Synthesis of nanorods and mixed shaped copper ferrite and their applications as liquefied petroleum gas sensor

Present paper reports the preparation and characterization of nanorods and mixed shaped (nanospheres/nanocubes) copper ferrite for liquefied petroleum gas (LPG) sensing at room temperature. The structural, surface morphological, optical, electrical as well as LPG sensing properties of the copper ferrite were investigated. Single phase spinel structure of the CuFe₂O₄ was confirmed by XRD data. The minimum crystallite size of copper ferrite was found 25 nm. The stoichiometry was confirmed by elemental analysis and it revealed the presence of oxygen, iron and copper elements with 21.91, 12.39 and 65.70 atomic weight percentages in copper ferrite nanorods. The band gap of copper ferrite was 3.09 and 2.81 eV, respectively for nanospheres/nanocubes and nanorods. The sensing films were made by using screen printing technology and investigated with the exposure of LPG. Our results show that the mixed shaped CuFe₂O₄ had an improved sensing performance over that of the CuFe₂O₄ nanorods, of which a possible sensing mechanism related to a surface reaction process was discussed. Sensor based on mixed shaped copper ferrite is 92% reproducible after one month. The role of PEG in the synthesis for obtaining nanospheres/nanocubes has also been demonstrated.     

Surface study of fine MgFe2O4 ferrite powder prepared by chemical methods

To study surface behaviors, MgFe₂O₄ ferrite materials having different grain sizes were synthesized by two different chemical methods, i.e., a polymerization method and a reverse coprecipitation method. The single phase of the cubic MgFe₂O₄ was confirmed by the X-ray diffraction method for both the precursors decomposed at 600-1000 °C except for a very small peak of Fe₂O₃ was detected for the samples calcined at 600 and 700 °C by the polymerization method. The crystal size and particle size increased with an increase in the sintering temperature using both methods. The conductance of the MgFe₂O₄ decreased when the atmosphere was changed from ambient air to air containing 10.0 ppm NO₂. The conductance change, C = G(air)/G(10 ppm NO₂), was reduced with an increase in the operating temperature. For the polymerization method, the maximum C-value was ca. 40 at 300 °C for the samples sintered at 900 °C. However, the samples sintered at 1000 °C showed a low conductance change in the 10 ppm NO₂ gas, because the ratio of the O₂ gas adsorption sites on the particle surface is smaller than those of the samples having a high C-value. The low Mg content on the surface affects the low ratio of the gas adsorption sites. For the reverse coprecipitation method, the particle size was smaller than that of the polymerization method. Although a stable conductance was obtained for the sample sintered at 900 and 1000 °C, its conductance change was less than that of the polymerization method.     

Investigations on Pd:SnO2/porous silicon structures for sensing LPG and NO2 gas

P-type porous silicon (PS) structure has been prepared by anodic electrochemical etching process under optimized conditions. Photoluminescence studies of the PS structure show emission at longer wavelengths (red) for the excitation at 365 nm. Scanning electron microscope investigations of the PS surface confirm the formation of uniform porous structure, and the pore diameter have been estimated as 25 μm. Pd:SnO₂/PS/p-Si heterojunction with top gold ohmic contact developed by conventional methods has been used as the sensor device. Sensing properties of the device towards liquefied petroleum gas (LPG) and NO₂ gas have been investigated in an indigenously developed sensor test rig. The response and recovery characteristics of the sensor device at different operating temperatures show short response time for LPG. From the studies, maximum sensitivity and optimum operating temperature of the device towards LPG and NO₂ gas sensing has been estimated as 69% at 180 °C and 52% at 220 °C, respectively. The developed sensor device shows a short response time of 25 and 57 s for sensing LPG and NO₂ gases, respectively. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamilnadu, India, Dec. 7–9, 2006.     

High temperature and low current density synthesis of Mn3O4 porous nano spheres: Characterization and electrochemical properties

Uniform and single-crystalline Mn₃O₄ nano-spheres were synthesized by cathodic electrodeposition at high temperature (80 °C) and low current density (0.25 mA cm⁻¹) on steel electrode. Further the annealed samples were characterized for their structural and morphological properties by means of X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) studies. TEM and SEM images showed that particles have spherical shapes and the average diameter size was about 50 nm. Formation of Mn₃O₄ compound was confirmed from FTIR studies. The XRD pattern showed that the Mn₃O₄ exhibit tetragonal hausmannite structure. The results of N₂ adsorption-desorption analysis indicated that Mn₃O₄ nano-sphere has BET surface area of about 177.6 m² g⁻¹ and average pore diameters of 3 and 4 nm. The possible formation mechanism of Mn₃O₄ nanostructures has been discussed. The supercapacitive properties of Mn₃O₄ sample in 0.5 M Na₂SO₄ electrolyte showed maximum supercapacitance of 235.4 Fg⁻¹ at scan rate 10 mV s⁻¹. Coulumbic efficiency could be kept about 90% during 1000 cycles at 10 mV s⁻¹.     

