Studies on the preparation and ethanol gas sensing properties of spinel Zn0.6Mn0.4Fe2O4 nanomaterials

Zn_1−xMn_xFe₂O₄ (x = 0, 0.2 and 0.4) nanomaterials were synthesized by sol–gel citrate method and studied structural and gas sensing properties. The structural characteristics of synthesized nanomaterials were studied by X-ray diffraction measurement (XRD) and transmission electron microscope (TEM). The results revealed that the particle size is in the range of 30–35 nm for Mn–Zn ferrite with good crystallinity. The gas sensing properties were studied towards reducing gases like LPG, CH_4, CO and ethanol and it is observed that Mn–Zn ferrite shows high response to ethanol at relatively lower operating temperature. The Zn_0.6Mn_0.4Fe₂O₄ nanomaterial shows better sensitivity towards ethanol at an operating temperature 300 °C. Incorporation of 1.5 wt.% Pd improved the sensitivity, selectivity, response time and reduced the operating temperature from 300 °C to 230 °C for ethanol sensor. The response time of 200 ppm ethanol in air is about 10s.     

Combustion synthesis of nano-sized tungsten carbide powder and effects of sodium halides

The synthesis of nano-size tungsten carbide powder has been investigated with a WO₃ + Mg + C + carbonate system using alkali halides. The effects of different types of alkali halides on combustion temperature and tungsten carbide formation were discussed. Sodium fluoride had a notable effect on the particle size of the product and the degree of transformation from the initial mixture. A small amount of ammonium carbonate activated the carburization of tungsten carbide by the gas phase carbon transportation. X-ray diffraction data and particle analysis showed that the final product synthesized from a WO₃–Mg–C–(NH₄)₂CO₃–NaF system contains pure-phase tungsten carbide with a particle size of 50–100 nm.     

Effect of annealing temperature on the photocatalytic activity of WO3 for O2 evolution

Commercial WO₃ powder was annealed in air at four different temperatures and characterized by XRD and BET. The samples were used for the photooxidation of H₂O to O₂ under visible light irradiation (λ > 420 nm) in the presence of IO₃⁻ and the evolved gases were analyzed by gas chromatography. The results showed that the WO₃ photocatalyst of monoclinic phase, which was obtained by annealing at 750 °C for 4 h, displayed the best activity in terms of O₂ evolution among all the samples. Moreover, the activity was also found to be slightly affected by the grain size of the WO₃ samples.     

Surface plasmon resonance in nano-gold antimony glass–ceramic dichroic nanocomposites: One-step synthesis and enhanced fluorescence application

A single-step melt-quench in situ thermochemical reduction technique has been used to synthesize a new series of Au° nanoparticles embedded antimony glass–ceramic (K₂O–B₂O₃–Sb₂O₃–ZnO) dichroic nanocomposites. X-ray and selected area electron diffractions manifest growth of Au° nanoparticles along (2 0 0) planes. The particle sizes obtained from X-ray diffraction patterns are found to vary in the range 4–21 nm. Dichroic behavior is attributed to the elliptical shape gold nanoparticles having aspect ratio 1.2, as observed from the transmission electron microscopy (TEM) images. The Au° nanoparticles exhibit surface plasmon resonance band (SPR) around 600 nm, which experiences red-shifts with increasing Au concentration. These nanocomposites when co-doped with Sm₂O₃ and excited at 949 nm, exhibit 2-fold intensification of 636 nm red emission transition (⁴G_5/2 → ⁶H_9/2) due to SPR induced local field enhancement of Au° nanoparticles and are promising materials for display applications.     

XPS study of WC formation process

The surface composition and chemical bonding state of WO₃ carburized in CO at 700°C have been investigated with X-ray photoelectron spectroscopy, in order to clarify the mechanism of WC formation. The experimental results show that the carburization process is based on a direct reaction of WO_x (x≦3) with free carbon which accumulates on the WO_x surface by the disproportionation of CO. A model for the WC formation process is also presented.     

