Influence of film thickness on the properties of sprayed ZnO thin films for gas sensor applications

Transparent conducting ZnO films were prepared at substrate temperature 400 degrees C with different film thicknesses by nebulizer spray pyrolysis method on glass substrates. XRD studies reveal that the films are polycrystalline in nature having hexagonal crystal structure with preferred grain orientations along (0 0 2) and (1 0 1) directions. The crystallite size increases along (0 0 2) plane with the thickness increase and attains a maximum 109 nm for 913 nm film thickness. Analysis of structural parameters indicates that the films having thickness 913 nm are found to have minimum dislocation density and strain values. The HRSEM measurements show that the surface morphology of the films also changes with film thickness. EDAX estimates the average atomic percentage ratio of Zn and O in the ZnO films. Optical studies reveal the band gap energy decrease from 3.27 to 3.14 eV with increase of film thickness. Room temperature PL spectra show the near-band-edge emission and deep-level emission due to the presence of defects in the ZnO thin films. Impedance spectroscopy analysis indicates that grain boundary resistance decreases with the increasing ammonia concentration up to 500 ppm and the maximum sensitivity is found to be 1.7 for 500 ppm of ammonia. (C) 2014 Elsevier Ltd. All rights reserved.

Enhancing the photocatalytic efficiency of sprayed ZnO thin films through double doping (Sn plus F) and annealing under different ambiences

Doubly (Sn + F) doped zinc oxide (ZnO:Sn:F) thin films were deposited onto glass substrates using a simplified spray pyrolysis technique. The deposited films were annealed at 400 degrees C under two different ambiences (air and vacuum) for 2 h. The photocatalytic activity of these films was assessed through photocatalytic decolorization kinetics of Methylene Blue (MB) dye and the decolorization efficiency of the annealed films was compared with that of their as-deposited counterpart. The photocatalytic studies reveal that the ZnO:Sn:F films annealed under vacuum environment exhibits better photocatalytic efficiency when compared with both air annealed and as-deposited films. The SEM and TEM images depict that the surface of each of the films has an overlayer comprising of nanobars formed on a bottom layer, having spherical grains. The studies show that the diameter of the nanobars plays crucial role in enhancing the photocatalytic activity of the ZnO:Sn:F films. The structural, optical and electrical studies substantiate the discussions on the photocatalytic ability of the deposited films. (C) 2014 Elsevier B.V. All rights reserved.

Effect of Pt doping on the gas sensing properties of porous chromium oxide films through a kinetic response analysis approach

The effect of doping trace amounts of noblemetals (Pt) on the gas sensing properties of chromium oxide thin films, is studied. The sensors are fabricated by depositing chromium oxide films on a glass substrate using a modified spray pyrolysis technique and characterized using X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The films are porous and nanocrystalline with an average crystallite size of similar to 30 nm. The typical p-type conductivity arises due to the presence of Cr vacancies, formed as a result of Cr non-stoichiometry, which is found to vary upon Pt doping. In order to analyze the effect of doping on the gas sensing properties, we have adopted a kinetic response analysis approach, which is based on Langmuir Adsorption isotherm (LA) theory. The sensor response is analyzed with equations obtained from LA theory and time constants as well as energies of adsorption-desorption are evaluated. It is seen that, Pt doping lowers the Schottky barrier height of the metal oxide semiconductor sensor from 222 meV to 172 meV. Subsequently the reduction in adsorption and desorption energies led to enhancement in sensor response and improvement in the kinetics of the sensor response i.e. the response time as well as recovery times of the sensor.

