Preparation of nanocrystalline nickel oxide thin films by sol–gel process for hydrogen sensor applications

Preparation of nanocrystalline NiO thin films by sol–gel method and their hydrogen (H₂) sensing properties were investigated. The thin films of NiO were successfully deposited on the glass and SiO₂/Si substrate by a sol–gel coating method. The films were characterized for crystallinity, electrical properties, surface topography and optical properties as a function of calcination temperature and substrate material. It was found that the films produced by this method were polycrystalline and phase pure NiO. The H₂ gas sensitivity of these films was studied as a function of H₂ concentration and calcination temperature. The results indicated that the sol–gel derived NiO films could be used for the fabrication of H₂ gas sensors to monitor low concentration of H₂ in air quantitatively at low temperature range (< 200 °C).     

Synthesis,characterization and gas sensing performance of SnO<Subscript>2</Subscript> thin films prepared by spray pyrolysis

In this work, SnO₂ thin films were deposited onto alumina substrates at 350°C by spray pyrolysis technique. The films were studied after annealing in air at temperatures 550°C, 750°C and 950°C for 30 min. The films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and optical absorption spectroscopy technique. The grain size was observed to increase with the increase in annealing temperature. Absorbance spectra were taken to examine the optical properties and bandgap energy was observed to decrease with the increase in annealing temperature. These films were tested in various gases at different operating temperatures ranging from 50–450°C. The film showed maximum sensitivity to H ₂S gas. The H₂S sensing properties of the SnO₂ films were investigated with different annealing temperatures and H ₂S gas concentrations. It was found that the annealing temperature significantly affects the sensitivity of the SnO₂ to the H ₂S. The sensitivity was found to be maximum for the film annealed at temperature 950°C at an operating temperature of 100°C. The quick response and fast recovery are the main features of this film. The effect of annealing temperature on the optical, structural, morphological and gas sensing properties of the films were studied and discussed.     

Room temperature synthesis and ammonia sensing of monodispersed hierarchical 1 and 3-dimensional Co3O4 nanostructures: switching from p to n-type sensing

This study report on a sonochemical synthesis of 1- and 3-dimensional hierarchical nanostructured cobalt oxide systems (Co₃O₄) and their application in ammonia sensing at room temperature (i.e., 30 °C). The Co₃O₄ nanostructures were synthesized via a room temperature-assisted precipitation and subsequent thermal treatment of the oxalate precursor. The resulted nanostructures were characterized by SEM, XRD, TEM, FTIR spectroscopy, BET, and TGA/DTA. The synthesis mechanism was proposed on the basis of morphology analyzed at various stages of the particle growth. It was observed that the final hierarchical microspheres structure resulted from the self-aggregation of the initially formed nanorods. The microspheres and nanorods were used as efficient room temperature gas sensors for ammonia detection in the concentration range of 0.01–500 ppm. The nanorod-based sensor showed an unusual n-type sensing behavior to ammonia in a temperature range of 30–300 °C. This transition of p to n-type was correlated to the formation of successive layers of physisorbed water molecules at the surface of the synthesized Co₃O₄. However, in case of the microspheres, the n-type behavior and superior sensitivity were observed at 30 °C followed by a negligible response up to 200 °C, while the intrinsic p-type behavior was recorded at an elevated temperature (200–300 °C). The observed unusual sensing performance may be associated with the crystallographic nature and lattice strain in the material structures. Additionally, the large specific surface area and the change in crystalline structure with temperature made the as prepared novel hierarchical Co₃O₄ structures a distinctive material for sensing ammonia at 30 °C.

     

Effect of reaction temperature on crystallite size and sensing response of chromium oxide nanoparticles

Nanoparticles of chromium oxide have been synthesized following a precipitation technique at reaction temperatures 5, 27 and 65 °C. Synthesized powders were characterized using X-ray diffraction, transmission electron microscope and Brunauer–Emmett–Teller techniques to carry out structural and morphological analysis. The reaction temperature has been found to be playing a crucial role in controlling particle size. It has been observed that Cr₂O₃ nanoparticles synthesized at 27 °C were smaller as compared to those synthesized at 5 and 65 °C. Chromium oxide samples thus prepared were deposited as thick films on alumina substrates to act as gas sensors and their sensing response to ethanol vapour was investigated at different operable temperatures. It has been observed that all the sensors exhibited optimum response at 250 °C. The investigations revealed that sensing response of Cr₂O₃ nanoparticles synthesized at 27 °C was exceptionally higher than that of Cr₂O₃ nanoparticles synthesized at 5 and 65 °C.     

