Elucidating iron doping induced n- to p- characteristics of Strontium titanate based ethanol sensors

A series of pure and iron doped strontium titanate, (SrFe_xTi_1-xO₃; x = 0, 0.1 and 0.2) powders were synthesized, characterized and used to fabricate ethanol sensors for low concentration. X-Ray Diffraction (XRD) technique was used to confirm the single phase formation. Microstructural properties of the powders were investigated using scanning electron microscopy (SEM). Electrical conductivity of all the samples at room temperature (RT) was measured. Sensors were optimized for best responsiveness by varying the operating temperature from 350 °C to 500 °C.The sensor with doping x = 0.2 exhibited best sensing response at 400 °C for ethanol gas. The undoped sensor demonstrated a decrease in resistance on exposure to ethanol gas whereas Fe-doped sensors showed increase in resistance. The doping induced changeover from n to p behavior in the sensing response on doping has been investigated and corroborated with an observed shift in the Fermi level position by X-ray photoelectron spectroscopy (XPS). The disparity in gas sensing response clearly demonstrates inter-connection of multiple influencing factors such as electrical conductivity, morphology, porosity and change in chemical composition on doping. The sensors were exposed to ethanol, nitrogen dioxide, carbon monoxide, butane gases at concentration between 5 ppm and 50 ppm. The sensor exhibited much reduced relative response to all gases other than ethanol which can be utilized for wide range of applications.     

Enhanced acetone gas sensing performance of the multiple-networked Fe2O3-functionalized In2O3 nanowire sensor

In₂O₃ nanowires functionalized with Fe₂O₃ nanoparticles were synthesized by the thermal evaporation of In₂S₃ powders in an oxidizing atmosphere followed by the solvothermal deposition of Fe₂O₃ and their acetone gas sensing properties were examined. The pristine and Fe₂O₃-functionalized In₂O₃ nanowires exhibited responses of 141–390% and 298–960%, respectively, to 10–500 ppm acetone at 200 °C. The Fe₂O₃-functionalized In₂O₃ nanowire sensor showed stronger electrical response to acetone gas at 200 °C than the pristine In₂O₃ nanowire counterpart. The former showed more rapid response but slower recovery than the latter. Both the pristine and Fe₂O₃-functionalized In₂O₃ nanowire sensors showed the strongest response to acetone gas at 200 °C. The underlying mechanism for the enhanced sensing performance of the Fe₂O₃-functionalized In₂O₃ nanowire sensor towards acetone gas is discussed.     

Hybrid inorganic–organic proton conducting membranes for fuel cells and gas sensors

We developed new fast proton conducting membranes based on a hybrid inorganic–organic phosphosilicate polymer synthesized from othophosphoric acid, dichlorodimethylsilane, and tetraethoxysilane. The membranes were amorphous, translucent, and flexible. A high concentration of –OH groups and short distances between them promoted fast proton conductivity in dry atmosphere at increased temperatures. The proton conductivity was measured using the electrochemical impedance spectroscopy. Its value increased with rising temperature following the Arrhenius dependence with the activation energy 20 kJ/mol. In dry conditions at 120 °C, the conductivity was 1.6 S/m. The tests in a H₂/O₂ fuel cell confirmed that the membrane was able to operate at temperatures from 100 to 130 °C using dry input gas streams. The cell performance significantly improved with increasing temperature. The membrane was also tested in a potentiometric gas sensor with the TiH_x reference electrode and the Pt sensing electrode. The sensor exhibited fast, stable, and reproducible response to dry H₂ and O₂ gases at temperatures above 100 °C. We expect the application of our membrane in intermediate temperature fuel cells and gas sensors operating in dry conditions.     

Microstructure and performance of novel Ni anode for hollow fibre solid oxide fuel cells