A novel in-situ polymer derived nano ceramic MMC by friction stir processing

Fiction stir processing (FSP) is a solid state technique used for material processing. Tool wear and the agglomeration of ceramic particles have been serious issues in FSP of metal matrix composites. In the present study, FSP has been employed to disperse the nanoscale particles of a polymer-derived silicon carbonitride (SiCN) ceramic phase into copper by an in-situ process. SiCN cross linked polymer particles were incorporated using multi-pass ESP into pure copper to form bulk particulate metal matrix composites. The polymer was then converted into ceramic through an in-situ pyrolysis process and dispersed by ESP. Multi-pass processing was carried out to remove porosity from the samples and also for the uniform dispersion of polymer derived ceramic particles. Microstructural observations were carried out using Field Emission Scanning Electron Microscopy (FE-SEM) and Transmission Electron Microscopy (TEM) of the composite. The results indicate a uniform distribution of similar to 100 nm size particles of the ceramic phase in the copper matrix after ESP. The nanocomposite exhibits a five fold increase in microhardness (260HV(100)) which is attributed to the nano scale dispersion of ceramic particles. A mechanism has been proposed for the fracturing of PDC particles during multi pass FSP. (C) 2015 Elsevier Ltd. All rights reserved

Gasification of wood particles in a co-current packed bed: Experiments and model analysis

This study focuses on addressing the propagation front movement in a co-current downdraft gasification system. A detailed single particle modeling analysis extended to the packed bed reactor is used to compare with the experimental measurement as well those available in the literature. This model for biomass gasification systems considered pyrolysis process, gas phase volatile combustion, and heterogeneous char reactions along with gas phase reactions in the packed bed. The pyrolysis kinetics has a critical influence on the gasification process. The propagation front has been shown to increase with air mass flux, attains a peak and then decreases with further increase in air mass flux and finally approaches negative propagation rate. This indicates that front is receding, or no upward movement() bra her it is moving downward towards the char bed. The propagation rate correlates with mass flux as (m) over dot `'(0.883) during the increasing regimes of the front movement The study clearly identifies that bed movement is an important parameter for consideration in a co-current configuration towards establishing the effective bed movement. The study also highlights the importance of surface area to volume ratio of the particles in the packed bed and its influence on the volatile generation. Finally, the gas composition for air gasification under various air mass fluxes is compared with the experimental results. (C) 2016 Elsevier B.V. All rights reserved.

Mechanistic studies on the pyrolysis and combustion of polystyrene/ammonium perchlorate propellants in the presence of transition metal oxides

The effect of transition metal oxides (Fe2O3, MnO2, Ni2O3 and Co2O3) on polystyrene/ammonium perchlorate propellant systems has been examined. The mechanism of action of the oxides in increasing the burning rate was examined by studying the effect of the oxides on the thermal decomposition and combustion of the oxidizer and the propellant. It has been concluded that one of the mechanisms by which the oxides act is by promoting the charge-transfer process, which is indicated by the enhancement of the electron-transfer process in ammonium perchlorate and by the correlation between the redox potential of the metal ions and the corresponding burning rates of the propellant.

Effect of temperature, pressure and additives on pyrolysis of polystyrene peroxide

Some aspects of the pyrolysis of polystyrene peroxide (PSP) have been examined. Low-temperature decomposition studies at 60°C and 70°C have been carried out to elucidate the ageing behaviour of PSP. The exothermic decomposition was found to be complete in 44 h at 70°C suggesting that all peroxide bonds have broken. Enthalpy measurements of the aged samples were carried out as a function of storage time. Ageing was also followed by infrared spectroscopy, and the intensity of the peroxide absorption around 1050 cm−1 was found to decrease with ageing time. Benzaldehyde formed as a result of PSP pyrolysis is readily converted into benzoic acid, which crystallizes during the ageing process. Pyrolysis—gas chromatographic studies have shown that up to 450°C the basic decomposition mechanism (i.e., the formation of benzaldehyde and formaldehyde as the major products) does not change. No effect of pressure on the decomposition exotherm in differential thermal analysis was observed, suggesting that peroxide composition involves only condensed phase reactions. Hydroquinone, p-aminophenol and cadmium sulphide were found to retard the thermal decomposition of PSP, suggesting that these compounds would be potential antioxidants for polymers.

Deposition of ZnO Films by Combustion Flame Pyrolysis of Solution Precursors

The structural features,including preferred orientation and surface morphology of zinc oxide (ZnO) films deposited by combustion flame pyrolysis were investigated as a function of process parameters, which include precursor solution concentration, substrate-nozzle (S-N) distance, gas flow rate, and duration of deposition. In this technique, the precursor droplets react within the flame and form a coating on an amorphous silica substrate held in or near the flame. Depending on the process parameters, the state of decomposition at which the precursor arrives on the substrate varies substantially and this in turn dictates the orientation and microstructure of the films.