Synthesis of carbon nanotubes at low temperature by filament assisted atmospheric CVD and their field emission characteristics

Multiwalled carbon nanotubes (MWNTs) were synthesized using a hot filament assisted chemical vapor deposition (CVD) at the atmospheric pressure at a substrate temperature of 550 °C. The size of nanotubes was controlled by changing the size of catalyst particles. The structure and composition of these nanotubes were investigated using scanning electron microscopy, transmission electron microscopy, and Raman spectroscopy. The electron field emission current of MWNTs was also measured. It was found that the nanotubes with smaller the diameter had higher the emission current levels though synthesis conditions except catalyst particles were the same. These as-grown MWNTs had emission current densities of 6.5 mA/cm² and 2.5 mA/cm² at 1 V/μm for 5-8 nm and 20 nm size carbon nanotube samples, respectively. The results indicated that the MWNTs synthesized had low emission threshold voltages and high emission current levels that are favorable properties for field emission-based display device applications.     

Preparation of high-yield multi-walled carbon nanotubes by catalytic decomposition of mixture of natural gas and propylene and their electrothermal properties

Abstract

Multi-walled carbon nanotubes (MWNTs) with high-yield were prepared by pyrolysis of mixture of natural gas (NG) and propylene (C₃H₆) over Fe-Ni/Al₂O₃-MgO catalyst. For C₃H₆/NG flow rate ratio ranging from 0 to 0.33, the carbon yield was increased from 903% to 4400%. The synthesized MWNTs after purification were dispersed by ball milling method and mixed with waterborne polyurethane to fabricate the electrothermal film. The mass fraction of CNT filler in the cured electrothermal film was controlled at 50%. The coating after drying was ca. 6?μm and the coating’s volume resistivity was 0.053 Ω·cm. The time-dependent temperature curves indicated that the heating rate of the electrothermal film was very fast under different low voltage and the steady-state temperatures were achieved within 100?s. The steady-state temperature reached 47.9?°C, 76.8?°C, and 102.8?°C, respectively at 10?V, 15?V, and 18?V.     

Synthesis of nano-carbon (nanotubes,nanofibres, graphene) materials

In the present study, we report the synthesis of carbon nanotubes (CNTs) using a new natural precursor: castor oil. The CNTs were synthesized by spray pyrolysis of castor oil-ferrocene solution at 850°C under an Ar atmosphere. We also report the synthesis of carbon nitrogen (C-N) nanotubes using castor oil-ferrocene-ammonia precursor. The as-grown CNTs and C-N nanotubes were characterized through scanning and transmission electron microscopic techniques. Graphitic nanofibres (GNFs) were synthesized by thermal decomposition of acetylene (C₂H₂) gas using Ni catalyst at 600°C. As-grown GNFs reveal both planar and helical morphology. We have investigated the structural and electrical properties of multi-walled CNTs (MWNTs)-polymer (polyacrylamide (PAM)) composites. The MWNTs-PAM composites were prepared using as purified, with ball milling and functionalized MWNTs by solution cast technique and characterized through SEM. A comparative study has been made on the electrical property of these MWNTs-PAM composites with different MWNTs loadings. It is shown that the ball milling and functionalization of MWNTs improves the dispersion of MWNTs into the polymer matrix. Enhanced electrical conductivity was observed for the MWNTs-PAM composites. Graphene samples were prepared by thermal exfoliation of graphite oxide. XRD analysis confirms the formation of graphene.     

Facile tailoring of titanate nanostructures at low alkaline concentration by a solvothermal route

Nanostructured titanates with different morphologies such as nanoflakes, nanotubes, and nanofibers have been selectively synthesized by a simple solvothermal treatment of commercial anatase TiO₂ using the mixed water–ethanol cosolvent at low alkaline concentration. The effects of solvothermal temperature, volume ratio of H₂O to C₂H₅OH, amount of NaOH and solvents on the formation of titanate nanostructures have been systematically studied through X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). At low concentration of NaOH solution (the actual concentration of OH⁻ in the solution is only 0.58 M), different titanate nanostructures are achieved by simply changing the volume ratio of H₂O to C₂H₅OH at 180 °C and titanate nanotubes can be synthesized between 100 and 180 °C. A probable formation mechanism is proposed based on XRD, SEM and TEM analysis. The influence of cosolvent on the transformation from anatase TiO₂ to titanate is also investigated.     

