Effect of preparation technique on the properties of Mo-containing Al-MCM-41

The Al-MCM-41 has been used as support to prepare Mo-containing catalysts. The 12- molybdophosphoric heteropoly acid (HPMo) is used as initial compound. The catalysts are synthesized by two different methods: incipient impregnation with aqueous solution of the acid and mechanochemical synthesis. The samples were tested in the reaction of the thiophene hydrodesulfurization after activation with mixture H₂ + H₂S. The effect of the preparation method of the catalysts on their physicochemical and catalytic properties has been studied. A partial destruction of the loaded compound is observed in mechanochemically treated sample whereas the aggregates are formed from the particles of different size in the impregnated sample. The specific surface area of the sample prepared by mechanical–chemical treatment decreases 2–3 times, while the total pore volume is about four times lower. The HDS activity is higher on the impregnated sample than on the mechanochemically treated one.     

On structural and high temperature electrochemical properties of ZrO2 thin film coating on Zr metal produced by carbonate melt

Melt of NaCO₃ can favor oxidation of Zr to form ZrO₂ thin film on Zr surface, which is used to make Zr/ZrO₂ oxidation/reduction electrode of pH sensor for testing elevated temperature aqueous solutions. Using SEM, EPMA, XPS, EXAFS and HRTEM, we found that ZrO₂ film is tightness and solid with 20 μm thickness composed by nanometer-sized monoclinic crystals. Zr/ZrO₂ interface is characterized of zoning structure according to topography and chemical composition in five zones: oxygen-rich ZrO₂, ZrO₂, oxygen-rich Zr metal, oxygen-bearing Zr and Zr from outmost to center. Melt oxidation process of Zr involved oxidation time, air and temperature. The air is important effect on structural and electrochemical properties of ZrO₂ thin film for making elevate temperature electrochemical sensor. If oxygen air largely presented in carbonate melting process, ZrO₂ thin film is not tightness and not for oxidation/reduction electrode.     

Study of the hydrolysis and condensation of γ-Aminopropyltriethoxysilane by FT-IR spectroscopy

The hydrolysis and condensation reactions of γ-APS have been studied in different acid content aqueous solution by using Fourier Transform infrared (FT-IR) spectroscopy. The hydrolysis of γ-APS under the studied conditions can be followed by the increase of the ethanol band located at 882 cm⁻¹ and the decrease of the band due to the ρ(CH₃) of γ-APS molecules located at 959 cm⁻¹. Hydrolysis reaction is faster by increasing both H₂O and acid concentrations, and it is completed when 3 moles of H₂O per mole of γ-APS are used. The increase of the vibrational band located at 1146 cm⁻¹ shows that condensation of the hydrolysed γ-APS molecules take place forming linear chains in poorly cross-linked structures. Besides, both 8-membered cyclic siloxane formations and poorly cross-linked structures are formed and increase as the water and acid content are increased. On the other hand, highly connected cross-linked structures do not appear due to the steric hindrance of the non-hydrolysable aminopropyl group. The silanol band shows that hydrolysis is faster than condensation except for samples with the lowest H₂O content.     

Optimized hydrogen positions for aluminium and iron containing hydroxide minerals

The structures of a number of hydroxide and oxyhydroxide minerals have previously been reported without the hydrogen positions explicitly defined. Here we use two atomic scale computer simulation techniques, one based on classical ionic potentials, the other on density functional theory (DFT), to predict these positions. The aim is not only to provide data that can be used as the basis for future experimental structure optimizations but also model parameters that can be used to predict complex hydroxide structures. The efficacy of the approach is demonstrated through the comparison of predicted and experimental data for minerals whose hydrogen positions are known.     

Electrical characterization of carbon nanotube Y-junctions: a foundation for new nanoelectronics

A review on the syntheses and electrical characterization of Y-shaped multi-walled carbon nanotube morphologies is presented. Modified thermal CVD processes, using Ti precursors, are used to grow Y-junctions of different geometries and distribution of catalyst particles. It has been established that novel electrical switching behavior is feasible, where any one of the three branches of the Y-junction can be used for modulating the electrical current flow through the other two branches. Current blocking behavior, leading to perfect rectification, is seen which could be related to the interplay of the carrier lifetime and the transit time. The overall goal is to investigate the possibility of obtaining novel functionality at the nanoscale, which can lead to new device paradigms.     

