Studies of adsorption equilibria and kinetics in the systems: Aqueous solution of dyes-mesoporous carbons

Two carbonaceous materials were synthesized by using the method of impregnation of mesoporous silicas obtained by applying the Pluronic copolymers as pore-creating agents. The isotherms of adsorption of methylene blue and methyl orange from aqueous solutions were measured by the static method. The profiles of adsorbate concentration change in time were obtained from the UV-vis spectra. The adsorption isotherms and kinetic dependence were discussed in the terms of theory of adsorption on heterogeneous surfaces.     

Enhanced activity of mesoporous Nb2O5 for photocatalytic hydrogen production

The mesoporous Nb₂O₅ photocatalysts were synthesized via an evaporation-induced self-assembly (EISA) method. The mesoporous structure of the as-made samples was studied by small-angle X-ray diffraction, N₂ adsorption-desorption isothermal and transmission electron microscopy. The increase of the calcination temperature during the synthesis resulted in enhanced crystallization, but decreased mesoporosity of the samples. The later was found to have a crucial influence on the photocatalytic activity by bringing on decreased BET surface area and especially increscent pore wall thickness. The advantage of the mesoporous Nb₂O₅ was also proved by performing 20 times higher photocatalytic activity than a bulk Nb₂O₅ without any porosity. A model was given to describe the effect of mesoporosity on the transportation and recombination of carriers.     

Fabrication of metal nano-structures using anodic alumina membranes grown in phosphoric acid solution: Tailoring template morphology

The influence of experimental parameters on the morphology of the porous structure and on the formation kinetics has been investigated for anodic alumina membranes (AAM) grown in aqueous H₃PO₄ at 160 V. It was found that pore aspect ratio and membrane porosity on the solution-side surface are influenced by tensiostatic charge, bath temperature and the presence of Al³⁺ ions in solution. Morphological and kinetic data, recorded in different conditions, give useful information on the growth mechanism of pore channels in phosphoric acid solution.Nickel nano-structures have been fabricated using AAM as template. Electroless deposition, performed by adding the reducing agent to a suitable bath in several steps, resulted in the formation of short metal nanotubes (about 5 μm long) in the upper part of the channels. Long Ni nanowires (up to 25 μm) with aspect ratio higher than 100 were obtained by pulsed unipolar electrodeposition from a Watt bath. In this case, both the influence of some experimental parameters on the nanowires growth and the fast current transients during the electrodeposition steps were analyzed.     

Preparation of Ni-doped carbon nanospheres with different surface chemistry and controlled pore structure

In classic carbon supports is very difficult to control pore size, pore size distribution, and surface chemical properties at the same time. In this work microporous carbons derived from furfuryl alcohol are used as support to prepare Ni-doped carbon materials. The N₂ flow rate used during the carbonisation process of the precursor influences on the size of the nanospheres obtained but not in their textural properties. Microporous carbon nanospheres have been synthesised with a narrow pore size distribution centred in 5.5 Å. The surface chemistry of these materials can be easily modified by different treatments without detriment of the pore structure of the doped carbon nanospheres.     

Alumina-zirconium ceramics synthesis by selective laser sintering/melting

In the present paper, porous refractory ceramics synthesized by selective laser sintering/melting from a mixture of zirconium dioxide, aluminum and/or alumina powders are subjected to optical metallography and X-ray analysis to study their microstructure and phase composition depending on the laser processing parameters. It is shown that high-speed laser sintering in air yields ceramics with dense structure and a uniform distribution of the stabilizing phases. The obtained ceramic-matrix composites may be used as thermal and electrical insulators and wear resistant coating in solid oxide fuel cells, crucibles, heating elements, medical tools. The possibility to reinforce refractory ceramics by laser synthesis is shown on the example of tetragonal dioxide of zirconium with hardened micro-inclusion of Al₂O₃. By applying finely dispersed Y₂O₃ powder inclusions, the type of the ceramic structure is significantly changed.     

