• Volume 31, Issue 5

October 2008,   pages  713-824

• Effect of ferrous/ferric ions molar ratio on reaction mechanism for hydrothermal synthesis of magnetite nanoparticles

Magnetite nanoparticles were prepared by hydrothermal synthesis under various initial ferrous/ferric molar ratios without adding any oxidizing and reducing agents in order to clarify effects of the molar ratio on the reaction mechanism for the formation of magnetite nanoparticles. The magnetite nanoparticles prepared were characterized by a scanning electron microscope, powder X-ray diffractometer, and superconducting quantum interference device (SQUID). At the molar ratio corresponding to the stoichiometric ratio in the synthesis reaction of magnetite from ferrous hydroxide and goethite, the nucleation of magnetite crystals progressed rapidly in an initial stage of the hydrothermal synthesis, resulting in formation of the magnetite nanoparticles having a smaller size and a lower crystallinity. On the other hand, at higher molar ratios, the particle size and crystallinity increased with increasing molar ratio because using surplus ferrous hydroxide the crystallites of magnetite nanoparticles grew up slowly under hydrothermal conditions according to the Schikorr reaction. The magnetite nanoparticles prepared under various molar ratios had good magnetic properties regardless of the molar ratio.

• Synthesis, characterization, sintering and dielectric properties of nanostructured perovskite-type oxide, Ba2GdSbO6

Nanoparticles of barium gadolinium antimonate (Ba2GdSbO6), a complex perovskite-type oxide, has been synthesized using an auto ignition combustion process for the first time. The nanoparticles thus obtained have been characterized by powder X-ray diffraction, thermogravimetric analysis, differential thermal analysis, Fourier transform infrared spectroscopy and transmission electron microscopy. The XRD studies have shown that the as-prepared powder is phase pure Ba2GdSbO6 and has a complex cubic perovskite (A2BB′O6) crystalline structure with lattice constant, 𝑎 = 8.449 Å. The TEM image reveals that the particle size of the as-prepared nano powder was in the range 30–60 nm. The nanocrystals of Ba2GdSbO6 synthesized by the combustion technique could be sintered to 96% of the theoretical density by heating at a temperature of 1560°C for a short duration of 3 h. The surface morphology of the sintered pellet has been studied by scanning electron microscope (SEM). The dielectric constant ($\varepsilon_{r}$) was 20 and the loss factor (tan𝛿) was 0.03 at 3 MHz. By the present combustion technique a phase pure nanopowder of Ba2GdSbO6 could be obtained by a single step process without the need of any calcination step.

• Thermodynamic analysis of growth of iron oxide films by MOCVD using tris(𝑡-butyl-3-oxo-butanoato)iron(III) as precursor

Thermodynamic calculations, using the criterion of minimization of total Gibbs free energy of the system, have been carried out for the metalorganic chemical vapour deposition (MOCVD) process involving the 𝛽-ketoesterate complex of iron [tris(𝑡-butyl-3-oxo-butanoato)iron(III) or Fe(tbob)3] and molecular oxygen. The calculations predict, under different CVD conditions such as temperature and pressure, the deposition of carbon-free pure Fe3O4, mixtures of different proportions of Fe3O4 and Fe2O3, and pure Fe2O3. The regimes of these thermodynamic CVD parameters required for the deposition of these pure and mixed phases have been depicted in a CVD phase stability diagram’. In attempts at verification of the thermodynamic calculations, it has been found by XRD and SEM analysis that, under different conditions, MOCVD results in the deposition of films comprising pure and mixed phases of iron oxide, with no carbonaceous impurities. This is consistent with the calculations.

• Electroless deposition, post annealing and characterization of nickel films on silicon

Electroless deposition of nickel (EN) films on 𝑛-type silicon has been investigated under different process conditions. The interface between the film and substrate has been characterized for electrical properties by probing the contact resistances. X-ray diffraction and atomic force microscopy have been performed to obtain information about the structural and morphological details of the films. As a comparative study, nickel films have also been sputter deposited on silicon substrates. An as-deposited electroless film is observed to form non-ohmic contact while in a sputtered film prepared without the application of substrate heating, the formation of metal–insulating–semiconductor type junction is seen.

• Simulation studies on the effect of a buffer layer on the external parameters of hydrogenated amorphous silicon 𝑝–𝑖–𝑛 solar cells

Device modeling of 𝑝–𝑖–𝑛 junction amorphous silicon solar cells has been carried out using the amorphous semiconductor analysis (ASA) simulation programme. The aim of the study was to explain the role of a buffer layer in between the 𝑝- and 𝑖-layers of the 𝑝–𝑖–𝑛 solar cell on the external parameters such as dark current density and open circuit voltage. Investigations based on the simulation of dark 𝐼–𝑉 characteristics revealed that as the buffer layer thickness increases the dark current for a given voltage decreases.

