Enhanced performance of γ-Fe2O3:WO3 nanocomposite towards selective acetone vapor detection

Metal oxide nanocomposite sensors based on γ-Fe₂O₃ and WO₃ were investigated in acetone vapor of various concentrations (1–100 ppm) at operating temperatures between 250 and 350 °C. The composites were prepared by simple solid state mixing and porous thick-film gas sensors were fabricated on alumina substrates. The γ-Fe₂O₃:WO₃ (50:50) nanocomposite showed a marked enhancement in sensing response down to 1 ppm acetone vapor detection at 300 °C. The response was ~2-fold better compared to pure WO₃ or pure γ-Fe₂O₃ with a very fast response (1 s) and very short recovery time (3 s). No appreciable sensitivity was observed towards alcohol vapor (an interfacing agent for diabetics) and in moisture (present in breath). The enhanced performance was due to n–n heterojunction effect.     

Mixed-potential type NO2 sensor based on La10Si6O27 electrolyte and WO3 sensing electrode with different morphologies

A novel mixed-potential type NO₂ sensor was fabricated using La₁₀Si₆O₂₇ electrolyte and WO₃ sensing electrode (SE). The sinterability of La₁₀Si₆O₂₇ was significantly improved by the introduction of Y₂O₃ as sintering aid. WO₃ with different morphologies prepared by the citric acid (CA) assisted hydrothermal method was examined as the sensing electrodes of the mixed-potential type NO₂ sensors based on La₁₀Si₆O₂₇ electrolyte. The results showed that 6 wt% Y₂O₃ added La₁₀Si₆O₂₇ electrolyte sample could get quite dense at a temperature as low as 1500 °C. The morphologies and phase constituents of WO₃ were influenced by the CA content. The sensor showed good response–recovery characteristics. Compared with the sensor based on the irregular WO₃ particles or nanorods, the sensor using WO₃ nanosheets-SE with hexagonal structure exhibited much higher sensitivity (195.6 mV/decade) to NO₂ at 550 °C. The response signals of the sensor were slightly affected by coexistent O₂ varying from 5 to 20 vol%.     

Pyrochlore structure and dielectric properties of bismuth zinc niobate thin films prepared by RF sputtering

Bi_1.5Zn_1.0Nb_1.5O₇ (BZN) thin films with thickness from 60 nm to 200 nm were prepared by radio-frequency magnetron sputtering and post-annealed from 550 °C to 650 °C. The x-ray diffraction results indicated that the BZN thin films possessed a cubic pyrochlore phase. The BZN thin films exhibited thickness-independent dielectric properties with dielectric constant of ~180 and low loss tangent less than 1% at 10 kHz as the film thickness decreased to 60 nm. The BZN thin films with thickness of 200 nm and post-annealed at 650 °C had a tunability of 32.7% at a DC bias field of 1.5 MV/cm. The results suggest that the BZN thin films have promising applications on the embedded capacitors, tunable devices and energy storage devices.     