径向生长的具有分级结构的四氧化三钴微晶及其在气体传感上的应用

通过在水热合成后追加退火处理,制备了径向生长的具有分级结构的树枝状三维Co₃O₄晶体,并用X射线衍射仪、扫描电子显微镜和透射电子显微镜对其结构和形貌进行了表征. 在110 oC对其气体探测性能的研究表明这种Co₃O₄分级结构对氨气有较高的探测灵敏度和响应速度(10 s),性能稳定并具有可重复性. 同时,还在较低的探测温度下对酒精、丙酮和苯进行了气敏探测.     

Response improvement for In2O3-TiO2 thick film gas sensors

In₂O₃ is introduced into TiO₂ by sol-gel method to improve the response/recovery rate and expand the operating temperature, when the In₂O₃-TiO₂ mixed system is exposed to H₂/O₂. The sensor is fabricated by thick film technology. Influence of In₂O₃ on the film phase composition, microstructure and sensing characteristics is discussed. Dynamic response properties show that the operating temperature of the mixed system is at 500-800 °C, which is about 600-800 °C for pure TiO₂. Response time of the sensor is about 200-260 ms (millisecond) while recovery time is in a narrow range of 60-280 ms at 600-800 °C. The promoting mechanism is suggested to arise from the introduction of In₂O₃ and grain size effect of the sensing film. Then In₂O₃-TiO₂ thick films are surface-modified by Pt using chloroplatinic acid. The promoting effect of Pt dispersed on the mixed system is also investigated.     

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.     

Effect of BiFeO3 addition on Bi2O3–ZnO–Nb2O5 based ceramics

In this paper, low temperature sintering of the Bi₂(Zn_1/3Nb_2/3)₂O₇ (β-BZN) dielectric ceramics was studied with the use of BiFeO₃ as a sintering aid. The effects of BiFeO₃ contents and the sintering temperature on the phase structure, density and dielectric properties were investigated. The results showed that the sintering temperature could be decreased and the dielectric properties could be retained by the addition of BiFeO₃. The structure of BiFeO₃ doped β-BZN was still the monoclinic pyrochlore phase. The sintering temperature of BiFeO₃ doped β-BZN ceramics was reduced from 1000 °C to 920 °C. In the case of 0.15 wt.% BiFeO₃ addition, the β-BZN ceramics sintered at 920 °C exhibited good dielectric properties, which were listed as follows: ε_r = 79 and tan δ = 0.00086 at a frequency of 1 MHz. The obtained properties make this composition to be a good candidate for the LTCC application.     

Magnetic and electrical properties of bulk BaTiO3+MgFe2O4 composite

BaTiO₃+MgFe₂O₄ material system was synthesized by hybrid chemical process using chlorides and nitrates of barium, titanium, iron, and magnesium. Magnetic properties of the composite samples measured as a function of annealing conditions indicated soft magnetic behavior. Saturation specific magnetization from 8 21 emu/g was observed for samples annealed at temperature between 950 and 1150 °C. Variation of specific saturation magnetization with respect to annealing temperature was related with the distribution of Fe cations in the tetrahedral and octahedral sites of MgFe₂O₄. Electrical properties of the samples annealed at different temperatures were measured to analyze the coexistence of ferroelectric phase. Dielectric constant varying from 15 to 200 with respect to frequency was observed for samples annealed from 950 to 1150 °C.     

Synthesis and magnetic properties of hard magnetic (CoFe2O4)-soft magnetic (Fe3O4) nano-composite ceramics by SPS technology

CoFe₂O₄/Fe₃O₄ nano-composite ceramics were synthesized by Spark Plasma Sintering. The X-ray diffraction patterns show that all samples are composed of CoFe₂O₄ and Fe₃O₄ phases when the sintering temperature is below 900 °C. It is found that the magnetic properties strongly depend on the sintering temperature. The two-step hysteresis loops for samples sintered below 500 °C are observed, but when sintering temperature reaches 500 °C, the step disappears, which indicates that the CoFe₂O₄ and Fe₃O₄ are well exchange coupled. As the sintering temperature increases from 500 to 800 °C, the results of X-ray diffractometer indicate the constriction of crystalline regions due to the ion diffusion at the interfaces of CoFe₂O₄/Fe₃O₄ phases, which have great impact on the magnetic properties.     