• Characterization and photocatalytic activity of boron-doped TiO2 thin films prepared by liquid phase deposition technique

Boron doped TiO2 thin films have been successfully deposited on glass substrate and silicon wafer at 30°C from an aqueous solution of ammonium hexa-fluoro titanate and boron trifluoride by liquid phase deposition technique. The boric acid was used as an 𝐹 scavenger. The resultant films were characterized by XRD, EDAX, UV and microstructures by SEM. The result shows the deposited film to be amorphous which becomes crystalline between 400 and 500°C. The EDAX and XRD data confirm the existence of boron atom in TiO2 matrix and a small peak corresponding to rutile phase was also found. Boron doped TiO2 thin films can be used as photocatalyst for the photodegradation of chlorobenzene which is a great environmental hazard. It was found that chlorobenzene undergoes degradation efficiently in presence of boron doped TiO2 thin films by exposing its aqueous solution to visible light. The photocatalytic activity increases with increase in the concentration of boron.

• Effects of Ni doping on photocatalytic activity of TiO2 thin films prepared by liquid phase deposition technique

The TiO2 thin films doped by Ni uniformly and non-uniformly were prepared on glass substrate from an aqueous solution of ammonium hexa-fluoro titanate and NiF2 by liquid phase deposition technique. The addition of boric acid as an 𝐹 scavenger will shift the equilibrium to one side and thereby deposition of the film is progressed. The rate of the reaction and the nature of deposition depend on growing time and temperature. The resultant films were characterized by XRD, EDAX, UV and SEM. The result shows that the deposited films have amorphous background, which becomes crystalline at 500°C. The EDAX data confirms the existence of Ni atoms in TiO2 matrix. XRD analysis reveals the peaks corresponding to Ni but no peak of crystalline NiO was found. The transmittance spectra of Ni uniformly and non-uniformly doped TiO2 thin films show blue shift and red shift’, respectively. Ni-doped TiO2 thin films can be used as photocatalyst for the photodegradation of methyl orange dye. It was found that, organic dye undergoes degradation efficiently in presence of non-uniformly Ni-doped TiO2 thin films when compared to uniformly doped films and pure TiO2 films under visible light. The photocatalytic activity increases with increase in the concentration of Ni in case of nonuniformly doped thin films but decreases with the concentration when uniformly doped thin films were used.

• 𝑝-AgCoO2/𝑛-ZnO heterojunction diode grown by rf magnetron sputtering

𝑃-type transparent semiconducting AgCoO2 thin films were deposited by rf magnetron sputtering of sintered AgCoO2 target. The AgCoO2 films grown by rf sputtering were highly 𝑐-axis oriented showing only (001) reflections in the X-ray diffraction pattern unlike in the case of amorphous films grown by pulsed laser deposition (PLD). The bulk powder of AgCoO2 was synthesized by hydrothermal process. The optical bandgap was estimated as 4.15 eV and has a transmission of about 50% in the visible region. The temperature dependence of conductivity shows a semiconducting behaviour. The positive sign of Seebeck coefficient (+220 𝜇VK–1) indicates 𝑝-type conductivity. Transparent 𝑝–𝑛 heterojunction on glass substrate was fabricated by rf magnetron sputtering of 𝑝-AgCoO2 and 𝑛-type ZnO : Al thin films. The structure of the diode was glass/ITO/𝑛-ZnO/𝑝-AgCoO2. The junction between 𝑝-AgCoO2 and 𝑛-ZnO was found to be rectifying.

• Strain induced anomalous red shift in mesoscopic iron oxide prepared by a novel technique

Nano magnetic oxides are promising candidates for high density magnetic storage and other applications. Nonspherical mesoscopic iron oxide particles are also candidate materials for studying the shape, size and strain induced modifications of various physical properties viz. optical, magnetic and structural. Spherical and nonspherical iron oxides having an aspect ratio, ∼2, are synthesized by employing starch and ethylene glycol and starch and water, respectively by a novel technique. Their optical, structural, thermal and magnetic properties are evaluated. A red shift of 0.24 eV is observed in the case of nonspherical particles when compared to spherical ones. The red shift is attributed to strain induced changes in internal pressure inside the elongated iron oxide particles. Pressure induced effects are due to the increased overlap of wave functions. Magnetic measurements reveal that particles are superparamagnetic. The marked increase in coercivity in the case of elongated particles is a clear evidence for shape induced anisotropy. The decreased specific saturation magnetization of the samples is explained on the basis of weight percentage of starch, a nonmagnetic component and is verified by TGA and FTIR studies. This technique can be modified for tailoring the aspect ratio and these particles are promising candidates for drug delivery and contrast enhancement agents in magnetic resonance imaging.