Synthesis and properties of nanocomposites of WO3 and exfoliated g-C3N4

The nanocomposites of WO₃ nanoparticles and exfoliated graphitized C₃N₄ (g-C₃N₄) particles were prepared and their properties were studied. For this purpose, common methods used for characterization of solid samples were completed with dynamic light scattering (DLS) method and photocatalysis, which are suitable for study of aqueous dispersions.The WO₃ nanoparticles of monoclinic structures were prepared by a hydrothermal method from sodium tungstate and g-C₃N₄ particles were prepared by calcination of melamine forming bulk g-C₃N₄, which was further thermally exfoliated. Its specific surface area (SSA) was 115 m² g⁻¹.The nanocomposites were prepared by mixing of WO₃ nanoparticles and g-C₃N₄ structures in aqueous dispersions acidified by hydrochloric acid at pH = 2 followed by their separation and calcination at 450 °C. The real content of WO₃ was determined at 19 wt%, 52 wt% and 63 wt%. It was found by the DLS analysis that the g-C₃N₄ particles were covered by the WO₃ nanoparticles or their agglomerates creating the nanocomposites that were stable in aqueous dispersions even under intensive ultrasonic field. Using transmission electron microscopy (TEM) the average size of the pure WO₃ nanoparticles and those in the nanocomposites was 73 nm and 72 nm, respectively.The formation of heterojunction between both components was investigated by UV–Vis diffuse reflectance (DRS) and photoluminescence (PL) spectroscopy, high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), photocatalysis and photocurrent measurements. The photocatalytic decomposition of phenol under the LED source of 416 nm identified the formation of Z-scheme heterojunction, which was confirmed by the photocurrents measurements. The photocatalytic activity of the nanocomposites decreased with the increasing content of WO₃, which was explained by shielding of the g-C₃N₄ surface by bigger WO₃ agglomerates. This study also demonstrates a unique combination of various characterization techniques working in solid and liquid phase.     

Synthesis of reduced graphene oxide/tungsten trioxide nanocomposite electrode for high electrochemical performance

A facile and well-controllable reduced graphene oxide/tungsten trioxide (rGO/WO₃) nanocomposite electrode was successfully synthesized via an electrostatic assembly route at 350 rpm for 24 h. In this study, hexagonal-phase WO₃ (h-WO₃) nanofiber was well distributed on rGO sheets by applying optimal processing parameters. The as-synthesized rGO/WO₃ nanocomposite electrode was compared with pure h-WO₃ electrode. A maximum specific capacitance of 85.7 F g⁻¹ at a current density of 0.7 A g⁻¹ was obtained for the rGO/WO₃ nanocomposite electrode, which showed better electrochemical performance than the WO₃ electrode. The incorporation of WO₃ into rGO could prevent the restacking of rGO and provide favourable surface adsorption sites for intercalation/de-intercalation reactions. The impedance studies demonstrated that the rGO/WO₃ nanocomposite electrode exhibited lower resistance because of the superior conductivity of rGO that improved ion diffusion into the electrode. To evaluate the contribution of WO₃ to the rGO/WO₃ nanocomposite, the influence of mass loading of WO₃ on the capacitance was investigated.     

Superparamagnetic zinc ferrite spinel–graphene nanostructures for fast wastewater purification

Superparamagnetic ZnFe₂O₄/reduced graphene oxide (rGO) composites containing ZnFe₂O₄ nanoparticles (with ∼5–20 nm sizes) attached onto rGO sheets (with ∼1 μm lateral dimensions) were synthesized by hydrothermal reaction method. By increasing the graphene content of the composite from 0 to 40 wt%, the size as well as the number of the ZnFe₂O₄ nanoparticles decreased and the saturated magnetization of the composites reduced from 10.2 to 1.8 emu/g, resulting in lower responses to external magnetic fields. Concerning this, the time needed for 90% separation of ZnFe₂O₄/rGO (40 wt%) composite from its solution (2 mg/mL in ethanol) was found 60 min in the presence of an external magnetic field (∼1 Tesla), while using ZnFe₂O₄/rGO (15 wt%), only 2 min was required (comparable to the separation time of pure ZnFe₂O₄ nanoparticles). Correspondingly, the magnetic separation time of 10 μM methyl orange and rhodamine B from aqueous solutions containing 2 mg/mL ZnFe₂O₄/rGO (15 wt%) was found <6 min, while using the ZnFe₂O₄/rGO (40 wt%) only 15–20% of the dyes could be separated after 16 min. Although the pure ZnFe₂O₄ nanoparticles could magnetically separate nearly whole of the dyes from the solutions, the separation time was too longer (>16 min).     

