Volume 32 (2014): Issue 2 (June 2014)

Metamaterials with negative compressibility are a very promising group of novel materials with a wide variety of potential application. A recent model proposed construction of the structures with three-dimensional negative compressibility by utilizing successive destabilization of stable or metastable states and inducing phase transitions mimicking negative compressibility. Here, we would like to show that similar concept is used by the nature and a nice example of this kind of metamaterial can be seen even in a glass of water.

Sol-gel method was successfully used for synthesis of ZnO nanoparticles doped with 10 % Mg or Cu. The structure, morphology and optical properties of the prepared nanoparticles were studied as a function of doping content. The synthesized ZnO:(Mg/Cu) samples were characterized using XRD, TEM, FTIR and UV-Vis spectroscopy techniques. The samples show hexagonal wurtzite structure, and the phase segregation takes place for Cu doping. Optical studies revealed that Mg doping increases the energy band gap while Cu incorporation results in decrease of the band gap. The antibacterial activities of the nanoparticles were tested against Escherichia coli (Gram negative bacteria) cultures. It was found that both pure and doped ZnO nanosuspensions show good antibacterial activity which increases with copper doping, and slightly decreases with adding Mg.

This research evaluates the effects of sulfuric acid hard coat anodising parameters, such as acid concentration, electrolyte temperature, current density and time, on the hardness and thickness of the resultant anodised layers. A small scale anodising facility was designed and set up to enable experimental investigation of the anodising parameters. An experimental design using the Taguchi method to optimise the parameters within an established operating window was performed. Qualitative and quantitative methods of characterisation of the resultant anodised layers were carried out. The anodised layer’s thickness, and morphology were determined using a light optical microscope (LOM) and field emission gun scanning electron microscope (FEG-SEM). Hardness measurements were carried out using a nano hardness tester. Correlations between the various anodising parameters and their effect on the hardness and thickness of the anodised layers were established. Careful evaluation of these effects enabled optimum parameters to be determined using the Taguchi method, which were verified experimentally. Anodised layers having hardness varying between 2.4–5.2 GPa and a thickness of between 20–80 μm were produced. The Taguchi method was shown to be applicable to anodising. This finding could facilitate on-going and future research and development of anodising, which is attracting remarkable academic and industrial interest.

In order to overcome limitations in the processing parameters of powder compaction method, a novel processing technique based on sol-gel route has been developed to produce near-net-shaped prototype fine zirconia minispheres with required properties that could potentially be used as grinding media. Impact of magnesia concentration and sintering temperature on the final product has been analyzed in detail. Zirconia minispheres have been characterized to establish a correlation between physical, structural and mechanical properties. Sintering temperature, soaking period, heating rate and viscosity of the sol apparently influence the characteristics of the magnesia stabilized zirconia minispheres. The phase identification, density variation, chemical decomposition, functional group specification, surface area, porosity, shrinkage and microstructural features of the dried and sintered final product have been studied. It has been observed that magnesia content, sintering temperature, density and the grain size of the sintered minispheres have a significant impact on the mechanical properties of the final product.

In this study, an external electric field was used to facilitate the growth of vertically aligned ZnO crystal rods on the surface of indium tin oxide (ITO) glass substrates in an aqueous solution. We used Zn(NO3) and C6H12N4 as precursor and reagent. We found that the external electric field generated by DC potential of 5 kV between two electrodes that were placed outside the bottle could facilitate the growth of homogeneous, high density and vertically aligned ZnO crystal rods. Position of the substrate during the growth of crystal was found to be important to obtain well aligned crystal. The crystals that were grown near the negative electrode had the best properties. Photoluminescence measurement at room temperature revealed sharp peaks at around 360 and 380 nm and a broad peak around 420 nm that indicated good properties of ZnO crystals grown with external electric field.