• Development and characterization of nickel–zinc spinel ferrite for microwave absorption at 2.4 GHz

This paper deals with the development and characterization of nickel–zinc spinel ferrite (Ni(1–𝛿) Zn𝛿Fe2O4) for microwave absorption at 2.4 GHz (ISM band). The ferrite powder was prepared by dry attrition and sintering process. Complex permittivity and permeability of the prepared sample have been determined by measuring its scattering parameters with the help of a vector network analyser. The measured parameters have been used to determine its wave absorption properties over a frequency range 2.1–2.6 GHz.

• A novel method for preparation of hollow and solid carbon spheres

Hollow and solid carbon spheres were prepared by the reaction of ferrocene and ammonium carbonate in a sealed quartz tube at 500°C. The morphology and microstructure of the product were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy. The carbon spheres are amorphous and their diameters range from 0.8–2.8 𝜇m. The shell thickness of the hollow carbon spheres is not uniform and ranges from 100–180 nm. It is suggested that ammonium carbonate is crucial for the formation of carbon spheres and its amount also influences the morphology of the product. The method may be suitable for large scale preparation of carbon spheres.

• Fourier transform infrared spectroscopic estimation of crystallinity in SiO2 based rocks

We present here optical properties and crystallinity index of quartz (SiO2) in natural rocks samples from the Mikir and Khasi hills, Assam, India. Infrared spectroscopy has been used to study the structure of quartz in rock samples and estimate the mining quality of quartz mineral, which is substantiated by calculating the crystallinity index. Systematic investigations of structure have been carried out in between 10 𝜇m (1000 cm–1) and 20 𝜇m (500 cm–1) bands of silicates. Investigation is based on the assignment of infrared bands to certain structural groups of SiO4 tetrahedra. The crystallinity of samples has been ascertained by comparing the ratio of intensity of the characteristic peak at 778 and 695 cm–1 with the corresponding ratio for a standard sample. The crystallinity parameter is calculated by using a standard procedure which can be used to estimate the distribution of quartz in various rocks for mining purpose. The infrared spectroscopic investigation is found to be an ideal tool for structure elucidation and for estimating quartz crystallinity of the natural samples.

• Low-frequency Raman scattering in alkali tellurite glasses

Raman scattering has been employed to study the alkali-cation size dependence and the polarization characteristics of the low-frequency modes for the glass-forming tellurite mixtures, 0.1M2O–0.9TeO2 (M = Na, K, Rb and Cs). The analysis has shown that the Raman coupling coefficient alters by varying the type of the alkali cation. The addition of alkali modifier in the tellurite network leads to the conversion of the TeO4 units to TeO3 units with a varying number of non-bridging oxygen atoms. Emphasis has also been given to the lowfrequency modes and particular points related to the low-frequency Raman phenomenology are discussed in view of the experimental findings.

• Synthesis of TiO2-doped SiO2 composite films and its applications

The TiO2-doped SiO2 composite films were prepared by two-step sol–gel method and then it was applied in the degradation of methylene red (MR) as photocatalysts. In XRD, FT–IR, and TEM investigations of these TiO2-doped SiO2 composite films, the titanium oxide species are highly dispersed in the SiO2 matrixes and exist in a tetrahedral form. And special attention has been focused on the relationship between the local structure of the titanium oxide species in the TiO2-doped SiO2 composite films and the photocatalytic reactivity in order to provide vital information for the design and application of such highly efficient photocatalytic systems in the degradation of toxic compounds diluted in a liquid phase.

• Mechanical properties of natural fibre reinforced polymer composites

During the last few years, natural fibres have received much more attention than ever before from the research community all over the world. These natural fibres offer a number of advantages over traditional synthetic fibres. In the present communication, a study on the synthesis and mechanical properties of new series of green composites involving Hibiscus sabdariffa fibre as a reinforcing material in urea–formaldehyde (UF) resin based polymer matrix has been reported. Static mechanical properties of randomly oriented intimately mixed Hibiscus sabdariffa fibre reinforced polymer composites such as tensile, compressive and wear properties were investigated as a function of fibre loading. Initially urea–formaldehyde resin prepared was subjected to evaluation of its optimum mechanical properties. Then reinforcing of the resin with Hibiscus sabdariffa fibre was accomplished in three different forms: particle size, short fibre and long fibre by employing optimized resin. Present work reveals that mechanical properties such as tensile strength, compressive strength and wear resistance etc of the urea–formaldehyde resin increases to considerable extent when reinforced with the fibre. Thermal (TGA/DTA/DTG) and morphological studies (SEM) of the resin and biocomposites have also been carried out.

