/L of the groove. The simulation reveals that the wetting effect of brushes and the shape of confinement geometries play important roles in determining the morphologies of the system. Our results improve the applications in the directed self-assembly of diblock copolymer for fabricating the irregular structures.     

Intermediate structures in two-dimensional molecular self-assembly

We discuss the occurrence of transition structures observed in molecular self-assembly at surfaces. The increasing surface coverage transitions from low coverage structures to high coverage structures are a common phenomenon. However, often observed and not perfectly understood is the formation of intermediate structures, sometimes with lower lateral density than the initial phase. We will present different examples from our recent work and discuss the possible mechanisms of intermediate phase formation. In addition, we present intermediate structures occurring due to temperature-controlled reversible phase transitions.     

Non-equilibrium steady structures of confined liquid crystals driven by a dynamic boundary

Steady structures originating from dynamic self-assembly have begun to show their advantages in new generation materials, and pose challenges to equilibrium self-assembly. In view of the important role of confinement in self-assembly, here, we propose a new type of confinement leading to dynamic steady structures, which opens a new window for the conventional confinement.In our model, we consider the self-assembly of ellipsoids in 2D circular confinement via the boundary performing periodically stretching and contracting oscillation. Langevin dynamics simulations reveal the achievement of non-equilibrium steady structures under appropriate boundary motions, which are novel smectic structures with stable topological defects. Different from the confinement with a static boundary, ellipsoids close to the boundary have variable orientations depending on the boundary motion.Order-order structural transitions, accompanied by the symmetry change and varied defect number, occur with the change of oscillating amplitude and/or frequency of the boundary. Slow and fast dynamics are distinguished according to whether structural rearrangements and energetic adjustment happen or not. The collective motion of confined ellipsoids, aroused by the work performed on the system, is the key factor determining both the structure and dynamics of the self-assembly. Our results not only achieve novel textures of circular confined liquid crystals, but also inspire us to reconsider the self-assembly within the living organisms.     

Possibilities of the formation of carbides and borides by ion implantation

In the system of boron and carbon, the formation of boron carbide was investigated after ion implantation of 25 keV B ions into carbon or of 25 keV C ions into boron and subsequent annealing. TEM and electron diffraction studies showed that the crystallization of boron carbide begins only at temperatures above 1050°C. By implantation of 20 keV C ions into iron (ion dose 10¹⁷ C ions/cm²) only the metastable ε-Fe₂O will be generated, which at above 220°C transforms into the stable cementite Fe₃C. After implantation of 20 keV B ions into iron, no formation of iron boride could be found. These experimental facts can be understood qualitatively with the help of the thermal-spike model. The energy density or the temperature in the thermal spikes is not sufficient for the generation of cementite iron boride or boron carbide.     

Photo–induced processes in Ag and Eu β-diketonates incorporated into aerogel matrix of silicon dioxide by supercritical fluid impregnation

Samples of silicon dioxide aerogel with embedded Ag and Eu β-diketonate molecules are obtained by impregnation in supercritical carbon dioxide (SC-CO₂). The sample impregnated by Eu(tta)₃ molecules possesses photoluminescence properties. Moreover, adsorption of Eu(tta)₃ on the walls of the pores results in a strong broadening of the Stark components of its photoluminescence spectra. It is found that aerogel impregnation by AgFOD molecules followed by laser irradiation causes the formation of Ag nanoparticles in the sample volume as a result of AgFOD photolysis and subsequent diffusion self-assembly. The Ag nanoparticles assemble into filament structures due to self-organization as they focus laser radiation.     

Surface energy anisotropy of iron surfaces by carbon adsorption

To investigate the surface energy anisotropy of carbon-adsorbed iron surfaces related to carbon nanotube growth we have performed self-consistent pseudopotential density-functional calculations. The iron particle’s equilibrium shape is obtained from the Wulff construction using the calculated surface energies. We investigate the adsorption and diffusion of carbon atoms on the iron surfaces. It is found that the desorption energy of the carbon atoms and the activation energy for carbon diffusion are very different on different facets. Using the energetics of carbon-adsorbed iron surfaces, we evaluate the formation energies of the surfaces as a function of carbon chemical potential. Since the surface energies of the low-index iron facets are affected differently by the presence of carbon, the crystal shape is changed correspondingly.     