Organic nonlinear optical single crystals of hexamethylenetetramine (HMT; 10 × 10 × 5 mm3) were prepared by crystallization from methanol solution. The grown crystals were subjected to various characterization techniques such as single crystal XRD, powder XRD, UV-Vis and electrical studies. Single crystal XRD analysis confirmed the crystalline structure of the grown crystals. Their crystalline nature was also confirmed by powder XRD technique. The optical transmittance property was identified from UV-Vis spectrum. Dielectric measurements were performed as a function of frequency at different temperatures. DC conductivity and photoconductivity studies were also carried out for the crystal. The powder second harmonic generation efficiency (SHG) of the crystal was measured using Nd:YAG laser and the efficiency was found to be two times greater than that of potassium dihydrogen phosphate (KDP).

In 2011, we proposed a novel magnetron sputtering method. It involved the use of pulsed injection of working gas for the initiation and control of gas discharge during reactive sputtering of an AlN layer (Gas Injection Magnetron Sputtering — GIMS). Unfortunately, the presence of Al-Al bonds was found in XPS spectra of the AlN layers deposited by GIMS onto Si substrate. Our studies reported in this paper proved that the synchronization of time duration of the pulses of both gas injection and applied voltage, resulted in the elimination of Al-Al bonds in the AlN layer material, which was confirmed by the XPS studies. In our opinion the most probable reason of Al-Al bonds in the AlN layers deposited by the GIMS was the self-sputtering of the Al target in the final stage of the pulsed discharge.

An electrospinning technology have been developed to obtain zinc oxide nanofibres doped with aluminum. Properties of the obtained nanostructures can be controlled by both the composition of a precursor and subsequent annealing treatment. The gas sensors manufactured with the use of ZnO:Al nanofibres exhibit good response to NO2 at relatively low operating temperatures. For some samples it was observed that interaction with ambient NO2 gas causes the change of conductivity from n-type to p-type at higher operating temperatures. This phenomenon was not observed for the samples annealed at higher temperature.

Nano-SnO2 flat-type coplanar 2-Methyl-2,4-pentanediol (MPD) gas sensor arrays were fabricated by a screen-printing technique based on nano-SnO2 powders prepared by a hydrothermal method. The results show that the fabricated gas sensor arrays have good MPD gas sensing characteristics, such as good selectivity and response-recovery characteristics. Especially, they can be used for detecting the concentration of MPD gas as low as 1 ppm which is much lower than the legal concentration of 20 ppm or 25 ppm. The good sensing properties indicate that the SnO2 gas sensor arrays have great potential for on-line or portable monitoring of MPD gas in practical environments.

We report on electron spin resonance (ESR) investigations of a FeVO4 single crystal. Temperature and angular dependences of ESR resonance positions were measured and calculated in temperature range of 35–100 K. The spectra show rich angular dependences of the linewidth, the shape and the resonance field. They consist of a single broad line with asymmetric distortion. Due to the low symmetry of the crystal lattice this distortion can be explained by taking into account the influence of non diagonal dynamic susceptibility.

Composites of hematite (α-Fe2O3) nanoparticles with different materials (NiO, TiO2, MnO2 and Bi2O3) were synthesized. Effects of different materials on the microstructure and optical band gap of α-Fe2O3 nanoparticles were studied. Crystallite size and strain analysis indicated that the pure α-Fe2O3 nanoparticles were influenced by the presence of different materials in the composite sample. Crystallite size and strain estimated for all the samples followed opposite trends. However, the value of direct band gap decreased from ∼2.67 eV for the pure α-Fe2O3 nanoparticles to ∼2.5 eV for α-Fe2O3 composites with different materials. The value of indirect band gap, on the other hand, increased for all composite samples except for α-Fe2O3/Bi2O3.