Experimental and numerical analysis of an air-cooled double-lift NH3–H2O absorption refrigeration system

The prototype of an air-cooled double-lift NH₃–H₂O absorption chiller driven by hot water at low temperature is presented. The main objective of the study is to illustrate the experimental performances of the prototype under different operating conditions. A mathematical model of the cycle is developed, along with a procedure for the identification of otherwise difficult to measure data, with the purpose of providing the complete picture of the internal thermodynamic cycle. The combined experimental and numerical data allowed assessing the effects on the thermodynamic cycle with varying operating conditions. The unit operated steadily with chilled water inlet 12 °C, outlet 7 °C, air temperature between 22 °C and 38 °C, and hot water driving temperatures between 80 °C and 90 °C. The reference cooling capacity at air temperature of 30 °C is 2.5 kW, with thermal COP about 0.3 and electrical COP about 10.     

Electrical resistivity of bulk multi-walled carbon nanotubes synthesized by an infusion chemical vapor deposition method

Multi-walled carbon nanotubes (MWNTs) were synthesized by infusing alcohol into a tube furnace. A nickel catalyst preparation was made by a reduction reaction of NiO powder by ethanol vapor at 450 °C for 30 min before the MWNT synthesis at 700 °C for 1–18 h. The as-grown MWNTs were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction and Raman spectroscopy. Large quantities of MWNTs, having a diameter in the range of 20–50 nm can be produced from ethanol vapor without a carrier gas by this technique. A method to measure an electrical resistance of bulk MWNTs was carried out under stress between two conducting plates. The result shows an exponentially correlation between the resistivity and the D-band/G-band intensity ratio, suggesting that the measuring method provides a simple tool to monitor the degree of structural defects of MWNTs.     

Effect of Ni loading and reaction temperature on the formation of carbon nanotubes from methane catalytic decomposition over Ni/SiO<Subscript>2</Subscript>

Since their discovery carbon nanotubes (CNT) have attracted much attention due to their singular physical, mechanical and chemical properties. Catalytic chemical vapor deposition (CCVD) of hydrocarbons over metal catalysts is the most promising method for the synthesis of CNT, because of the advantages of low cost and large-scale production and the relatively low temperature used in the process, compared to the other methods (laser ablation and discharge between graphite electrodes). In this study, CNT were synthesized by CCVD using Ni supported on SiO₂ as a catalyst. The carbon deposited in the reaction was analyzed by Raman spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The effects of reaction temperature and Ni loading on the carbon nanotube formation were evaluated. The catalyst with 5% Ni favored high yield of CNT at lower temperature, with abundant “multi-walled carbon nanotubes” (MWNTs) at 625 °C, while single-walled carbon nanotubes (SWNTs) and MWNTs were obtained at 650 °C. With an increase in the reaction temperature a marked decrease in the yield of CNT was observed, probably due to the sintering of the catalyst. The catalyst with 1% Ni gave SWNTs with a high degree of order at all reaction temperatures, but in low quantity.     

Properties of Co0.5Ni0.5Fe2O4/carbon nanotubes/polyimide nanocomposites for microwave absorption

High-temperature microwave absorbing materials are of great interest due to their ability to withstand high temperatures. Multi-walled carbon nanotubes (MWNTs) were surface modified by Ar plasma and Co_0.5Ni_0.5Fe₂O₄ nanoparticles were doped onto the surface of the MWNTs by a chemical co-precipitation method. Co_0.5Ni_0.5Fe₂O₄/MWNTs powders were then added to polyimide to prepare nanocomposites for microwave absorption. After plasma modification, the surface of the MWNTs produced carboxyl groups, which are beneficial for interfacial bonding between the MWNTs and PI. The glass transition temperature of the nanocomposites was 261 °C and their thermostability was preserved up to 500 °C. The maximum reflection loss (RL) value of nanocomposites containing 0.75 wt% modified MWNTs was ?24.37 dB and the frequency range where the RL value was less than ?10 dB was 5.1 GHz from 7.8 to 12.9 GHz.     

Sodium niobate particles with controlled morphology synthesized by hydrothermal method and their use as templates in KNN fibers

Sodium niobate – NN (NaNbO₃) powders were synthesized by hydrothermal process to be used as template particles in the fabrication of textured lead free piezoelectric ceramics. Sodium hexaniobate–Na₈Nb₆O₁₉⋅13H₂O particles with rod-like morphology were synthesized at 120 °C. Particles with needle-like morphology and Na₂(Nb₂O₆)(H₂O) phase started to form at temperatures of 130 °C and above. Synthesis at 150 °C yields particles with totally needle-like morphology and consisting entirely of the Na₂(Nb₂O₆)(H₂O) phase. Sodium niobate–NaNbO₃ particles with cubic morphology were synthesized at temperatures of 160 °C and above. Rod-like and needle-like morphology was retained even after annealing at 400 °C for 1 h. A preliminary study was also done to integrate these anisometric template particles in the preparation of textured potassium sodium niobate (KNN) fibers.     