Catalyst influence on the flame synthesis of aligned carbon nanotubes and nanofibers

Since prepared substrates offer an appropriate method for the selective production of uniform arrays of aligned CNTs and CNFs, it is important to illustrate the influence of different catalysts on the resulting nanostructures. This investigation characterizes the activity of three catalysts—iron in alloyed form as stainless steel, nickel, and platinum—on carbon nanostructure formation under identical conditions in an ethylene/air nonpremixed flame. We have synthesized well-aligned multi-walled CNTs (on Ni) and CNFs (on stainless steel). The third transition metal Pt produces CNF structures of a different kind, and its activity has not been previously characterized in flames. The catalyst and gas-phase conditions leading to the formation of these different structures are discussed.     

Anisotropic formation mechanism and nanomechanics for the self-assembly process of cross-β peptides

Nanostructures self-assembled by cross-β peptides with ordered structures and advantageous mechanical properties have many potential applications in biomaterials and nanotechnologies. Quantifying the intra-and inter-molecular driving forces for peptide self-assembly at the atomistic level is essential for understanding the formation mechanism and nanomechanics of various morphologies of self-assembled peptides. We investigate the thermodynamics of the intra-and inter-sheet structure formations in the self-assembly process of cross-β peptide KIIIIK by means of steered molecular dynamics simulation combined with umbrella sampling. It is found that the mechanical properties of the intra-and inter-sheet structures are highly anisotropic with their intermolecular bond stiffness at the temperature of 300 K being 5.58 N/m and0.32 N/m, respectively. This mechanical anisotropy comes from the fact that the intra-sheet structure is stabilized by enthalpy but the inter-sheet structure is stabilized by entropy. Moreover, the formation process of KIIIIK intra-sheet structure is cooperatively driven by the van der Waals(VDW) interaction between the hydrophobic side chains and the electrostatic interaction between the hydrophilic backbones, but that of the inter-sheet structure is primarily driven by the VDW interaction between the hydrophobic side chains. Although only peptide KIIIIK is studied, the qualitative conclusions on the formation mechanism should also apply to other cross-β peptides.     

Low temperature synthesis of iron containing carbon nanoparticles in critical carbon dioxide

We develop a low temperature, organic solvent-free method of producing iron containing carbon (Fe@C) nanoparticles. We show that Fe@C nanoparticles are self-assembled by mixing ferrocene with sub-critical (25.0 °C), near-critical (31.0 °C) and super-critical (41.0 °C) carbon dioxide and irradiating the solutions with UV laser of 266-nm wavelength. The diameter of the iron particles varies from 1 to 100 nm, whereas that of Fe@C particles ranges from 200 nm to 1 μm. Bamboo-shaped structures are also formed by iron particles and carbon layers. There is no appreciable effect of the temperature on the quantity and diameter distributions of the particles produced. The Fe@C nanoparticles show soft ferromagnetic characteristics. Iron particles are crystallised, composed of bcc and fcc lattice structures, and the carbon shells are graphitised after irradiation of electron beams.     

Microwave plasma CVD-grown graphene–CNT hybrids for enhanced electron field emission applications

The growth and electron emission characteristics were investigated from a hybrid structure of multiwalled carbon nanotubes (MWCNTs) and multilayer layer graphene (MLG) deposited on silicon substrate coated with iron catalyst and an interlayer of aluminium. The hybrid structures were synthesized in a two-step process by microwave plasma-enhanced chemical vapour deposition technique. The formation of MWCNTs takes place by absorption and precipitation of carbon radicals into the catalyst particles. Thereafter, ample carbon forms MLG on tip of the MWCNTs resulting in a MLG-MWCNTs hybrid nanostructure. MLG was observed to grow branching out of the tips and sidewalls of the MWCNTs and is expected to attach by Van der Walls bonds. Transmission electron microscopy and micro-Raman spectroscopy confirmed the crystalline nature of the hybrid structures. Electron emission studies were carried out using a diode-type field emission setup. The enhancement factor was found to be ~3,500 for bare MWCNTs, ~4,070 to ~5,000 for hybrid structures and ~6,500 for N-doped MLG-MWCNTs hybrid structures. Modification in the defects structure and enhancement of emission sites are suggested to be responsible for the increase of the field emission characteristics.     