Four samples of austenite coatings deposited by reactive magnetron sputtering on silicon substrate at four different temperatures and pressures were investigated by ferromagnetic resonance (FMR) method at room temperature. The expanded austenite phase S (γ N) layers with thickness in the 160–273 nm range and concentration of magnetic atoms: 72 % Fe, 18 % Cr and 10 % Ni, were obtained. The coatings with nanometric size grains were strongly textured and grown mostly in [100] direction, perpendicular to the sample surface. Intense FMR spectra were recorded at various angles between the static magnetic field direction and the sample surface. A strong magnetic anisotropy of the main uniform FMR mode was observed and the effective magnetization 4πM eff determined. Spin wave resonance (SWR) modes were observed in all investigated samples in out-of-plane geometry of the magnetic field. The resonance fields of SWR modes in our samples varied linearly with the spin wave mode number. The value of the effective magnon stiffness constant was determined assuming a parabolic shape of the magnetization variation across the sample thickness.

The copolymers containing carbazole unit and iridium complexes, such as (Ir(bpy)2Cl, Ir(mbpy)2Cl and Ir(Brbpy)2Cl, were synthesized via radical copolymerization of N-vinylcarbazole, methyl methacrylate and iridium complex. The synthesized copolymers were characterized by FT-IR, UV-Vis absorption spectroscopy and photoluminescence (PL) spectroscopy, respectively. According to the results, the copolymers (Ir(Brbpy)2Cl/PVK and Ir(mbpy)2Cl/PVK) exhibit yellow phosphorescence with an emission peak at around 553 nm under UV-visible light in the solid state. The results also reveal almost complete energy transfer from the host carbazole segments to the guest Ir complex in the copolymer film when the Ir content reaches 1.0 wt.%. The synthesized copolymers are good candidates as blue or yellow phosphorescent materials for PLED applications.

Titanium nitride (TiN) nano-particles were subjected to graft modification by silane coupling agent (KH-570) via a direct blending method. The hydroxyl groups on the surface of TiN nano-particles can interact with silanol groups [-Si-OCH3] of KH-570 forming an organic coating layer. The covalent bonds (Ti-O-Si) formation was testified by Fourier transform infrared spectra (FTIR) and X-ray photoelectron spectroscopy (XPS). Through transmission electron micrograph (TEM) observations, it was found that KH-570 could improve the dispersibility of nano-TiN particles in ethyl acetate. Thermo gravimetric analysis (TGA) and contact angle measurements indicated that KH-570 molecules were adsorbed or anchored on the surface of nano-TiN particle and the net efficiency of it was 22.76 %, which facilitated to hinder the aggregation of nano-TiN particles.

First-principles calculations of the lattice constants, bulk modulus, pressure derivatives of the bulk modulus and elastic constants of AlN and TiN compounds in rock-salt (B1) and wurtzite (B4) structures are presented. We have used the fullpotential linearized augmented plane wave (FP-LAPW) method within the density functional theory (DFT) in the generalized gradient approximation (GGA) for the exchange-correlation functional. Moreover, the elastic properties of cubic TiN and hexagonal AlN, including elastic constants, bulk and shear moduli are determined and compared with previous experimental and theoretical data. Our results show that the structural transition at 0 K from wurtzite to rock-salt phase occurs at 10 GPa and −26 GPa for AlN and TiN, respectively. These results are consistent with those of other studies found in the literature.

In this paper a method of determination of Pd in a carbon-palladium film (C-Pd film) deposited on a quartz substrate is presented. This method is based on energy dispersive X-ray spectroscopy (EDX) and all experiments were performed using a scanning electron microscope (SEM) equipped with EDX system. Qualitative and quantitative analyses were carried out for C-Pd films prepared by PVD method in different technological conditions. It was shown that results of the experiments depended on the structural model, film thickness and electron beam energy used for Pd content calculation.

This method enabled us to conclude on the homogeneity of palladium distribution in the whole volume of carbonaceous matrix, depending on the parameters of PVD process. Additionally, these studies showed that a different palladium concentration in C-Pd films had a significant impact on their topography and morphology.