One-dimensional structures of Bi2O3 synthesized via metalorganic chemical vapor deposition process

We have demonstrated the synthesis of one-dimensional (1D) structures of bismuth oxide (Bi₂O₃) by a reaction of a trimethylbismuth (TMBi) and oxygen (O₂) mixture at 450 °C. Scanning electron microscopy showed that the product consisted of 1D materials with width or diameters less than 1 μm and lengths up to several tens of micrometers. The X-ray energy dispersive spectroscopy revealed that the materials contained elements of Bi and O. The results of X-ray diffraction and selected area electron diffraction pattern indicated that the obtained Bi₂O₃ were crystalline with monoclinic structure.     

Effects of hydrogen etching process on the structural and optical properties of nano-crystalline diamond films

In this work, hydrogen etching method is applied to improve the quality of nano-crystalline diamond (NCD) films grown from hot-filament assisted chemical vapor deposition (HFCVD) system. From the characteristics of the structure and optical property, the grain size and surface roughness decrease while the optical transmission increase obviously under certain deposition parameters (gas pressure and substrate temperature) and longer etching time. Soft X-ray transmission measurements by synchrotron radiation are also carried out on the NCD films. The result shows that the X-ray transmission has an obvious improvement when the NCD film is fabricated from the hydrogen etching method. And the transmittance reaches 53.3% at X-ray photon energy of 258 eV, which has met the requirement for X-ray mask materials.     

Preparation and FMR analysis of Co nanowires in alumina templates

Magnetic and structural properties of a high aspect ratio Co nanowire (NW) array electrodeposited in free-standing porous alumina template with a pore diameter of ∼200 nm are studied. Considered collectively, X-ray diffraction analysis, magnetometer and ferromagnetic resonance (FMR) measurements indicate that both the c-axis of crystal structure and the easy axis of magnetization are aligned preferentially perpendicular to the NW axis. The FMR spectra are characterized with very broad (a few kG) breadths and exhibit asymmetric shape in low field region due to under-saturation effects. Surprisingly, FMR spectra also revealed the presence of a spin-wave mode (SWM) as the applied field direction approached parallel to the film plane, i.e. perpendicular to the NWs. A brief discussion on this observation is provided. Further, characteristic magnetic parameters of the studied NW array were obtained by fitting the field angle-dependent FMR spectra and resonance field by using an analytical model that considers various factors affecting the total anisotropy.     

Features of microarc oxidation coatings formation technology in slurry electrolytes

A group of electrolytes composed of different powders entered into electrolyte presents a separate direction in microarc oxidation (MAO) technology. This group of electrolytes is most complex and however it has not been sufficiently studied yet. This paper shows that addition of powders of different nature into electrolyte influences both on properties of obtained coatings and on speed of their formation. The MAO-coatings formed in similar electrolytes-suspensions or slurry electrolytes (SE) contain in their composition an essential share of powder material entered into electrolyte as corpuscles of disperse phase (DP). Different nonmetallic combinations are used: oxides, carbides, borides, nitrides of metals and others. The particular conditions of microarc discharge regime (high temperature and pressure in a zone of breakdown) cause a thermolysis of electrolyte together with weighed corpuscles of solid matter, the realization of plasma chemical reactions on oxidizing surface and provide the synthesis of chemical combinations in an oxide matrix. A new composition of slurry electrolyte which allows improving the quality of obtained coatings on the basis of held investigations was developed.     

Water vapour sorption on hydrophilic and hydrophobic nanoporous materials

The aim of this study is to compare water vapour sorption isotherms on various mesoporous materials in their pristine state and after silanisation. Commonly the pristine state is regarded as hydrophilic and the silanised one as hydrophobic. Water vapour sorption experiments are discussed for a highly ordered nanoporous aluminium oxide with straight cylindrical channels of ca. 25 nm diameter and for various controlled porous glasses (CPGs) with disordered pores in the range of 13 nm diameter. The water sorption isotherms exhibit in both cases a hysteresis over the entire humidity range. At higher humidities the pristine materials show capillary condensation whereas for the silanised samples this phase transition does not occur or even a loss of water is recorded as for the silanised Al₂O₃. Surprisingly, for the silanised Al₂O higher water uptake is observed in the low humidity region. Application of the excess surface work (ESW) method delivers a reduced structural component in the long range interaction of the water molecules with a hydrophobic surface. Inverse gas chromatography studies of the silanised CPGs result in an increased short range dispersive part of the surface energy with the increasing degree of silanisation.     