Eley–Rideal reaction dynamics between O atoms on β-cristobalite (1 0 0) surface: A new interpolated potential energy surface and classical trajectory study

We present a theoretical study of the collisions of atomic oxygen with O-precovered β-cristobalite (1 0 0) surface. We have constructed a multidimensional potential energy surface for the O₂/β-cristobalite (1 0 0) system based mainly on a dense grid of density functional theory points by using the interpolation corrugation-reducing procedure. Classical trajectories have been computed for quasithermal (100–1500 K) and state-specific (e.g., collision energies between 0.01 and 4 eV) conditions of reactants for different O incident angles (θ_v). Atomic sticking and O_2(adsorbed) formation are the main processes, although atomic reflection and Eley–Rideal (ER) reaction (i.e., O₂ gas) are also significant, depending their reaction probabilities on the O incident angle. ER reaction is enhanced by temperature increase, with an activation energy derived from the atomic recombination coefficient (γ_O(θ_v = 0°, T)) equal to 0.24 ± 0.02 eV within the 500–1500 K range, in close agreement with experimental data. Calculated γ_O(θ_v = 0°, T) values compare quite well with available experimental γ_O(T) although a more accurate calculation is proposed. Chemical energy accommodation coefficient β_O(T) is also discussed as a function of ER and other competitive contributions.     

Synthesis, characterization and magnetic properties on nanocrystalline BaFe12O19 ferrite

Single phase BaM (BaFe₁₂O₁₉) ferrites are prepared by using sol–gel method. The preparing conditions of samples are investigated in detail, such as acid/nitrate ratio, the value of pH and annealing temperature. The best conditions on preparing BaFe₁₂O₁₉, which can be obtained on a Fe/Ba ratio of 12, the citric acid contents R = 3, the starting pH of solution is 9, and annealing temperature 950 °C. The thermal decomposition behavior of the dried gel was examined by TG–DSC, the structure and properties of powders were measured respectively by XRD techniques. The magnetic properties of barium ferrites are emphatically researched about the changing crystallite size and annealing temperature by the vibrating sample magnetometer (VSM). Magnetic measurement shows that the barium ferrite samples annealed at 1000 °C has the maximal coercive field of 5691.91 Oe corresponding to the maximal remnant magnetization of 35.60 emu/g and the sample synthesized at 1000 °C has the maximal saturation magnetization of 60.75 emu/g.     

Probing of inversion symmetry site in Eu-doped GdPO4 by luminescence study: Concentration and annealing effect

Eu³⁺-doped gadolinium orthophosphate (GdPO₄) (Eu³⁺ at%=0, 2, 5, 7, 10, 15, 20 and 30) nanoparticles have been prepared by ethylene glycol route and subsequently heated at 500 and 900 °C. The crystallite size increases with increasing heat-treatment temperature. Luminescence study shows that magnetic dipole transition (⁵D₀→⁷F₁) is prominent over the electric dipole transition (⁵D₀→⁷F₂), which has been attributed to occupancy of inversion symmetry site by more Eu³⁺ ions in Eu³⁺-doped GdPO₄. The luminescence intensity is enhanced as heat-treatment temperature increases from 500 to 900 °C due to the improved crystallinity. Optimum luminescence is observed for 5–7 at% Eu³⁺ in GdPO₄ nanoparticles. Above this concentration, luminescence intensity decreases due to concentration quenching effect. This is supported by lifetime study.     

Magnetic properties of FexCo1−x/CoyFe1−yFe2O4 composite under hydrothermal condition