Highly sensitive room-temperature gas sensors based on hydrothermal synthesis of Cr2O3 hollow nanospheres

This paper reports that Cr₂O₃ hollow nanospheres（HNs） were synthesized via a hydrothermal approach and characterized by scanning electron microscopy,x-ray powder diffraction,transmission electron microscopy（TEM）,selective area electron diffraction and high resolution TEM,respectively.In addition,the room-temperature（RT） gas sensing properties of Cr2O3 HNs and conventional powders（CPs） were investigated by means of the surface photovoltage technique.The experimental data demonstrate that the RT gas sensor of the as-fabricated HNs reaches below 5 ppm whereas that of the CPs is about 40 ppm,which results from there being much more adsorbed and desorbed oxygen in HNs than in CPs at RT.The as-prepared Cr₂O₃ HNs could have potential applications as RT nanosensors.     

Effect of solution concentration on physicochemical and gas sensing properties of sprayed WO3 thin films

Sub-stoichiometric tungsten trioxide (WO₃) thin films are deposited onto the glass substrates by spray pyrolysis technique using ammonium metatungstate. Effect of solution concentration on structural, morphological, optical, electrical and NO₂ sensing properties of WO₃ thin films is studied. Films are polycrystalline with monoclinic crystal structure and sub-stoichiometric as observed form the XRD and XPS studies, respectively. The SEM and AFM images show micro grained structure and surface roughness increases with increase in solution concentration. The PL studies revealed that the majority of the defects are the oxygen vacancies. From XPS and PL studies it is observed that, oxygen vacancies decrease with increase in solution concentration. The dielectric constant of the films as a function of frequency is in concurrence with resistivity measurements. Films show reproducible and reversible gas response at various operating temperatures and gas concentrations. Highest sensor response (38%) towards 200 ppm NO₂ concentration is observed for the film with 15 mM solution concentration at moderate operating temperature (200 °C). Pd sensitization enhanced gas response to 68% and improved kinetics of the sensor. Films are highly selective towards NO₂ as compared with the various gases such as SO₂, LPG, NH₃ and H₂S.     

The effect of surface morphology on the response of Fe2O3-loaded vanadium oxide nanotubes gas sensor

The effect of surface morphology on the response of an ethanol sensor based on vanadium nanotubes surface loaded with Fe₂O₃ nanoparticles (Fe₂O₃/VONTs) was investigated in this work. The particle size of Fe₂O₃ loaded on VONTs was varied by using novel citric acid-assisted hydrothermal method. In the synthesis progress, citric acid was used as a surfactant and chelate agent, which ensured the growth of a uniform Fe₂O₃ loading on the nanotubes surface. The ethanol sensing properties was then measured for these Fe₂O₃/VONTs at 230-300 °C. The results showed that the sensor response increased with the particles size and the loading amount of Fe₂O₃. It appears that the load of Fe₂O₃ on the VONTs surface increases the concentration of oxygen vacancies and decreases the concentration of free electrons. The effects of morphology on the sensor resistance were interpreted in terms of the Debye length and the difference in the number of active sites.     

Influence of ceramic oxide materials on lithium based potentiometric CO2 sensors

In these potentiometric sensors, a mixed binary carbonate sensing material consisting of 90 mol% Li₂CO₃ and 10 mol% BaCO₃ was modified by adding ceramic oxide materials such as SiO₂, B₂O₃, La₂O₃, Bi₂O₃, CeO₂ and In₂O₃ in different mol% concentrations. Various sensors mixed with these external oxides have shown good performance at operating temperatures below 300 °C. Scanning electron microscopy reveals that a glassy sensing phase is formed in the sensing bi-carbonate by the addition of ceramic oxides and sintered at 600 °C for 1 h. The sensor mixed with SiO₂:B₂O₃:Bi₂O₃ in 1:2:1 mol% showed an excellent response and recovery characteristics and followed a fair Nernstian behavior with a ΔEMF/dec value of −48.18 at as low as 150 °C. The decrease in operating temperature is attributed to the enhanced lithium ion migration through the glassy sensing phase of the sensing electrode.     

Chemical synthesis of spinel nickel ferrite (NiFe2O4) nano-sheets

The present investigation is related to the deposition of single-phase nano-sheets spinel nickel ferrite (NiFe₂O₄) thin films onto glass substrates using a chemical method. Nano-sheets nickel ferrite films were deposited from an alkaline bath containing Ni²⁺ and Fe²⁺ ions. The films were characterized for their structural, surface morphological and electrical properties by means of X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and two-point probe electrical resistivity techniques. The X-ray diffraction pattern showed that NiFe₂O₄ nano-sheets are oriented along (3 1 1) plane. The FT-IR spectra of NiFe₂O₄ films showed strong absorption peaks around 600 and 400 cm⁻¹ which are typical for cubic spinel crystal structure. Microstructural study of NiFe₂O₄ film revealed nano-sheet like morphology with average sheet thickness of 30 nm. The room temperature electrical resistivity of the NiFe₂O₄ nano-sheets was 10⁷ Ω cm.     