Nickel anodes were deposited on hollow fibre yttria-stabilised zirconia (YSZ) electrolyte substrates for use in solid oxide fuel cells (SOFCs). The hollow fibres are characterised by porous external and internal surfaces supported by a central gas-tight layer (300 μm total wall thickness and 1.6 mm external diameter). The YSZ hollow fibres were prepared by a phase inversion technique followed by high temperature sintering in the range 1200 to 1400 °C. Ni anodes were deposited on the internal surface by electroless plating involving an initial catalyst deposition step with PdCl₂ followed by Ni plating (with a NiSO₄, NaH₂PO₂ and sodium succinate based solution at 70 °C). Fabrication and nickel deposition parameters (nature of solvents, air gap, temperature, electroless bath composition) and heat treatments in oxidising/reducing environments were investigated in order to improve anode and electrolyte microstructure and fuel cell performance. A parallel study of the effect of YSZ sintering temperature, which influences electrolyte porosity, on electrolyte/anode microstructure was performed on mainly dense discs (2.3 mm thick and 15 mm diameter). Complete cells were tested with both disc and hollow fibre design after a La_0.2Sr_0.8Co_0.8Fe_0.2O_3?δ (LSCF) cathode was deposited by slurry coating and co-fired at 1200 °C. Anodes prepared by Ni electroless plating on YSZ electrolytes (discs and hollow fibres) sintered at lower temperature (1000–1200 °C) benefited from a greater Ni penetration compared to electrolytes sintered at 1400 °C. Further increases in anode porosity and performance were achieved by anode oxidation in air at 1200–1400 °C, followed by reduction in H₂ at 800 °C.     

Fabrication and characterization of solid state proton conductor (NH4)2SiP4O13–NH4PO3 for fuel cells operated at 150–250 °C

NH₄PO₃–(NH₄)₂SiP₄O₁₃ composite, a potential electrolyte for intermediate temperature fuel cells that operated around 250 °C, was synthesized with a solid-state reaction method. Electromotive forces (emfs) as measured with hydrogen concentration cells showed that the composite was a pure proton conductor at hydrogen partial pressure from 10² to 10⁵ Pa. Its proton transference numbers were determined to be 1.0 at 150 °C, 0.99 at 200 °C, and 0.99 at 250 °C. Fuel cells that used NH₄PO₃–(NH₄)₂SiP₄O₁₃ as electrolytes were also fabricated. Maximum power density was 6.6 mW/cm² at 250 °C when dry hydrogen and dry oxygen were used as the fuel and oxidant, respectively. Improved cell performance is expected by increasing cathode activity, increasing the electrolyte density, and decreasing the electrolyte thickness.     

A simple MOD method to grow a single buffer layer of Ce0.8Gd0.2O1.9 (CGO) for coated conductors

A single Ce_0.8Gd_0.2O_1.9 (CGO) buffer layer was successfully grown on the home-made textured Ni–5 at.%W (Ni–5W) substrates for YBCO coated conductors by a simple metal–organic deposition (MOD) technique. The precursor solution was prepared using a newly developed process and only contained common metal–organic salts of both Ce and Gd dissolved into a propionic acid solvent. The precursor solution at 0.4 M concentration was spin coated on short samples of Ni–5W substrates and heat-treated at 1100 °C in a mixture gas of 5% H₂ in Ar for an hour. X-ray studies indicated that the CGO films had good out-of-plane and in-plane textures with full-width-half-maximum values of 4.18° and 6.19°, respectively. Atomic force microscope (AFM) investigations of the CGO films revealed that most of the grain boundary grooves on the Ni–5W surface were found to be well covered by CGO layers, which had a fairly dense and smooth microstructure without cracks and porosity. These results indicate that our MOD technique is very promising for further development of single buffer layer architecture for YBCO coated conductors, due to its low cost and simple process.     

Growth of single wall carbon nanotubes using PECVD technique: An efficient chemiresistor gas sensor

In this work, the uniform and vertically aligned single wall carbon nanotubes (SWCNTs) have been grown on Iron (Fe) deposited Silicon (Si) substrate by plasma enhanced chemical vapor deposition (PECVD) technique at very low temperature of 550 °C. The as-grown samples of SWCNTS were characterized by field emission scanning electron microscope (FESEM), high resolution transmission electron microscope (HRTEM) and Raman spectrometer. SWCNT based chemiresistor gas sensing device was fabricated by making the proper gold contacts on the as-grown SWCNTs. The electrical conductance and sensor response of grown SWCNTs have been investigated. The fabricated SWCNT sensor was exposed to ammonia (NH₃) gas at 200 ppm in a self assembled apparatus. The sensor response was measured at room temperature which was discussed in terms of adsorption of NH₃ gas molecules on the surface of SWCNTs. The achieved results are used to develope a miniaturized gas sensor device for monitoring and control of environment pollutants.     