Effects of adding different morphological carbon nanomaterials on supercapacitive performance of sol–gel manganese oxide films

In this study, the supercapacitive performances of manganese oxide films were investigated by adding different carbon nanomaterials, including carbon nanocapsules (CNC), multiwalled carbon nanotubes (MWCNTs) and multi-layered graphene. The manganese oxide films were prepared with manganese acetate precursor by sol–gel method, and the post-treatment effects were also examined. With a heat-treatment above 300 °C, the as-prepared amorphous films transformed to a compound of Mn₃O₄ and Mn₂O₃ phases, and the smooth surface became rough as well. Cyclic voltammogram (CV) tests showed that the manganese oxide film, which was mixed with 0.05 wt% MWCNTs and annealed at 350 °C for 1 h, exhibited the optimized specific capacitance, 339.1 F/g. During 1000CV cycles, the specific capacitances of original manganese oxide film decreased gradually from 198.7 to 149.1 (75%) F/g. After same number of cycle tests, the modified films containing 0.025 wt% CNC, 0.05 wt% MWCNTs and 0.1 wt% graphene retained 201.8 (64.2%), 267.4 (78.9%) and 193.1 (57.4%) F/g respectively. The results indicates that the supercapacitive performance of manganese oxide films were significantly modified by carbon nanomaterials; in addition, the MWCNTs additive could also reduce the decay rate.     

Thermal stability of nanostructured 13 wt% Al2O3–8 wt% Y2O3–ZrO2 thermal barrier coatings

Nanostructured 13 wt% Al₂O₃–8 wt% Y₂O₃–ZrO₂ (13AlYSZ) coatings were developed by atmospheric plasma spraying (APS). The phase structure and the morphology of the 13AlYSZ coatings were characterized using X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). It was found that the as-sprayed coatings mainly consisted of tetragonal zirconia, with the Al element solid solution in ZrO₂. Heat treatment at 1100 °C increased the average grain size of the ZrO₂ phase from 61 to 120 nm and decreased the porosity from 23.8 to 18%. The addition of the nano-Al₂O₃ can effectively inhibit the grain growth of the zirconia phase. The mechanism on inhibiting the grain growth of nanostructured 8 wt% Y₂O₃–ZrO₂ thermal barrier coatings has been discussed in detail.     

Dielectric properties and bright red emission of Y3+/Eu3+-codoped ZrO2 thin films prepared by chemical solution deposition

We report on an effective combination of good dielectric properties with bright red emission in Y³⁺/Eu³⁺-codoped ZrO₂ thin films. The thin films were deposited on fused silica and Pt/TiO₂/SiO₂/Si substrates using a chemical solution deposition method. The crystal structure, surface morphology, electrical and optical properties of the thin films were investigated in terms of annealing temperature, and Y³⁺/Eu³⁺ doping content. The 5%Eu₂O₃–3%Y₂O₃–92%ZrO₂ thin film with 400 nm thickness annealed at 700 °C exhibits optimal photoluminescent properties and excellent electrical properties. Under excitation by 396 nm light, the thin film on fused silica substrate shows bright red emission bands centered at 593 nm and 609 nm, which can be attributed to the transitions of Eu³⁺ ions. Dielectric constant and dissipation factor of the thin films at 1 kHz are 30 and 0.01, respectively, and the capacitance density is about 65.5 nf/cm² when the bias electric field is less than 500 kV/cm. The thin films also exhibit a low leakage current density and a high optical transmittance with a large band gap.     

Coating of nano-sized ionically conductive Sr and Ca doped LaMnO3 films by sol–gel route

In this study, Sr and Ca doped LaMnO₃ thin ceramic films were coated on Al₂O₃ substrates by using a sol–gel route as the cathode material for SOFC. Nitrate precursors were used for the preparation of the thin film coating solution, and methanol and acetyl acetone were also used as the solvent and chelating agent, respectively. After the solution was prepared, an Al₂O₃ single crystal substrate was dipped into the solution. Then it was fired at 500 °C and annealed at 1025 °C for the crystallization. Coated films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), focused ion beam (FIB) and atomic force microscopy (AFM). Conductivity of the coated films was measured by the four probe Van der Pauw method. XRD, SEM, AFM and FIB characterizations of the coated film showed that the LaMnO₃ phase was formed, surface of the films was uniform and had homogenously distributed pores sized about 10 nm, mean grain size was about 60–80 nm and the film thickness was about 180 nm. The specific resistivity of the film was calculated to be 0.524 Ω m.     