Primary pyrolysis products of thiokol liquid polysulfide

An analysis of the primary degradation products of the widely used commercial polysulfide polymer Thiokol LP-33 by direct pyrolysis-mass spectrometry (DP-MS) is reported. The mechanism of degradation is through a radical process involving the random cleavage of a formal C-O bond followed by backbiting to form the cyclic products.

Regimes of spray formation in gas-centered swirl coaxial atomizers

Spray formation in ambient atmosphere from gas-centered swirl coaxial atomizers is described by carrying out experiments in a spray test facility. The atomizer discharges a circular air jet and an axisymmetric swirling water sheet from its coaxially arranged inner and outer orifices. A high-speed digital imaging system along with a backlight illumination arrangement is employed to record the details of liquid sheet breakup and spray development. Spray regimes exhibiting different sheet breakup mechanisms are identified and their characteristic features presented. The identified spray regimes are wave-assisted sheet breakup, perforated sheet breakup, segmented sheet breakup, and pulsation spray regime. In the regime of wave-assisted sheet breakup, the sheet breakup shows features similar to the breakup of two-dimensional planar air-blasted liquid sheets. At high air-to-liquid momentum ratios, the interaction process between the axisymmetric swirling liquid sheet and the circular air jet develops spray processes which are more specific to the atomizer studied here. The spray exhibits a periodic ejection of liquid masses whose features are dominantly controlled by the central air jet.

Effect of liquid precursor pyrolysis on phase selection in the MgO-MgAl2O4 system

Aqueous solutions of Al and Mg nitrates have been spray pyrolysed at 673 K to synthesize powders with compositions varying between MgO and MgAl2O4. This has been carried out with the aim of studying phase selection and phase evolution in this system. The powders have been subsequently heat treated and the sequence of phases characterised by X-ray diffraction and transmission electron microscopy. Metastable extensions of the different phase fields have been calculated based on functions which predict the equilibrium phase diagram accurately. The appearance of phases is closely related to the temperature and to the non-stoichiometry in different compositional ranges of the system. The sequence of phase evolution has been correlated to the thermodynamics of nucleation in the system.

Breakup and coalescence characteristics of a hollow cone swirling spray

This paper deals with an experimental study of the breakup characteristics of water emanating from hollow cone hydraulic injector nozzles induced by pressure-swirling. The experiments were conducted using two nozzles with different orifice diameters 0.3 mm and 0.5 mm and injection pressures (0.3-4 MPa) which correspond to Rep = 7000-26 000. Two types of laser diagnostic techniques were utilized: shadowgraph and phase Doppler particle anemometry for a complete study of the atomization process. Measurements that were made in the spray in both axial and radial directions indicate that both velocity and average droplet diameter profiles are highly dependent on the nozzle characteristics, Weber number and Reynolds number. The spatial variation of diameter and velocity arises principally due to primary breakup of liquid films and subsequent secondary breakup of large droplets due to aerodynamic shear. Downstream of the nozzle, coalescence of droplets due to collision was also found to be significant. Different types of liquid film breakup were considered and found to match well with the theory. Secondary breakup due to shear was also studied theoretically and compared to the experimental data. Coalescence probability at different axial and radial locations was computed to explain the experimental results. The spray is subdivided into three zones: near the nozzle, a zone consisting of film and ligament regime, where primary breakup and some secondary breakup take place; a second zone where the secondary breakup process continues, but weakens, and the centrifugal dispersion becomes dominant; and a third zone away from the spray where coalescence is dominant. Each regime has been analyzed in detail, characterized by timescale and Weber number and validated using experimental data. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4773065]

Optical, Electrochemical, and Structural Properties of Spray Coated Dihexyl Substituted Poly (3,4 propylene dioxythiophene) Film for Optoelectronics Devices