Catalyst free rutile phase TiO2 nanorods as efficient hydrogen sensor with enhanced sensitivity and selectivity

Using a low-cost hydrothermal method, we demonstrated the fabrication of phase pure rutile phase high-density vertically aligned TiO₂ nanorods-based catalyst-free hydrogen (H₂) gas sensor. The synthesized TiO₂ nanorods on FTO are decorated with the aluminum interdigitated electrode pattern for electrical measurements. TiO₂ nanorods-based hydrogen sensor showed the optimum response of ∼53.18% at 150 ppm H₂ concentration relative to air at 100 °C. The measured response and recovery time of TiO₂ nanorods are 85 and 620 s, respectively. The TiO₂ nanorods-based H₂ gas sensor showed a relatively better response, good reproducibility, and stability at moderate temperatures, i.e., 50 and 100 °C. The electrochemical impedance measurements showed a small variation in the surface characteristics of TiO₂ nanorods before and after exposing H₂ gas. The carrier lifetime at 50 °C and 100 °C at 150 ppm are 5 μs and 3 μs, respectively. Interestingly, H₂ selectivity is also observed against H₂S, CO, and NH₃ gases, suggesting that high-density vertically aligned TiO₂ nanorods can be a good candidate for efficient hydrogen sensing at relatively low temperatures.     

Mössbauer and magnetic studies on nanocrystalline NiFe2O4 particles prepared by ethylene glycol route

NiFe₂O₄ nanoparticles have been synthesized by co-precipitation method at 145°C in N₂ atmosphere using ethylene glycol as solvent and capping agent. This gives the promising synthesis route for nanoparticles at low temperature. The as-synthesized NiFe₂O₄ is subsequently heated at 400°C, 500°C, 700°C and 800°C. Crystallite size increases with the heat treatment temperature. The heat treatment temperature has direct effect on the electron paramagnetic resonance and intrinsic magnetic properties. The room temperature Mössbauer spectrum of the 800°C heated sample shows the two sextets pattern indicating that the sample is ferrimagnetic and Fe^3?+? ions occupy both tetrahedral and octahedral sites of spinel structure.     

On the incorporation of fluorine into the manganese spinel cathode lattice

A series of spinel oxy-fluorides with the formula LiMn_1.8Li_0.1Ni_0.1O_4 ? ηF_η have been synthesized by both the conventional high-temperature (800 °C) firing method with LiF and a low temperature (450 °C) firing process with NH₄HF₂. Interestingly, the samples obtained by the high temperature (800 °C) procedure show no fluorine in the sample as revealed by the chemical analysis data, but an increase in lattice parameter and capacity values was observed due to a decrease in lithium content caused by the volatilization of LiF during the high temperature (800 °C) firing process. In contrast, the low-temperature fluorine doping approach was successful in incorporating fluorine into the spinel lattice, and the sample LiMn_1.8Li_0.1Ni_0.1O_3.85F_0.15 exhibits a significant increase in discharge capacity compared to the oxide analog.     

Synthesis of corundum structure ITO nanocrystals by hydrothermal process at low pressure and low temperature

The corundum structures of In₂O₃:Sn (ITO) nanoparticles were synthesized by hydrothermal processing of InCl₃ and SnCl₄·5H₂O precursor at low temperature of 250 °C and 40 bar pressure for 3 h. The precursor was precipitated in a white gel of InOOH. After drying at 150 °C in air, it was crystallized in orthorhombic structure. InOOH powder was transformed into dark-gray rhombohedral In₂O₃ by sintering at 420 °C in forming gas for 1 h. The samples were characterized by means of XRD, SEM, and TEM. The particle size of the resulted ITO powder was about 32 nm.     

Genesis of supported carbon-coated Co nanoparticles with controlled magnetic properties,prepared by decomposition of chelate complexes