V2O3 and amorphous carbon composites (V2O3/C composites) with different morphologies (e.g. nanospheres, nanorods and nanosheets) were, for the first time, successfully synthesized by a facile hydrothermal route and subsequent calcination. The as-obtained samples were characterized by X-ray powder diffraction (XRD), energy dispersive spectrometery (EDS), elemental analysis (EA), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The morphology of V2O3/C composites could be easily controlled by varying the reaction time, and, as a result, V2O3/C composites with nanospheres, nanorods and nanosheets were selectively synthesized. Furthermore, the phase transition property of V2O3/C composites was measured by differential scanning calorimetry (DSC), suggesting that V2O3/C composites exhibit the phase transition similar to V2O3, which could expand the potential applications of materials related to V2O3 in the future.

Synthesis of graphene directly on MgO has been carried out and the structural properties of the obtained material have been investigated. Few-layered graphene was produced by simple thermal decomposition of methane over MgO powder at 950 °C in a CVD reactor. The samples were purified by 10 N HNO3 treatment, and studied by TEM, Raman spectroscopy, EDAX and SEM. TEM clearly indicated the formation of graphene. EDAX showed that the purified sample contained only carbon and no traces of MgO. The characteristic Raman features of graphene were also seen as D-band at 1316 cm−1, G-band at 1602 cm−1, and a small 2D-band at 2700 cm−1 in the Raman spectra. The strong D-band suggests that the graphene possess large number of boundary defects. The small 2D-band indicates the formation of few-layered graphene.

Studies on electromigration phenomenon in thick-film structures on alumina and LTCC substrates are presented in this paper. The effects of storage of Au and Ag electrode patterns in temperature range up to 300 °C under voltage bias were examined. The leakage characteristics of electrodes with 100 μm spacing at 50 V dc bias as a function of time and temperature are presented and analyzed. Scanning electron microscope (SEM) equipped with the energy-dispersive X-ray spectroscopy (EDX) detector was applied for determination of metal ions transport. Test structures with Au-based conductive material are much more resistant to electromigration than Ag-based layers.

This report concerns the properties of an interface formed between Pd films deposited onto the surface of (0001)-oriented n-type GaN at room temperature (RT) under ultrahigh vacuum. The surface of clean substrate and the stages of Pd-film growth were characterized in situ by X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), ultraviolet photoelectron spectroscopy (UPS), and low energy electron diffraction (LEED).

As-deposited Pd films are grainy, cover the substrate surface uniformly and reproduce its topography. Electron affinity of the clean n-GaN surface amounts to 3.1 eV. The work function of the Pd-film is equal to 5.3 eV. No chemical interaction has been found at the Pd/GaN interface formed at RT. The Schottky barrier height of the Pd/GaN contact is equal to 1.60 eV.

The study shows the advisability of using a mechanochemical synthesis method, based on a high-energy planetary ball milling, to a modification of barium titanate by a vanadium doping. This method improves useful properties of BaTi0:95V0:05O3 as a capacitor material. It has a high value of electric permittivity ɛ′ in the wide range of temperature and low dielectric losses ɛ″ as well as a low electrical conductivity.

A new route of emulsifier-free emulsion polymerization based on the homogenous mechanism was investigated to prepare magnetic nanoparticles coated by poly (methyl methacrylate) (PMMA). The experimental results confirm the formation of PMMA thin and unique layers covering magnetite cores. The polymer layer thickness, determined from transmission electron microscopy (TEM) images, increases from 4.3 nm to 6.8 nm with increasing mass ratio of MMA to magnetite from 3:1 to 11:1. The increase of the polymer thickness results in the decrease in magnetization saturation of polymeric coated magnetic particles. However, this reduction, no more than 13 emu g−1, is much lower compared to that in other studies with the presence of surfactants or emulsifiers. Besides, the dispersion stability of the prepared particles is significantly improved.