Metallization of Al2O3 ceramic by magnetron sputtering Ti/Mo bilayer thin films for robust brazing to Kovar alloy

Ti/Mo bilayer thin films were deposited onto Al₂O₃ ceramic by magnetron sputtering with a subsequent high temperature sintering to ensure the robust brazing of Al₂O₃ ceramic to Kovar (Fe–Ni–Co) alloy. The interface reaction process between Ti film and Al₂O₃ ceramic as well as the joining strength between metallized Al₂O₃ ceramic and Kovar alloy were investigated systematically using X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, transmission electron microscopy, and electronic universal testing machine. The results show that the active Ti film can react with Al₂O₃ ceramic to form Ti₃Al and TiO during high-temperature sintering process, in which the amount, size and morphology of TiO crucially depend on the sintering temperature. As the sintering temperature reaches 1200 °C, a plenty of spherical TiO nanoparticles with ~ 150 nm in diameter and metallic nature can be created across the Ti/Al₂O₃ interfaces, which can effectively act as ‘bridges’ to join Ti film to Al₂O₃ substrate firmly. Hence, the optimal joining strength of 69.6±3.1 MPa between metallized Al₂O₃ ceramic and Kovar alloy can be obtained, much better than those counterparts metallized at 900 °C and 1050 °C almost without the existence of observable TiO.     

Piezoelectric properties of highly densified 0.01Pb (Mg1/2W1/2)O3–0.41Pb (Ni1/3Nb2/3)O3–0.35PbTiO3–0.23PbZrO3+0.1 wt% Y2O3+1.5 wt% ZnO thick films on alumina substrate

This paper reports on the formation of highly densified piezoelectric thick films of 0.01Pb(Mg_1/2W_1/2)O₃–0.41Pb(Ni_1/3Nb_2/3)O₃–0.35PbTiO₃–0.23PbZrO₃+0.1 wt% Y₂O₃+1.5 wt% ZnO (PMW–PNN–PT–PZ+YZ) on alumina substrate by the screen-printing method. To increase the packing density of powder in screen-printing paste, attrition milled nano-scale powder was mixed with ball milled micro-scale powder, while the particle size distribution was properly controlled. Furthermore, the cold isostatic pressing process was used to improve the green density of the piezoelectric thick films. As a result of these processes, the PMW–PNN–PT–PZ+YZ thick film, sintered at 890 °C for 2 h, showed enhanced piezoelectric properties such as P_r=42 μC/cm², E_c=25 kV/cm, and d₃₃=100 pC/N, in comparison with other reports. Such prominent piezoelectric properties of PMW–PNN–PT–PZ+YZ thick films using bi-modal particle distribution and the CIP process can be applied to functional thick films in MEMS applications such as micro actuators and sensors.     

Effects of WO3 on the microstructure and optical transmittance of PLZT ferroelectric ceramics

The influence of the WO₃ addition as sintering aids on the structural, microstructural and optical properties of (Pb,La)(Zr,Ti)O₃—PLZT based ceramics was investigated. Ferroelectric (Pb_0.9La_0.1)(Zr_0.65Ti_0.35)_0.975O₃ + x wt% WO₃ (x = 0.0, 0.5, 1.5 and 2.0) ceramics were densified by oxygen assisted uniaxial hot pressing. From the XRD results it was found that the hot pressed samples displayed single pseudocubic perovskite phase. EDS analysis evidenced the presence of WO₃ rich phase at the grain boundaries. An inhibition of grain growth and an evolution from transgranular to intergranular fracture behavior was observed, as a consequence of the formation of a PbO–WO₃ liquid phase, as the amount of WO₃ addition was increased. The optical transmittance in the visible and infrared range was decreased due to the presence of the liquid phase in grain boundaries, for WO₃ content lower than 2.0 wt%.     