Following procedures formerly developed for the preparation of supported heterogeneous catalysts, carbon-coated cobalt nanoparticles dispersed on porous alumina have been prepared by impregnation of γ-Al₂O₃ with (NH₄)₂[Co(EDTA)] and thermal decomposition in inert atmosphere. Below 350 °C, Co(II) ions are complexed in a hexa-coordinated way by the EDTA ligand. The thermal treatment at 400–900 °C leads to the EDTA ligand decomposition and recovering of the support porosity, initially clogged by the impregnated salt. According to X-ray absorption spectroscopy, and due to in situ redox reactions between the organic ligand and Co(II), both oxidic and metallic cobalt phases are formed. Characterisation by transmission electron microscopy, X-ray diffraction and magnetic measurements reveals that an increase in the treatment temperature leads to an increase of the degree of cobalt reduction as well as to a growth of the cobalt metal particles. As a consequence, the samples prepared at 400–700 °C exhibit superparamagnetism and a saturation magnetisation of 1.7–6.5 emu g⁻¹ at room temperature, whilst the sample prepared at 900 °C has a weak coercivity (0.1 kOe) and a saturation magnetisation of 12 emu g⁻¹. Metal particles are homogeneously dispersed on the support and appear to be protected by carbon; its elimination by a heating in H₂ at 400 °C is demonstrated to cause sintering of the metal particles. The route investigated here can be of interest for obtaining porous magnetic adsorbents or carriers with high magnetic moments and low coercivities, in which the magnetic nanoparticles are protected from chemical aggression and sintering by their coating.     

Dielectric permittivity of nickel ferrites at microwave frequencies 1 MHz to 1.8 GHz

NiFe₂O₄ prepared via the sol–gel technique were pre-sintered at 900 °C and synthesized at different sintering temperatures from 1,000 °C to 1,200 °C at 100 °C intervals. The samples were characterized for microwave dielectric properties. These samples were measured using Agilent Impedance/Material Analyzer at frequencies 1 MHz to 1.8 GHz. Results showed a decrease in the dielectric constant and loss factor with frequency except at the turning point, around 150 MHz, where the loss factor showed a gradual increase. However, both the dielectric constant and loss factor increase with increasing sintering temperature. The grain size and density also increased with increasing sintering temperature, but the porosity and grain boundary density showed a decrease. This paper was presented at the International Conference on Solid State Science and Technology 2006, Kuala Terengganu, Malaysia, Sept. 4–6, 2006.     

Characterization and gas-sensing properties of NiO nanowires prepared through hydrothermal method

NiO nanowires with high aspect ratio and dispersive distribution have been synthesized by a hydrothermal reaction of NiCl₂ with Na₂C₂O₄ and H₂O in the simultaneous presence of ethylene glycol (EG) and polyethylene glycol (PEG). Then the products were obtained by the subsequent annealing at 400 °C in air. The effect of –OH from EG and –O– from PEG in the formation of nanowires was discussed. And the gas sensing properties of the as-prepared NiO nanowires toward ethanol were investigated. A novel formation mechanism of nanowires was presented and the NiO nanowires were proved to have an excellent gas sensing performance.     

Synthesis of V O2(A) nanobelts by the transformation of V O2(B) under the hydrothermal treatment and its optical switching properties

V O₂(A) nanobelts had been successfully synthesized by the transformation of V O₂(B) using H₂O as the solvent under the hydrothermal approach at 280 °C for 48 h. Some parameters, such as the reaction temperature and time, had been briefly discussed to reveal the transition from V O₂(B) to V O₂(A). It was found that H₂O played a crucial role in the transition from V O₂(B) to V O₂(A). The phase transition of V O₂(A) nanobelts was at 162 °C. The optical switching properties of V O₂(A) were studied by the variable-temperature infrared spectra for the first time. In addition, V O₂(A) nanobelts were calcined at 700 °C for 2 h under a high purity Ar (99.999%) atmosphere to obtain V O₂(M) which exhibited a strong crystallographic transition at around 65 °C.     

Anatase TiO2 films fabricated by pulsed laser deposition using Ti target

TiO₂ films were prepared by pulsed laser deposition using a metallic Ti target in an O₂ gas ambient. The microstructure along with optical and photocatalytic properties of the deposited films were systematically studied by changing the deposition parameters and substrates. It was found that TiO₂ films having nearly pure anatase phase grew effectively in O₂ atmosphere. When the films were fabricated at a substrate temperature of 400°C, their phase structures were greatly affected by the O₂ gas pressure, and nearly pure anatase phase with typical (101) and (004) peaks can be obtained under an O₂ pressure of 15 Pa. For the deposition at 700°C, the crystal structure of the TiO₂ films exhibited a strong anatase (004) peak and was inert to the oxygen pressures. Two modes, namely a substrate-temperature-controlled mode and an oxygen-pressure-controlled mode, were considered for the growth of the anatase TiO₂ films under different substrate temperatures. In addition, the optical and photocatalytic properties were found to be sensitive to both the microstructure and grain size of the TiO₂ films.     