Effects of oscillatory shear flow on chain-like cluster dynamics in ferrofluids without magnetic fields

Brownian dynamics simulations of interacting magnetic particles in a quasi-two-dimensional ferrofluid system are performed at zero temperature, under the influence of oscillatory shear flow in the absence of external magnetic fields. Starting from chain-like clusters of the particles, we study the time-dependent behavior of both magnetization and microstructures of the ferrofluid by changing values of two parameters, the shear rate strength and frequency of oscillatory shear flow. Simulation results show that there are three different dynamical regimes for the chain clusters dynamics, depending on these two parameters. Scaling behavior of the asymptotic magnetization is also observed for a certain range of parameters.     

Synthesis and characterization of spherical and narrow size distribution indium oxide nanoparticles

This work reports the synthesis of indium oxide nanoparticles and their thermal, structural, microstructural and optical characterization. The preparation method is based on a surfactant-free room temperature soft chemistry route. Spherical indium oxide nanoparticles (about 8 nm in diameter) were obtained after thermal treatment of gels at 400 °C for 2 h, as shown by X-ray diffraction experiments and nitrogen adsorption measurements. Transmission electron microscopy observations confirm the single-crystalline nature of the produced nanoparticles. The photoluminescence emission spectrum at room temperature shows a broad peak with onset at approximately 315 nm as a result of quantum size effect as revealed by small-angle X-ray scattering.     

Large-area silica nanotubes with controllable geometry on silicon substrates

The synthesis of a highly uniform, large-scale nanoarrays consisting of silica nanotubes above embedded nanohole arrays in silicon substrates is demonstrated. In situ anodized aluminium oxide (AAO) thin film masks on Si substrates were employed, and the nanotubes were fabricated by Ar ion milling through the masks. The geometries of the nanoarrays, including pore diameter, interpore distance and the length of both nanopores and nanotubes could be controlled by the process parameters, which included that the outer pore diameter of silica tube was tuned from ∼80 nm to ∼135 nm while the inner tube diameter from ∼40 nm to ∼65 nm, the interpore distance of the nanotube arrays was from 100 nm to 180 nm and the length of silica tube changed from ∼90 nm to ∼250 nm. The presented nanostructure fabrication method has strong potential for application in intensity and frequency adjustable high luminescence efficiency optoelectronic devices.     

Thermochemical process in preparation of ZnO film by TFA-MOD method

The excess weight loss due to the evaporation of zinc compound is observed in the growth of ZnO film by trifluoroacetate metalorganic deposition (TFA-MOD) method. Higher temperature (>90 °C) aging and/or addition of monoethanolamine (MEA) are effective to prevent the evaporation of zinc compound and increase the yield of ZnO. The mechanism of preventing evaporation is that zinc trifluoroacetate is hydrolyzed into Zn₄O(CF₃COO)₆. A three-dimensional structure of Zn₄O(CF₃COO)₆ is proposed. It is shown that higher temperature aging does harm to the surface morphology of ZnO films. The addition of MEA reduces the required aging temperature thus improves the surface morphology.     

The current of a particle along a microtubule in microscopic plasma

Transport of a particle along the axis of a microtubule in a plasma-enhanced chemical vapor deposition (PECVD) system is investigated. The current, respectively, as a function of the temperature, the magnetic field and the external force is obtained. The value and direction of the current may be controlled by changing the above parameters.     