Modification of the electronic structure of graphene by intercalation of iron and silicon atoms

The ab initio calculations of the electronic structure of low-dimensional graphene–iron–nickel and graphene–silicon–iron systems were carried out using the density functional theory. For the graphene–Fe–Ni(111) system, band structures for different spin projections and total densities of valence electrons are determined. The energy position of the Dirac cone caused by the p _z states of graphene depends weakly on the number of iron layers intercalated into the interlayer gap between nickel and graphene. For the graphene–Si–Fe(111) system, the most advantageous positions of silicon atoms on iron are determined. The intercalation of silicon under graphene leads to a sharp decrease in the interaction of carbon atoms with the substrate and largely restores the electronic properties of free graphene.

     

Driven self-assembly of hard nanoplates on soft elastic shells

The driven self-assembly behaviors of hard nanoplates on soft elastic shells are investigated by using molecular dynamics(MD) simulation method, and the driven self-assembly structures of adsorbed hard nanoplates depend on the shape of hard nanoplates and the bending energy of soft elastic shells. Three main structures for adsorbed hard nanoplates,including the ordered aggregation structures of hard nanoplates for elastic shells with a moderate bending energy, the collapsed structures for elastic shells with a low bending energy, and the disordered aggregation structures for hard shells,are observed. The self-assembly process of adsorbed hard nanoplates is driven by the surface tension of the elastic shell,and the shape of driven self-assembly structures is determined on the basis of the minimization of the second moment of mass distribution. Meanwhile, the deformations of elastic shells can be controlled by the number of adsorbed rods as well as the length of adsorbed rods. This investigation can help us understand the complexity of the driven self-assembly of hard nanoplates on elastic shells.     

Recent Notable Approaches to Study Self-Assembly of Nanoparticles with X-Ray Scattering and Electron Microscopy

Self-assembly of nanoparticles (NPs) has evolved into a powerful tool for the synthesis of superstructures with tailored properties. The quality, diversity, and complexity of synthesized structures are continuously improving and fascinating new collective properties are demonstrated. At the same time, the rapid development of electron microscopy and synchrotron sources for X-rays has enabled new exciting experimental approaches to study structure and structure formation in the context of NP self-assembly. In this review, some recent studies and what can be learned from them are highlighted and discussed. It is started with a general introduction covering important concepts, experimental approaches, commonly obtained structures, the ideas of artificial atoms, and emerging properties are discussed. Recent experimental in situ and ex situ approaches with state-of-the-art electron microscopy and X-ray diffraction and scattering that helped to obtain a detailed picture of NP self-assembly processes and resulting structures are then presented.     

Molecular dynamics simulations of diffusion of carbon into iron

Molecular dynamics (MD) simulations of diffusion couple tests were conducted between carbon (diamond/graphite) and iron at three different temperatures (300, 800 and 1600 K) and contact times (0, 40 and 80 ps) to investigate the chemical interaction between carbon and iron. Two different carbon structures, namely, diamond (cubic) and graphite (hexagonal), were considered. Diffusion of carbon into iron was observed only when a graphite interlayer was added to the diamond surface. When diamond alone was used, no diffusion was observed. This result provides corroborating evidence that diamond tool wear in the machining of iron occurs via a mechanism that involves an initial graphitization of diamond followed by diffusion of the newly formed graphite into the iron workpiece.     

PVP Assisted Shape-Controlled Synthesis of Self-Assembled 1D ZnO and 3D CuO Nanostructures

Self-assembled one-dimensional (1D) zinc oxide (ZnO) rods and three-dimensional (3D) cupric oxide (CuO) cubes like nanostructures with a mean crystallite size of approximately 33 and 32 nm were synthesized through chemical route in the presence of polyvinylpyrrolidone (PVP) under mild synthesis conditions. The technique used for the synthesis of nanoparticles seems to be an efficient, inexpensive and easy method. X-Ray diffraction patterns confirmed well crystallinity and phase purity of the as prepared samples, followed by the compositional investigation using Fourier Transform Infrared (FT-IR) spectroscopy. The formation of ZnO nanorods and CuO nanocubes like structures were through Scanning Electron Microscopy (SEM) images. The mechanism and the formation factors of the self-assembly were discussed in detail. It was clearly observed from results that the concentration of precursors and PVP were important factors in the synthesis of self-assembly ZnO and CuO nanostructures. These self-assembly nanostructures maybe used as novel materials in various potential applications.