Enhancement of conductivity in La2Mo2O9 ceramics fabricated by a novel three-stage thermal processing method

Pure and dense La₂Mo₂O₉ ceramic electrolytes with grain sizes of 1–3 μm were fabricated from nanocrystalline powders by a novel three-stage, one-cycle, pressureless thermal processing method at temperatures as low as 600 °C. Phase formation, microstructure and grain size of the samples were examined using X-ray diffraction and scanning electron microscopy. Density of the sintered samples was determined as in the range of 94–96% of the theoretical density by weight/geometric measurements. Impedance spectroscopy was used to characterize the electrical properties of the sintered samples. The conductivity of the three-stage sintered samples reaches a value of 0.018 S/cm at 600 °C and 0.05 S/cm at 700 °C, much higher than that of the samples fabricated by conventional solid-state reaction method, but similar to that of the samples sintered at 950 °C for 12 h from the same nanocrystalline powders. The high conductivity of these samples was attributed to the co-operation of the excellent performance of nanocrystalline powders and the advantages of the novel three-stage low-temperature thermal processing.     

Hydrothermal synthesis and gas sensing properties of?single-crystalline ultralong ZnO nanowires

Ultralong ZnO nanowires were successfully synthesized by a simple hydrothermal reaction of Zn foil and aqueous Na₂C₂O₄ solution at 140°C. The as-synthesized ZnO nanowires are single crystalline with the wurtzite structure and grow in the [0001] direction. The role of Na₂C₂O₄ in the formation of ultralong ZnO nanowires was investigated, and a possible mechanism was also proposed to account for the formation of the ultralong ZnO nanowires. The gas sensor fabricated on the basis of the ultralong ZnO nanowires showed excellent response characteristics towards NH₃ and N(C₂H₅)₃ vapors with low concentration, and its detection limits for NH₃ and N(C₂H₅)₃ are about 0.2 and 0.15 ppm at the working temperature of 180°C, respectively. This result suggests potential applications of the ultralong ZnO nanowires in monitoring flammable, toxic and corrosive gases.     

Microstructure and electrode properties of La0.6Sr0.4Co0.2Fe0.8O3-δ spin-coated on Ce0.8Sm0.2O2?δ electrolyte

Fine and uniform La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ powder was synthesized by a glycine–nitrate combustion process. La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ electrodes were prepared on dense Ce_0.8Sm_0.2O_2−δ electrolyte substrates using a spin-coating technique by sintering at 900–1,000 °C. The electrode properties of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ were investigated by electrochemical impedance spectroscopy and chronopotentiometry techniques with respect to preparation conditions and the resulting microstructures. The results indicate a significant effect of the microstructure on the electrode processes and polarization characteristics. The oxygen adsorption and dissociation process acted as a larger contribution to the overall electrode polarization R _p in magnitude compared with the charge transfer process due to relatively low porosity levels of the electrodes. It was detected that the grain size of the electrodes exhibited a crucial role on the electrocatalytic reactivity. At 800 °C, the electrode sintered at 950 °C attained a polarization resistance of 0.18 Ω cm², an overpotential of 27 mV at a current density of 200 mA cm⁻², and an exchange current density of 308 mA cm⁻².     

Crystallization and conductivity of 2CaO–La2O3–5P2O5 glass–ceramic with Al2O3 addition

Al₂O₃ was added to a 2CaO–La₂O₃–5P₂O₅ metaphosphate, to replace 10% of the Ca²⁺ ions by Al³⁺, forming a phosphate with the nominal composition 1.8CaO–0.1Al₂O₃–La₂O₃–5P₂O₅. The effect of Al₂O₃ addition and heat treatment on the microstructure and conductivity of the resulting glass–ceramics was investigated by XRD, SEM, TEM, and AC impedance spectroscopy. Upon transformation from glass to glass–ceramic, conductivities increased significantly. The glasses were isochronally transformed at 700 and at 800 °C for 1 h or 5 h, in air, following heating at 3 or 10 °C/min. With Al₂O₃ addition, after a heat treatment at 700 °C, 100–300 nm nano-domains of LaP₃O₉ crystallized from the glass matrix. Annealing at 800 °C produced a further order of magnitude conductivity increase for the Al-free glass, but less so for the Al-containing glass.