An influence of both porous and electron structure on the processes in an electric double layer (EDL) determining the main working parameters of carbon-based supercapacitors has been studied in order to improve them. The investigations involved impedance spectroscopy, X-ray small angle scattering, confocal micro-Raman spectroscopy, infra-red and Mössbauer spectroscopy. Fe2+- and Er2+-intercallative modifications of nanoporous carbon were performed. It was found that the modification process characteristics correlated with the structure parameters of the EDL.

In this study, the Taguchi robust design method is used for optimizing ball milling parameters including milling time, rotation speed and ball to powder weight ratio in the planetary ball milling of nanostructured nickel ferrite powder. In fact, the current work deals with NiFe2O4 nanoparticles mechanochemically synthesized from NiO and Fe2O3 powders. The Taguchi robust design technique of system optimization with the L9 orthogonal array is performed to verify the best experimental levels and contribution percentages (% ρ) of each parameter. Particle size measurement using SEM gives the average particle size value in the range of 59–67 nm. X-ray diffraction using Cu Kα radiation is also carried out to identify the formation of NiFe2O4 single phase. The XRD results suggest that NiFe2O4 with a crystallite size of about 12 nm is present in 30 h activated specimens. Furthermore, based on the results of the Taguchi approach the greatest effect on particle size (42.10 %) is found to be due to rotation speed followed by milling time (37.08 %) while ball to powder weight ratio exhibits the least influence.

Graphene, a single atom thick sheet is considered a key candidate for the future nanotechnology, due to its unique extraordinary properties. Researchers are trying to synthesize bulk graphene via chemical route from graphene oxide precursor. In the present work, we investigated a safe and efficient way of monolayer graphene oxide synthesis. To get a high degree of oxidation, we sonicated the graphite flakes before oxidation. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) results confirmed graphene oxide formation and high degree of oxidation. Raman spectroscopy and atomic force microscopy (AFM) results revealed a monolayer of graphene oxide (GO) flakes. The sheet like morphology of the GO flakes was further confirmed by scanning electron microscopy (SEM). The Hall effect measurements were performed on the GO film on a silica substrate to investigate its electrical properties. The results obtained, revealed that the GO film is perfectly insulating, having electrical resistivity up to 8.4 × 108 (Ω·cm) at room temperature.

Ca2Ce2Ti5O16 dielectric ceramics prepared by conventional solid-state ceramic route was investigated. Phase composition and microwave dielectric properties were measured using XRD and Vector network analyzer, respectively. XRD analysis of the calcined and sintered samples revealed the formation of CeO2 and another unidentified phase (that vanished at ≥ 1400 °C) as secondary phases along with the parent Ca2Ce2Ti5O16 phase. The amount of the parent Ca2Ce2Ti5O16 phase increased with increasing sintering temperature from 1350 °C to 1450 °C accompanied by a decrease in the apparent density. The density decreased but ɛr and Qu f o increased with sintering temperature. An er ~ 81.5, Qu fo ~5915 GHz and t f ~ 219 GHz were achieved for the sample sintered at 1450 °C.

Nanocomposite materials based on vinylidene fluoride-hexafluoropropylene copolymer and organically modified montmorillonite Cloisite®15A were prepared by two different methods: melt mixing and co-precipitation. The changes taking place in crystalline structure, tensile strength, thermal behavior and the formation of piezoelectric b-phase as a result of the polymer system dissolution in dimethyl sulfoxide were studied. The technological specificity of each method has certain effect on the properties of the obtained nanocomposites. The highest content of b-phase — 95 % was achieved by co-precipitation from the solution of vinylidene fluoride-hexafluoropropylene copolymer in dimethyl sulfoxide and 6 mass % content of Cloisite®15A. Despite the common view that the use of solvents and prolonged technological procedure lead to overall higher expenses, the obtained nanocomposites could be promising for the preparation of new piezo-materials.