Photophysical properties and photoelectrochemical performances of sol-gel derived copper stannate (CuSnO3) amorphous semiconductor for solar water splitting application

Copper tin oxide, CuSnO₃ (CSO), is an amorphous oxide semiconductor with a band-gap of 2.0–2.5 eV, and it is an attractive material for diverse applications such as transparent conducting oxides, transistors, and optoelectronic devices. In this study, we fabricated CSO thin films on fluorine-doped tin oxide (FTO)/glass substrates using a facile sol-gel process, and their optical properties, band structure and photoelectrochemical (PEC) properties were investigated using UV–Vis spectroscopy, photocurrent-density-potential (J-V) curves, electrochemical impedance spectroscopy, and Mott-Schottky analysis. The CSO film synthesized at 500 °C had an amorphous phase and a band gap of ~ 2.3 eV with n-type behavior, while the films synthesized at 550 °C and 600 °C had a phase mixture (SnO₂ + CuO). We identified for the first time that the CSO film could be applied to photoelectrodes for photoelectrochemical water-splitting systems. Importantly, when combining the CSO with nanostructured WO₃ film, i.e., the bilayer heterojunction of the a-CSO/WO₃ showed enhanced PEC performances (cathodic shift of onset potential, increase of photocurrent generation and O₂ evolution) compared to the pristine WO₃ film.     

Effects of Bi2O3–Li2CO3 additions on dielectric and pyroelectric properties of Mn doped Pb(Zr0.9Ti0.1)O3 thick films

Pb(Zr_0.9Ti_0.1)O₃ pyroelectric thick films adding various amounts of the sintering aids Bi₂O₃–Li₂CO₃ have been deposited on the substrates Al₂O₃ by the screen-printing process, and the dependence of microstructure, dielectric and pyroelectric properties on the content of sintering aids has been studied. When the amount of Bi₂O₃–Li₂CO₃ increases from 0 wt% to 5.4 wt%, the sintering temperature of the thick films decreases from 1100 °C to 900 °C, and the grain size and the lattice constant decrease either, but the density and the dielectric constant increase. The Pb(Zr_0.9Ti_0.1)O₃ thick film with 5.4 wt% of Bi₂O₃–Li₂CO₃ sintered at 900 °C has the maximum pyroelectric coefficient 10.51×10^?8 C/cm^?2 K^?1 and the highest figure-of-merit 10.58×10^?5 Pa^?0.5.     

Structural,optical and methanol sensing properties of sprayed In2O3 nanoparticle thin films

Indium oxide (In₂O₃) nanoparticle thin films were grown on cleaned glass substrates by the chemical spray pyrolysis technique using the precursor solution of indium nitrate (In (NO₃)₃). The XRD studies confirm that the films are polycrystalline In₂O₃, possessing cubic structure with lattice parameters, a = b = c = 10.17 Å. The optical studies show a direct optical band gap of 3.32 eV and an indirect band gap of 2.6 eV in the prepared films. The films exhibit high optical transparency >80% in the visible region, reaching a maximum of 85% at 684 nm wavelength. Further, the gas sensing properties of the films have been investigated for various concentrations of methanol in air at different operating temperatures. At 300 °C the film exhibits a very high response 99% to methanol vapor at a concentration of 40 ppm in air, which is ideal to be used as a methanol sensor. The film shows fast response and recovery to methanol vapor at higher operating temperatures. A possible methanol sensing mechanism has been proposed.     