LLDPE’s grown with Metallocene and Ziegler–Natta catalysts: events in the melt and FTIR analysis

LLDPE samples synthesized with Ziegler–Natta (ZN) and Metallocene (MT) catalysts have been analyzed to investigate a potential catalyst-dependent morphology and to find an explanation for the difficult processing of MT. Slow calorimetry at v = 0.02 K/min and IR at RT and in the melt are used. The differences between MT and ZN are assigned to their different composition, MT not having the linear segments, which are present in ZN. Slow calorimetry is effectively a drawing process of the melt with chain orientation followed by decay. The later event, characterized by an endotherm, ΔH _network, occurs at higher temperatures for MT, the presence of a regular distribution of methyl groups slowing down the process. The rocking, gauche, bending and stretching regions of the IR spectra are analyzed. The nascent MT has more strained bands in the rocking region. The wagging region reveals the more homogeneous environment of MT through the maximum absorbance at 1,368 cm⁻¹. Decomposition of bands is made for the rocking and wagging regions. The orthorhombic crystallinity, α_c (FTIR), measures the sum of long- and short-range orthorhombic order, the latter being obtained by α_c (FTIR)-α_c (X-rays). The values of α_c (FTIR) for MT and ZN are very similar in conditions of equilibrium. The justifications for the molecular origin of ΔH _network are presented: (i) the slow relaxation of long chains strained and oriented in the melt measured by other techniques, (ii) The correlation, for gels of a linear sample, made in different solvents, between the maximum drawability, λ_max, and ΔH _network in a slow T-ramp. The range is 80–270 for λ_max and 40–120 J/g for ΔH _network. (iii) The comparison of two traces of the same sample, between 140 °C and 270 °C, show that comparable events in the melt appear in the integrated absorbance and in the slow calorimetry signal. Analysis on thin films of the little-studied CH₂ stretching region reveals that their extinction coefficient, ε, and the shape of the bands are highly sensitive to the sample history, ε diminishing by a large factor in slowly crystallized samples. Events in the slow T-ramp, followed by a fast crystallization, on the other hand, leads to materials with standard characteristics. Slow calorimetry traces display more events (endothermic and exothermic) for MT than for ZN, a finding consistent with more flow irregularities during processing. Equilibrium conditions and better processing could be reached for MT by extending time in the melt or using higher temperatures.     

Critical slowing down in lead magnesium niobate–zirconate ceramic

Dielectric relaxation behaviour of (1 − x)PMN − xPZ, for x = 0.10, 0.30 and 0.40 have been studied. The nature of relaxational behaviour was found to change with PZ concentration. A crossover from a static freezing to critical slowing down like behaviour is observed with increase in Zr⁴⁺ concentration. We have used Glazounov and Tangastev criterion to distinguish freezing and critical slowing down like behaviour.     

Probing the thermal decomposition process of layered double hydroxides through in situ <Superscript>57</Superscript>Fe Mössbauer and in situ X-ray diffraction experiments

The thermal decomposition properties of Mg–Fe hydrotalcites were studied through in situ ⁵⁷Fe Mössbauer spectroscopy and in situ X-ray diffraction. Abrupt changes in the quadrupolar splitting measured in the Mössbauer spectra revealed a phase transition from the starting lamellar structure to a new crystalline arrangement. By analyzing the Mössbauer parameters we show that the material is highly disordered in the 300–400 °C temperature range. This hypothesis is confirmed by the X-ray results whose diffractograms indicated the collapse of the lamellar structure and the formation of a solid solution.     

Modelling of effects of ultrastructural morphology on the hygroelastic properties of wood fibres

Wood fibres constitute the structural framework of e.g. wood, paper, board and composites, where stiffness and dimensional stability are of importance. An analytical modelling approach has been used for prediction of hygroelastic response, and assessment of the stresses in thick-walled cylinder models of wood fibres. A wood fibre was idealised as a multilayered hollow cylinder made of orthotropic material with helical orientation. The hygroelastic response of the layered assembly due to axisymmetric loading and moisture content changes was obtained by solving the corresponding boundary value problem of elasticity. A simple solution scheme based on the state space approach and the transfer matrix method was employed. This was combined with an analytical ultrastructural homogenisation method, used to link hygroelastic properties of constituent wood polymers to properties of each layer. Predicted hygroelastic response captured experimentally measured behaviour. Fibres that were constrained not to twist showed a stiffer response than fibres allowed twisting under uniaxial loading. It was also shown that the ultrastructure, i.e. the microfibril angle, will control the hygroexpansion in the same way as it controls the compliance of the cell wall. Qualitative failure trends comparable with experimental observations could be established with stress analysis and a simple plane-stress failure criterion.     

Synthesis and characterization of morphologically different high purity gallium oxide nanopowders

High purity gallium oxide nanopowders have been synthesized by using a simple precipitation technique with calcination at elevated temperature. From the X-ray pattern, the phase purity of the synthesized powders was confirmed as β-Ga₂O_3. Elemental quantification (stoichiometry) of Ga₂O₃ was also examined from the X-ray energy dispersive analysis (EDAX). Based on the recorded Fourier Transform Infrared (FTIR) spectrum of Ga₂O_3, the IR bands due to Ga–O bond and crystal lattice vibrations have been identified in the wavenumber range 400–4,000 cm⁻¹. From the measured SEM images, it is obvious to notice that the pH value has been playing a dominant role in obtaining morphologically different gallium oxide nanopowders. Thermogravimetric analysis reveals 8.3% of weight loss when the sample was heated to the temperature of 1,100 °C from the room temperature, which also shows a crystalline phase transformation. It is very interesting to report that a broad blue emission at 455 nm has been measured from the synthesized gallium oxide nanopowders.