The metal–ferrite composites Fe_xCo_1−x/Co_yFe_1−yFe₂O₄ are synthesized by using disproportion of Fe (II) and reduction of Co (II) by Fe⁰ under hydrothermal condition. The size of the particles of the composites decreases as the [KOH] decreasing. The composites are measured by TEM and it can be deduced that when [KOH] = 0.1, the size of the alloy body-centered cubic (BCC) in composites is 20 ± 7 nm, the size of the Cobalt ferrite (spinel) is 170 ± 50 nm. The maximal value of the saturation magnetization (Ms) of the composite is about 100.14 emu/g, which is synthesized under Co (II)/Fe (II) = 0.05, [KOH] = 1 N, T = 150 °C and t = 3 h. The value of Hc of the composite synthesized under Co (II)/Fe (II) = 0.5, t = 3 h, T = 150 °C and [KOH] = 10.2 mol/L is about 2878.19 Oe. The Fe–Co alloy is synthesized through a reduction reaction of the composites in a flowing gaseous mixture. There is a maximal value (302.9 emu/g) of the Ms for the alloys generated at 1000 °C, which is the Co_0.412Fe_0.588 alloy.     

Nano-sized polystyrene prepared using bifunctional vinyl urethane macromonomer in emulsion polymerization

The linear-type bifunctional vinyl urethane macromonomer (L-VUM: Mw; 40,453) was synthesized and applied to emulsion polymerization of styrene in DDI water. The structure of L-VUM was confirmed using ¹H NMR and FT-IR. The macromonomer served as a good nonionic surfactant resulted in stable polystyrene nanospheres. Polystyrene particles were prepared with various concentrations of macromonomoer (1–30 wt% refer to monomer), initiator (0.5–2 wt%) and different temperatures (60–80 °C). Monodisperse PS nanospheres with 30 wt% L-VUM have a number-average diameter (D_n) of 200 nm with good uniformity (1.011) and molecular weight (M_w) 231,180 g/mol. The particle morphology, molecular weight and distribution, uniformity and the stability of the nanospheres upon the reaction temperature and concentration of L-VUM will be thoroughly discussed.     

A new technique for the measurement of the product CO/CO2 ratio at the surface of char particles burning in a fluidized bed

A new experimental technique is proposed to measure the product CO/CO₂ ratio at the surface of spherical char particles during fluidized bed combustion. It is based on the measurement of the burning rate of a single char particle under low oxygen concentration conditions and on the use of an accurate prediction of the particle Sherwood number. This technique was applied to spherical char particles obtained from a bituminous coal which is characterized by a low attrition and fragmentation propensity. The product CO/CO₂ ratio was measured at a bed temperature of 850 °C and at a fluidization velocity of 0.3 m/s in a lab-scale apparatus operated with a bed of 0.5–0.6 mm sand. The char particle size was varied between 2 and 7 mm and the inlet oxygen concentration between 0.1% and 2.0%. Results showed that under the experimental conditions investigated carbon was mostly oxidized to CO₂ within the particle boundary layer, with a maximum fraction of carbon escaping as CO of 10–20% at the lowest oxygen concentrations and largest particle sizes.     

Transport properties and defect analysis of La1.9Sr0.1NiO4 + δ

The oxygen flux through La_1.9Sr_0.1NiO_4 + δ has been measured as a function of oxygen activity gradient and temperature (750–1000 °C). The oxygen nonstoichiometry was determined by thermogravimetry in the temperature range of 400–1000 °C and oxygen partial pressures of 0.0002–1 atm. The total conductivity was measured over a similar range of conditions. The oxide ion partial conductivity derived from the oxygen flux data is approximately 4 orders of magnitude lower than the total, mainly p-type electronic conductivity. The defect structure was derived based on the data. Combining the oxygen flux and oxygen nonstoichiometry, the self diffusion coefficient of oxygen interstitials was evaluated.     

Synthesis of multi-walled carbon nanotubes for NH3 gas detection

It has been recently demonstrated that carbon nanotubes (CNTs) represent a new type of chemical sensor capable of detecting a small concentration of molecules such as CO, NO₂, NH₃.In this work, CNTs were synthesized by chemical vapor deposition (CVD) on the SiO₂/Si substrate by decomposition of acetylene (C₂H₂) on sputtered Ni catalyst nanoparticles. Their structural properties are studied by atomic force microscopy, high-resolution scanning electron microscopy (HRSEM) and Raman spectroscopy. The CNTs grown at 700 °C exhibit a low dispersion in size, are about 1 μm long and their average diameter varies in the range 25–60 nm as a function of the deposition time. We have shown that their diameter can be reduced either by annealing in oxygen environment or by growing at lower temperature (less than 600 °C).We developed a test device with interdigital Pt electrodes on an Al₂O₃ substrate in order to evaluate the CNTs-based gas sensor capabilities. We performed room temperature current–voltage measurements for various gas concentrations. The CNT films are found to exhibit a fast response and a high sensitivity to NH₃ gas.     