Calibration of reaction parameters for the improvement of thermal stability and crystalline quality of multi-walled carbon nanotubes

The results of Raman analysis on multi-walled carbon nanotubes, prepared by catalysed chemical vapour deposition, are used as a guide for the calibration of the growth parameters, directed to improve crystalline quality and resulting thermal stability of nanotubes. Under selective growth conditions, the resistance to oxidation in air, as assessed by thermogravimetry measurements, is found to increase with the establishment of the long-range graphitic order in radial tube direction, as signalled by the Raman G′/G intensity ratio enhancement. In the range of parameters explored (synthesis temperature: 500–700 °C; growth atmosphere: 120 cc/min i-C₄H₁₀–H₂–He mixture with He at 0–25%; i-C₄H₁₀/H₂ flow ratio: 1–3; metal load and reduction temperature of Fe/Al₂O₃ catalysts: 17–40 wt%, and 500 and 700 °C, respectively), the best crystalline quality and the highest oxidative resistance are achieved by carrying out the synthesis reaction at 700 °C in 1:1:0 i-C₄H₁₀–H₂–He atmosphere over 29 wt% Fe catalysts reduced at 700 °C. An additional relevant finding is the strong correlation evidenced between results of thermogravimetry and Raman analyses, suggesting the use of Raman spectroscopy for non-destructively evaluating the thermal stability of any graphitically ordered carbon species.     

Low temperature preparation of the Zn<Subscript>2</Subscript>SiO<Subscript>4</Subscript> ceramics with the addition of BaO and B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The Zn₂SiO₄ ceramics with the addition of BaO and B₂O₃ are fabricated by traditional solid-state preparation process at a sintering temperature of 900 °C. The introduction of BaO and B₂O₃ to the binary system ZnO-SiO₂ is achieved by adding 10 and 20 wt. % flux BB to the mixed ZnO-SiO₂ ceramic powders pre-sintered at 1,100 °C, respectively. The chemical composition of the flux BB (50 wt.%BaO-50 wt.% B₂O₃) is located at a liquid phase zone with a temperature range of about 869–900 °C in the binary diagram BaO-B₂O₃. In addition, the introduction of BaO and B₂O₃ to the binary system ZnO-SiO₂ is also achieved by the means of a chemical combination of H₂SiO₃, H₃BO₃, ZnO and Ba(OH)₂·8H₂O, which can result in the formation of the hydrated barium borates with low melting characteristics. In turn, by the liquid sintering aid of the barium borate melts, the preparation process of the Zn₂SiO₄ ceramics can be further simplified. In the two preparation methods, the Zn₂SiO₄ ceramics with the 1.5–2.0 ZnO/SiO₂ molar ratios and the addition of a 10 wt. % flux BB can show good dielectric properties whereas the bending strength mainly depends on the microstructure of the Zn₂SiO₄ ceramics and SiO₂ content in the composition of the specimen.     

Effect of variation of sintering temperature on the gas sensing characteristics of SnO2:Cu (Cu=9 wt.%) system

The effect of variation of sintering temperature (600–800 °C/4 h) on the gas sensing characteristics of a SnO₂:Cu (Cu=9 wt.%) system (a high-performance temperature-selective composition) in the form of pellets is investigated systematically for the CO, H₂ and LPG gases at a concentration level of 1000 ppm. The XRD, SEM and half-bridge techniques were employed to establish the structural, morphological and gas sensing characteristics of the materials, respectively. A very high value of sensitivity factor (SF) equal to 1400 is obtained for CO gas at an optimal operating temperature of 160 °C for the pellets sintered at 750 °C. The selectivity values of CO gas against H₂ and LPG (S_CO/S_H2∼14 and S_CO/S_LPG∼280) at an optimum temperature of 160 °C are also improved considerably. This material (SnO₂:Cu, Cu=9 wt.% sintered at 750 °C with an optimal temperature of 160 °C) may prove to have tremendous potential for CO gas sensing applications.     