Melting mechanism of monolayers adsorbed in cylindrical pores: An influence of the pore wall roughness

We have analyzed the mechanism of melting of layers adsorbed in cylindrical pores of porous materials. The goal was to understand the melting mechanism of simple fluids adsorbed in pores with heterogeneous wall surface. The studied system was a monolayer of methane molecules adsorbed in MCM-41 pore of diameter d = 4 nm. Both experimental (neutron scattering) and simulation (Monte Carlo) results proved extremely strong influence of the wall roughness on the melting mechanism. The most striking difference between melting on smooth and rough surfaces was in the temperatures of the transition. The transformation between solid-like and liquid-like monolayer phases adsorbed on a rough surface was observed in a very large temperature range and the solid like properties were observed even above the bulk methane melting temperature.     

Dynamically tessellating algorithm for analysis of pore size distribution in particle agglomerates

We describe a novel physical application of the OctTree data structure [P. Meagher, Comput. Graphics Image Process 19(2) (1982) 129–147] in a dynamically tessellating algorithm, in conjunction with an object-oriented, constructive solid geometry library (DOC), to efficiently determine pore size distributions in large multi-particle systems. We apply the DOC library to investigate the evolving dynamics of pore formation in multi-particle systems, such as a mixture of smooth hard cubes and spheres and a collection of frictional soft spheres. We demonstrate that the algorithm is able to provide insight into the effect of structural changes on the porosity network; for example, during the uniaxial compaction of soft spheres, we find the number density of pores increases while the mean volume of the pores decreases. This trend is responsible for a shift in the distribution of the pore volumes to favour smaller volumes. We anticipate that the DOC method will have wider applications in the area of granular materials for studying the changes in pore structure in both experimental and numerical systems as a complement to the analysis of particle packing.     

Elasticity and thermodynamic properties of RuB2 under pressure

First-principles calculations of the crystal structure and the elastic properties of RuB₂ have been carried out with the plane-wave pseudopotential density functional theory method. The calculated values are in very good agreement with experimental data as well as with some of the existing model calculations. The elastic constants c_ij, the aggregate elastic moduli (B, G, E), Poisson's ratio, and the elastic anisotropy with pressure have been investigated. Through the quasi-harmonic Debye model considering the phonon effects, the isothermal bulk modulus, the thermal expansions, Grüneisen parameters, and Debye temperatures depending on the temperature and pressure are obtained in the whole pressure range from 0 to 60 GPa and temperature range from 0 to 1100 K as well as compared to available data.     

Study of electronic structures for Fe thin films deposited on Si- and C-faces of 4H-SiC substrates by soft X-ray emission spectroscopy

Silicon carbide (SiC) is a candidate material for electronic devices to operate upon crucial environment. Electronic states of silicides and/or carbide/graphite formed in metal/SiC contact system are fundamentally important from the viewpoint of device performance.We study interface electronic structure of iron thin film deposited on silicon (Si)- and carbon (C)-face of 4H-SiC(0 0 0 1) by using a soft X-ray emission spectroscopy (SXES). For specimens of Fe (50 nm)/4H-SiC (substrate) contact systems annealed at 700 and 900 °C, the Si L_2,3 emission spectra indicate different shapes and peak energies from the substrate depending on thermal-treated temperature. The product of materials such as silicides is suggested. Further, from comparison of Si L_2,3 emission spectra between Si- and C-face for the same annealing temperature at 700 °C, it is concluded that the similar silicides and/or ternary materials are formed on the two surfaces. However for those of 900 °C, the film on substrate is composed of the different silicide and/or ternary materials.     

Hydrolysis and stability of thin pulsed plasma polymerised maleic anhydride coatings

The stability of plasma polymerised layers has become important because of their widespread use. This study explored the hydrolysis and degradation stability of coatings of plasma polymerised maleic anhydride. Coatings made with different plasma parameters were exposed to aqueous media of different pH as a function of time. ATR-FTIR was used for structure analysis and a toluidine blue staining method allowed quantitative analysis of the hydrolysis of anhydride groups to acid groups. Coatings with constant thickness were obtained at different plasma powers and layers with varying thickness were obtained at constant plasma power by adjusting the polymerisation time. The results show that the hydrolysis resistance of the modified layer is determined by the power used in the plasma polymerisation, while changes in the chemistry of the modified layer are insignificant.