Conversion of egg shell membrane to inorganic porous CexZr1−xO2 fibrous network

The binary system CeO₂–ZrO₂ is thermally stable and has superior reduction–oxidation properties. It has been commonly used in the three-way catalytic converters for automobiles. In this work, an inorganic biomorphic porous Ce_xZr_1−xO₂ fibrous network was successfully synthesized by using the egg shell membrane (ESM) as templates, and its morphology was a perfect replica of the original ESM. The synthesis involved a simple infiltration and calcination process. A fresh ESM was peeled from a chicken egg shell. It was soaked in a Ce(NO₃)₃ and Zr(NO₃)₄ mixture before it was calcined at 700 °C in ambient environment. The fibers in the biomorphic network had diameter ranged from 1 to 4 μm, and they were composed of Ce_xZr_1−xO₂ nanocrystallites having an average grain size of 10 nm.     

Epitaxial growth of highly transparent and conducting Sc-doped ZnO films on c-plane sapphire by sol–gel process without buffer

Highly transparent and conductive scandium doped zinc oxide (ZnO:Sc) films were deposited on c-plane sapphire substrates by sol–gel technique using zinc acetate dihydrate [Zn(CH₃COO)₂·2H₂O] as precursor, 2-methoxyethanol as solvent and monoethanolamine as a stabilizer. The doping with scandium is achieved by adding 0.5 wt% of scandium nitrate hexahydrate [(ScNO₃·6H₂O)] in the solution. The influence of annealing temperature (300–550 °C) on the structural, optical and electrical properties was investigated. X-ray Diffraction study revealed that highly c-axis oriented films with full-width half maximum of 0.16° are obtained at an annealing temperature of 400 °C. The surface morphology of the films was judged by SEM and AFM images which indicated formation of grains. The average transmittance was found to be above 92% in the visible region. ZnO:Sc film, annealed at 400 °C exhibited minimum resistivity of 1.91 × 10⁻⁴ Ω cm. Room-temperature photoluminescence measurements of the ZnO:Sc films annealed at 400 °C showed ultraviolet peak at 3.31eV with a FWHM of 11.2 meV, which are comparable to those found in high-quality ZnO films. Reflection high-energy electron diffraction pattern confirmed the epitaxial nature of the films even without introducing any buffer layer.     

Oxide ion conductivity and relaxation in CaREZrNbO7 (RE = La, Nd, Sm, Gd, and Y) system

CaREZrNbO₇ (RE = La, Nd, Sm, Gd and Y) system changed from fluorite (F)-type to pyrochlore (P)-type structure when the ionic radius ratios, r(Ca²⁺–RE³⁺)_av/r(Zr⁴⁺–Nb⁵⁺)_av were larger than 1.34. Thus, the La, Nd, and Sm compounds have a cubic P-type structure and the Gd and Y ones have a defect F-type structure. The electrical conductivity was measured using complex-plane impedance analysis over a wide temperature (300–750 °C) and frequency (1 Hz–1 MHz) ranges. The conductivity relaxation phenomenon was observed in these compounds and the relaxation frequencies were found to show Arrhenius-type behavior and activation energies were in good agreement with those obtained from high temperature conductivity plots. These results support the idea that the relaxation process and the conductivity have the same origin. The ionic conductivity of CaREZrNbO₇ (RE = La, Nd, Sm, Gd and Y) system showed the maximum at the phase boundary between the F-type and P-type phases. On the other hand, the activation energy for the conduction decreased in the F-type phase and increased in the P-type phase with increasing ionic radius ratio. Among the prepared compounds, CaGdZrNbO₇ showed the highest ionic conductivity of 9.47 × 10^− 3 S/cm at 750 °C which was about twice as high as that observed in Gd₂Zr₂O₇ (4.2 × 10^− 3 S/cm at 800 °C). The grain morphology observation by scanning electron microscope (SEM) showed well-sintered grains. AC impedance measurements in various atmospheres further indicated that they are predominantly oxide ion conductors at elevated temperatures (> 700 °C).     