Development of NiO-based thin film structures as efficient H2 gas sensors operating at room temperatures

P-type NiO thin films have been developed on high resistivity Si and SiO₂ substrates by a pulsed laser deposition technique using an ArF^? 193 nm excimer laser at deposition temperature of 300 °C and in 40 Pa partial oxygen pressure. Structures based on such NiO films as host material in the form of Au-NiO Schottky diodes have been subsequently developed under vacuum. In a different procedure, an n-SnO₂ layer has been deposited by a CVD technique on a NiO film to produce a p/n heterojunction. The sensing properties of all above structures have been tested upon exposure to a H₂ flow in air ambient gas at various operating temperature ranging from 30 to 180 °C. For the NiO films, the optimum temperature was about 150 °C exhibiting a sensitivity of 94%. After surface sensitization of NiO by Au the NiO films showed an H₂ response at operating temperature of 30 °C. The sensitivity of p-NiO/n-SnO₂ heterojunction devices was extracted from I-V measurements in air and under H₂ flow mixed in air. In this case a dramatic increase of the sensitivity was achieved at operating temperature of 30 °C for a forward bias of 0,2 V.     

Ti/SiO2 composite fabricated by powder metallurgy for orthopedic implant

Titanium/silica (Ti/SiO₂) composites are fabricated using powder metallurgy (P/M). Nanoscale biocompatible SiO₂ particles are selected as reinforcement for the Ti/SiO₂ composite to enhance its biocompatibility and strength, especially when with high porosity. Effects of the SiO₂ particle addition and sintering temperature on mechanical properties of the Ti/SiO₂ composites are investigated. The results indicate that the mechanical property of Ti/SiO₂ composites sintered at 1100 °C are better than those at 900 and 1000 °C. The strength of the Ti/SiO₂ composites is significantly higher than that of pure titanium. The composite with the SiO₂ content of 2 wt% sintered at 1100 °C for 4 h shows an appropriate mechanical property with a relative density of 96.5%, a compressive strength of 1566 MPa and good plasticity (an ultimate strain of 15.96%). In vitro results reveal that the Ti/SiO₂ composite possesses excellent biocompatibility and cell adhesion. Osteoblast-like cells grow and spread well on the surfaces of the Ti/SiO₂ composites. The Ti/SiO₂ composite is a promising material for great potential used as an orthopedic implant material.     

Studies on optical,chemical, and electrical properties of rapid SiO2 atomic layer deposition using tris(tert-butoxy)silanol and trimethyl-aluminum

Rapid SiO₂ atomic layer deposition (ALD) was used to deposit amorphous, transparent, and conformal SiO₂ films using tris(tert-butoxy)silanol (TBS) and trimethyl-aluminum (TMA) as silicon oxide source and catalytic agent, respectively. The growth rate of the SiO₂ films drastically increased to a maximum value (2.3 nm/cycle) at 200 °C and slightly decreased to 1.6 nm/cycle at 275 °C. The SiO₂ thin films have C–H species and hydrogen content (～8 at%) at 150 °C because the cross-linking rates of SiO₂ polymerization may reduce below 200 °C. There were no significant changes in the ratio of O/Si (～2.1) according to the growth temperatures. On the other hand, the film density slightly increased from 2.0 to 2.2 although the growth rate slightly decreased after 200 °C. The breakdown strength of SiO₂ also increases from 6.20 ± 0.82 to 7.42 ± 0.81 MV/cm. These values suggest that high cross-linking rate and film density may enhance the electrical property of rapid SiO₂ ALD films at higher growth temperature.     

Effect of H2S on Fe corrosion in CO2-saturated brine

The effect of H₂S at ppm level concentrations on iron corrosion in 3 wt% NaCl solutions saturated with CO₂ in the temperature range of 25–85 °C is examined using electrochemical and surface science techniques. Small H₂S concentrations (5 ppm) have an inhibiting effect on corrosion in the presence of CO₂ at temperatures from 25 to 55 °C. At 85 °C, however, 50 ppm H₂S is needed to provide significant corrosion inhibition. At higher H₂S concentrations, the corrosion rate increases rapidly, while still remaining below the rate for the H₂S-free solution. Characterization of the iron surfaces after corrosion was carried out using X-ray photoelectron spectroscopy and X-ray diffraction. A sulfur peak (S2p) is observed at a binding energy of 161.8 eV in all cases, attributable to disulfide (\textS₂^2-) ({\text{S}}_{2}^{2-}) formation. Corrosion protection in the temperature range 25–55 °C can be attributed to Fe(II) bonded to S and O. At 85 °C, protection of the iron surface is most likely due to FeS₂ formation. Morphological changes on the iron surface after exposure to H₂S containing solutions were observed by SEM. A thin protective film was seen after exposure to solutions containing 5 ppm H₂S at 25 °C, while at 85 °C, with the addition of 50 ppm H₂S to CO₂-saturated brine solution, a dense protective film was formed on the iron surface.