Sunlight assisted photoelectrocatalytic degradation of benzoic acid using stratified WO3/TiO2 thin films

The stratified WO₃/TiO₂ thin films have been deposited onto glass and FTO coated glass substrates using simple chemical a spray pyrolysis method. The structural, morphological, compositional and photoelectrocatalytic properties of the stratified WO₃/TiO₂ thin films are studied. The photoelectrochemical (PEC) study shows that, both short circuit current (I_sc) and open circuit voltage (V_oc) are (I_sc =1.192 mA and V_oc =0.925 V) relatively high at 50 ml spraying quantity of TiO₂ solution on pre-deposited WO₃. XRD analysis confirms that films are polycrystalline with monoclinic and tetragonal crystal structures for WO₃ and TiO₂ respectively. Specific surface area of 72.14 m² g⁻¹ is measured by Brunauer-Emmett-Teller (BET) technique. Photoelectrocatalytic degradation of benzoic acid (BA) dye in aqueous solutions is studied. The end result shows that the degradation percentage of benzoic acid (BA) using stratified WO₃/TiO₂ photoelectrode has reached 66% under sunlight illumination after 320 min. The amount of degradation is confirmed by COD analysis.     

Microstructure and dielectric properties of the Ti-rich BaO–TiO2 thin films for microwave devices

Ti-rich BaO–TiO₂ thin films were grown on a Pt/Ti/SiO₂/Si substrate using rf sputtering and the structural and dielectric properties of the films were investigated. For the film grown at room temperature and rapidly thermal annealed (RTA) at 900 °C for 3 min, an amorphous phase with a small BaTi₅O₁₃ crystalline phase was formed. As the growth temperature increased, the amount of the BaTi₅O₁₁ crystalline phase increased. For the film grown at 350 °C and RTA at 900 °C for 3 min, the homogeneous BaTi₅O₁₁ phase was formed. The BaTi₄O₉ phase was developed when the growth temperature exceeded 450 °C. The thin film with the homogeneous BaTi₄O₉ phase was obtained when the film was grown at 550 °C and RTA at 900 °C for 3 min. The dielectric properties of the films were measured at 1–6 GHz range. The dielectric constant (ϵ_r) of the BaTi₅O₁₁ film was about 33 and the dissipation factor was about 0.01. The ϵ_r and the dissipation factor of the BaTi₄O₉ film were about 37 and 0.005, respectively.     

Highly resistive SiC ceramics sintered with Al2O3-AlN-Y2O3 additions

A polycrystalline SiC ceramic prepared by pressureless sintering of α-SiC powders with 3 vol% Al₂O₃-AlN-Y₂O₃ additives in an argon atmosphere exhibited a high electrical resistivity of ~10¹³ Ω cm at room temperature. X-ray diffraction revealed that the SiC ceramics consisted mainly of 6H- and 4H-SiC polytypes. Scanning electron microscopy and high resolution transmission electron microscopy investigations showed that the SiC specimen contained micron-sized grains surrounded by an amorphous Al-Y-Si-O-C-N film with a thickness of ~4.85 nm. The thick boundary film between the grains contributed to the high resistivity of the SiC ceramic.     

Ultraviolet pulsed laser crystallization of Ba0.8Sr0.2TiO3 films on LaNiO3-coated silicon substrates

In this work, Ba_0.8Sr_0.2TiO₃ (BST) films on LaNiO₃-buffered SiO₂/Si (LNO/SiO₂/Si) substrates were crystallized by pulsed laser irradiation. Solution-derived amorphous barium–strontium–titanate precursor layers were crystallized with a KrF excimer laser in oxygen ambient at fluences ranging from 50 to 75 mJ cm⁻². With the substrate temperature set to 500 °C, the number of pulses and film thickness were varied until high-quality crystallinity could be achieved. It was found that films with a thickness of 40 nm are fully crystallized with a uniaxial {00l} orientation which is predetermined by the LaNiO₃ orientation. On the other hand, for 160 nm thick films, crystallization was observed after 12,000 pulses in the 70 nm close to the surface, while the rest of the film remained amorphous. The large temperature difference between the film surface and interface due to the low thermal conductivity of the amorphous BST is suggested as the origin of this behavior. Films thicker than 80 nm cracked on crystallization due to the stress caused by the different thermal expansion coefficients of film and substrate, as well as the large temperature variations within the BST film.