Magnetic order in CaMn2Sb2 studied via powder neutron diffraction

This paper reports a neutron powder diffraction study of CaMn₂Sb₂ in the temperature range of 20–300 K. Collinear long-range antiferromagnetic order of manganese ions occurs below 85 K, where a transition is observed in the dc magnetic susceptibility measured with a single crystal. Short-range magnetic order, characterized by a broad diffraction peak corresponding to a d-spacing of approximately 4 Å (2θ≈22°), is also observed above 20 K. The long-range antiferromagnetic order is indexed by the chemical unit cell, indicating a propagation vector k=(0 0 0), with a refined magnetic moment of 3.38 μ_B at 20 K. Two possible magnetic models have been identified, which differ in spin orientation for the two manganese ions with respect to the ab plane. The model with spins oriented at a 25±2° angle relative to the ab plane gives an improved fit compared to the other model in which the spins are constrained to the ab plane. Representational analysis can account for a model involving a c-axis component only by the mixing of two irreducible representations.     

Preparation of WO3 nanoparticles and application to NO2 sensor

WO₃ nanoparticles were prepared by evaporating tungsten filament under a low pressure of oxygen gas, namely, by a gas evaporation method. The crystal structure, morphology, and NO₂ gas sensing properties of WO₃ nanoparticles deposited under various oxygen pressures and annealed at different temperatures were investigated. The particles obtained were identified as monoclinic WO₃. The particle size increased with increasing oxygen pressure and with increasing annealing temperature. The sensitivity increased with decreasing particle size, irrespective of the oxygen pressure during deposition and annealing temperature. The highest sensitivity of 4700 to NO₂ at 1 ppm observed in this study was measured at a relatively low operating temperature of 50 °C; this sensitivity was observed for a sensor made of particles as small as 36 nm.     

Oxygen vacancy-induced aging of Mn-doped Ba0.8Sr0.2TiO3 ceramics in paraelectric and ferroelectric state

The aging properties of 0.01 mol% Mn-doped Ba_0.8Sr_0.2TiO₃ ceramics have been investigated from 30 °C to 400 °C at various frequencies. Decreases in ε′(T) of the aged sample compared to the fresh one around the tetragonal–cubic transition and in the regime of diffusion have been observed. The activation energy E_a = 1.25 eV obtained from the J–T loop at zero electric field indicates that oxygen vacancies dominate in the aging. The symmetry-conforming principle of point defects was employed to explain the time and temperature dependence of aging in the dielectric constant and double/constricted P–E loops of the samples aged in the paraelectric and ferroelectric state.     

Synthesis, phase and microstructure characteristics of Pb(Zr0.52Ti0.48)O3–(Bi3.25La0.75)Ti3O12 ceramics

Ceramics with formula (1 − x)Pb(Zr_0.52Ti_0.48)O₃–x(Bi_3.25La_0.75)Ti₃O₁₂ (when x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) were prepared by a solid-state mixed-oxide method and sintered at temperatures between 950 °C and 1250 °C. It was found that the optimum sintering temperature was 1150 °C at which all the samples had densities at least 95% of theoretical values. Phase analysis using X-ray diffraction indicated the existence of BLT- as well as PZT-based solid solutions with corresponding lattice distortion. Scanning electron micrographs of ceramic surfaces showed a plate-like structure in BLT-rich phase while the typical grain structure was observed for PZT-rich phase. The grain sizes of both pure BLT and PZT ceramics were found to decrease as the relative amount of the other phase increased. This study suggested that tailoring of properties of this PZT–BLT system was possible especially on the BLT-rich side due to its large solubility limit.