Preparation, characterization and luminescence properties of porous Si3N4 ceramics with Eu2O3 as sintering additive

Porous Si₃N₄ ceramics with photoluminescence properties were prepared by pressureless sintering using α-Si₃N₄ powder as raw material and Eu₂O₃ as sintering additive. Chemical composition, phase formation, microstructure and photoluminescence properties of porous Si₃N₄ ceramics were studied by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), scanning electron microscopy (SEM) and photoluminescence measurements (PL/PLE). The results show that single Eu₂O₃ additive promotes α→β transformation but not significant densification. A broad band emission center at 570 nm assigned to Eu²⁺ is observed, Eu³⁺ in Eu₂O₃ is (partially) converted to Eu²⁺ by reaction with Si₃N₄, which results in a lower β aspect ratio and β-content compared to the other Ln (Ln=lanthanide) oxide additives.     

Microstructures and microwave dielectric properties of La1-xBx(Mg0.5Sn0.5)O3 ceramics

The microwave dielectric properties of La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were examined with a view to their exploitation for mobile communication. The La_1-xB_x(Mg_0.5Sn_0.5)O₃ ceramics were prepared by the conventional solid-state method with various sintering temperatures. The X-ray diffraction patterns of the La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics revealed no significant variation of phase with sintering temperatures. A maximum apparent density of 6.58 g/cm³, a dielectric constant (ε_r) of 19.8, a quality factor (Q × f) of 41,800 GHz, and a temperature coefficient of resonant frequency (τ_f) of −86 ppm/°C were obtained for La_0.995B_0.005(Mg_0.5Sn_0.5)O₃ ceramics that were sintered at 1500 °C for 4 h.     

Synthesis and photocatalytic oxidation of different organic dyes by using Mn2O3/TiO2 solid solution and visible light

Mn₂O₃/TiO₂ solid solution was prepared from two different oxides, manganese oxide (from KMnO₄ and ethanol) and TiO₂, these samples were characterized by BET, XRD, EDAX, SEM, FT-IR, ESR, XPS and UV–vis absorption spectroscopy. Photocatalytic activities of Mn₂O₃/TiO₂ powder was investigated by photooxidation of different dyes like Rhodamine B, thymol blue, methyl orange and Bromocresol green under visible light (300-W Xe lamp; λ > 420 nm). The results show that the alloy of TiO₂ with 1 mol% of Mn₂O₃ (MNT1) exhibit photocatalytic activity 3–5 times higher than that of P25 TiO₂ for oxidation of various dyes (RB, TB, MO and BG). The average particle size and crystallite size of MNT1 were found to be 100 nm and 12 nm measured from SEM and XRD, respectively. The EPR spectra of the Mn₂O₃/TiO₂ samples is a sharp five-line Mn(III) component centered on g_eff = 1.99.     

Can bowl-like B30 nanostructure sense toxic cyanogen gas in air?: a theoretical study

In this work, an attempt has been made to study sensing performance of bowl-like B₃₀ nanostructure towards toxic cyanogen gas using density functional theory (DFT) at B97D/6-31+G(d) computational level. The results reveal that B₃₀ nanostructure is a proper sensor for sensing of toxic cyanogen gas. The most favourite adsorption site of B₃₀ is the exterior boron atoms that lead to the adsorption energy of ?78.48 (kJ/mol) with the remarkable change in electronic properties of B₃₀. The competitive sensing of cyanogen gas in the presence of water, oxygen and nitrogen molecules is also considered. Significant changes in the electronic properties of B₃₀ due to adsorption of cyanogen in presence of O₂, H₂O and N₂ gases enable it to be used in the detection of toxic cyanogen gas in air.     

Effects of RE2O3 (RE = Tm, Sc, Yb) addition on the superconducting properties of ErBa2Cu3Oy

We investigated the effects of added Tm₂O₃, Sc₂O₃, and Yb₂O₃ on the superconducting properties of sintered Er123 samples. Tm₂O₃ addition caused the least T_c degradation, exhibiting a T_c above 90 K even for 17 vol% addition. Samples with added Sc₂O₃ maintained a T_c at above 90 K up to an addition of 7.2 vol%, while Yb₂O₃-containing samples showed a monotonic decrease in T_c with increased vol% of added Yb₂O₃. Tm₂O₃-containing samples exhibited a slight increase in J_c(0.1 T)/J_c(0) and had constant J_c values even for 17 vol% addition. XRD and SEM results indicate that the Tm₂O₃ is very stable in the superconducting matrix.