The dihexyl substituted poly (3,4-propylenedioxythiophene) (PProDOT-Hx(2)) thin films uniformly deposited by cost effective spray coating technique on transparent conducting oxide coated substrates. The electro-optical properties of PProDOT-Hx(2) films were studied by UV-Vis spectroscopy that shows the color contrast about 45% with coloration efficiency of approximate to 185cm(2)/C. The electrochemical properties of PProDOT-Hx(2) films were studied by cyclic voltammetry and AC impedance techniques. The cyclic voltammogram shows that redox reaction of films are diffusion controlled and ions transportation will be faster on the polymer film at higher scan rate. Impedance spectra indicate that polymer films are showing interface charge transfer process as well as capacitive behavior between the electrode and electrolyte. The XRD of the PProDOT-Hx(2) thin films revealed that the films are in amorphous nature, which accelerates the transportation of ions during redox process.

Impact of spray flux density and vacuum annealing on the transparent conducting properties of doubly doped (Sn plus F) zinc oxide films deposited using a simplified spray technique

In this investigation transparent conducting properties of as-deposited and annealed ZnO:Sn:F films deposited using different spray flux density by changing the solvent volume (10 mL, 20 mL ... 50 mL) of the starting solutions have been studied and reported. The structural analyses of the films indicate that all the films have hexagonal wurtzite structure of ZnO with preferential orientation along (002) plane irrespective of the solvent volume and annealing treatment whereas, the overall crystalline quality of the films is found to be enhanced with the increase in solvent volume as well as with annealing. This observed enhancement is strongly supported by the optical and surface morphological results. From the measurements of electrical parameters, it is seen that, the annealed films exhibit better electrical properties compared to the as-deposited ones. Annealing has caused agglomeration of grains as confirmed by the surface morphological studies. Also, the annealing process has led to an improvement in the optical transparency as well as band gap. It is found from the analyses of the characteristics of the as- deposited and annealed films that the annealed film deposited from starting solution having solvent volume of 50 mL is optimal in all respects, as it possesses all the desirable characteristics including the quality factor (1.60 x 10(-4) (Omega/sq.)(-1)). (C) 2014 Elsevier Ltd. All rights reserved.

SWEETENING OF BIOGAS IN SPRAY TOWERS FOR POWER GENERATION

This paper presents the experience of the new design of using impinging jet spray columns for scrubbing hydrogen sulfide from biogas that has been developed by Indian Institute of Science and patented. The process uses a chelated polyvalent metal ion which oxidizes the hydrogen sulfide to sulfur as a precipitate. The sulfur generated is filtered and the scrubbing liquid recycled after oxidation. The process involves in bringing contact the sour gas with chelated liquid in the spray columns where H2S reacts with chelated Fe3+ and precipitates as sulfur, whereas Fe3+ gets reduced to Fe2+. Fe2+ is regenerated to Fe3+ by reaction of oxygen in air in a separate packed column. The regenerated liquid is recirculated. Sulfur is filtered and separated as a byproduct. The paper presents the experience in using the spray towers for hydrogen sulfide removal and further use of the clean gas for generating power using gas engines. The maximum allowable limit of H2S for the gas engine is 200 ppm (v/v) in order to prevent any corrosion of engine parts and fouling of the lubricating oil. With the current ISET process, the hydrogen sulfide from the biogas is cleaned to less than 100 ppm (v/v) and the sweet gas is used for power generation. The system is designed for 550 NM3/hr of biogas and inlet H2S concentration of 2.5 %. The inlet concentration of the H2S is about 1 - 1.5 % and average measured outlet concentration is about 30 ppm, with an average gas flow of about 300 - 350 NM3/hr, which is the current gas production rate. The sweet gas is used for power generation in a 1.2 MWe V 12 engine. The average power generation is about 650 - 750 kWe, which is the captive load of the industry. The plant is a CHP (combined heat power) unit with heat from the cylinder cooling and flue being recovered for hot water and steam generation respectively. The specific fuel consumption is 2.29 kWh/m(3) of gas. The system has been in operation for more than 13,000 hours in last one year in the industry. About 8.4 million units of electricity has been generated scrubbing about 2.1 million m3 of gas. Performance of the scrubber and the engine is discussed at daily performance level and also the overall performance with an environment sustenance by precipitating over 27 tons of sulfur.