• Effect of heat treatment on structure and magnetic properties of FeCoNi/CNTs nanocomposites

Fe46Co35Ni19/CNTs nanocomposites have been prepared by an easy two-step route including adsorption and heat treatment processes. We investigated the effect of heat treatment conditions on structure, morphology, nanoparticle sizes and magnetic properties of the Fe46Co35Ni19 alloy nanoparticles attached on the carbon nanotubes by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), energy-disperse X-ray spectroscopy (EDS) and vibrating sample magnetometer (VSM). When the reducing temperature changes from 300–450°С, a transition of the crystalline structure from bcc phase to 𝑓𝑐𝑐–𝑏𝑐𝑐 dual phase and an increase in particle size of Fe46Co35Ni19 nanoparticles together with a local maximum at 350°С are observed. Meanwhile, the saturation magnetization (𝑀s) for Fe46Co35Ni19 nanoparticles increases with the increase of reducing temperature and the coercivity (𝐻c) decreases rapidly with a local minimum at 350°С. When the reducing time (𝑡𝑟) changes from 2–5 h, bcc phase is predominant in the Fe46Co35Ni19 alloy particles. Both the particle size and 𝑀s have a maximum at 𝑡𝑟 = 3 h, and the 𝐻c reaches a maximum at 𝑡𝑟 = 4 h.

• Characterization of PAN/ATO nanocomposites prepared by solution blending

Conducting nanocomposites of polyacrylonitrile (PAN) and antimony-doped tin oxide (ATO) were prepared by solution blending. Electrical properties of the nanocomposites were characterized by means of electrical conductivity measurements and the phase structures were investigated via scanning electron microscopy (SEM), X-ray diffraction (XRD), thermogravimetric analyses (TGA) and dynamical mechanical analysis (DMA). This study unveiled a remarkable, interpenetrating network of chainlike nano-ATO within the PAN matrix, consistent with the existence of connected conducting paths at content as low as 4 wt% of the nano-ATO. The storage modulus of the nanocomposites increased with increasing content of ATO, due to formation of immobilized layer between polymer and filler. The interactions between ATO and PAN molecules resulted in high tan 𝛿 for the PAN/ATO nanocomposites. Thermal stability of the nanocomposites was found remarkably enhanced by the incorporation of nano-ATO.

• Optical and mechanical properties of diamond like carbon films deposited by microwave ECR plasma CVD

Diamond like carbon (DLC) films were deposited on Si (111) substrates by microwave electron cyclotron resonance (ECR) plasma chemical vapour deposition (CVD) process using plasma of argon and methane gases. During deposition, a d.c. self-bias was applied to the substrates by application of 13.56 MHz rf power. DLC films deposited at three different bias voltages (–60 V, –100 V and –150 V) were characterized by FTIR, Raman spectroscopy and spectroscopic ellipsometry to study the variation in the bonding and optical properties of the deposited coatings with process parameters. The mechanical properties such as hardness and elastic modulus were measured by load depth sensing indentation technique. The DLC film deposited at –100 V bias exhibit high hardness (∼ 19 GPa), high elastic modulus (∼ 160 GPa) and high refractive index (∼ 2.16–2.26) as compared to films deposited at –60 V and –150 V substrate bias. This study clearly shows the significance of substrate bias in controlling the optical and mechanical properties of DLC films.

• Synthesis and characterization of electroless Ni–P coated graphite particles

Electroless alkaline bath is used to coat Ni–P graphite particles of average size, 150 𝜇m. Amorphous nickel and graphite phases are observed in X-ray diffraction of the coated particles. The crystallite size from diffraction peaks is found to be 9.56 nm. The microstructural studies are carried out with field emission scanning electron microscope (SEM) on the uncoated and coated graphite particles. Uncoated particles showed irregular and fractured surfaces while the surface of coated particles revealed the presence of Ni–P globules. Sizes of Ni–P globules are observed to be in the range 175–250 nm. The presence of Ni and P are confirmed by the energy dispersive spectrometer results. The effect of coating bath composition is studied and an increasing trend in deposition is observed up to 50 gl–1 of stabilizer as well as up to 20 gl–1 of the reducing agent, however, the trend reverses afterwards. The phenomena of nucleation and growth of the Ni–P layer over the graphite surface have been demonstrated through SEM studies and a model has been proposed to demonstrate the growth mechanism of Ni–P globules.

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