Low temperature CO sensitive nanostructured WO3 thin films doped with Fe

Nanostructured tungsten oxide thin film based gas sensors have been developed by thermal evaporation method to detect CO at low operating temperatures. The influence of Fe-doping and annealing heat treatment on microstructural and gas sensing properties of these films have been investigated. Fe was incorporated in WO3 film by co-evaporation and annealing was performed at 400oC for 2 hours in air. AFM analysis revealed a grain size of about 10-15 nm in all the films. GIXRD analysis showed that as-deposited films are amorphous and annealing at 400oC improved the crystallinity. Raman and XRD analysis indicated that Fe is incorporated in the WO3 matrix as a substitutional impurity, resulting in shorter O-W-O bonds and lattice cell parameters. Doping with Fe contributed significantly towards CO sensing performance of WO3 thin films. A good response to various concentrations (10-1000 ppm) of CO has been achieved with 400oC annealed Fe-doped WO3 film at a low operating temperature of 150oC.

Temperature-dependent growth mechanisms of low-dimensional ZnO nanostructures

One-dimensional ZnO nanostructures were successfully synthesized on single-crystal silicon substrates via a simple thermal evaporation and vapour-phase transport method under different process temperatures from 500 to 1000 °C. The detailed and in-depth analysis of the experimental results shows that the growth of ZnO nanostructures at process temperatures of 500, 800, and 1000 °C is governed by different growth mechanisms. At a low process temperature of 500 °C, the ZnO nanostructures feature flat and smooth tips, and their growth is primarily governed by the vapour-solid mechanism. At an intermediate process temperature of 800 °C, the ZnO nanostructures feature cone-shape tips, and their growth is primarily governed by the self-catalyzed and saturated vapour–liquid–solid mechanism. At a high process temperature of 1000 °C, the alloy tip appears on the front side of the ZnO nanostructures, and their growth is primarily governed by the common catalyst-assisted vapour–liquid–solid mechanism. It is also shown that the morphological, structural, optical, and compositional properties of the synthesized ZnO nanostructures are closely related to the process temperature. These results are highly relevant to the development of light-emitting diodes, chemical sensors, energy conversion devices, and other advanced applications.

Single-step, rapid low-temperature synthesis of Si quantum dots embedded in an amorphous SiC matrix in high-density reactive plasmas

A simple, effective and innovative approach based on low-pressure, thermally nonequilibrium, high-density inductively coupled plasmas is proposed to rapidly synthesize Si quantum dots (QDs) embedded in an amorphous SiC (a-SiC) matrix at a low substrate temperature and without any commonly used hydrogen dilution. The experimental results clearly demonstrate that uniform crystalline Si QDs with a size of 3-4 nm embedded in the silicon-rich (carbon content up to 10.7at.%) a-SiC matrix can be formed from the reactive mixture of silane and methane gases, with high growth rates of ∼1.27-2.34 nm s-1 and at a low substrate temperature of 200 °C. The achievement of the high-rate growth of Si QDs embedded in the a-SiC without any commonly used hydrogen dilution is discussed based on the unique properties of the inductively coupled plasma-based process. This work is particularly important for the development of the all-Si tandem cell-based third generation photovoltaic solar cells.

Increased size selectivity of Si quantum dots on SiC at low substrate temperatures : an ion-assisted self-organization approach

A simple, effective, and innovative approach based on ion-assisted self-organization is proposed to synthesize size-selected Si quantum dots (QDs) on SiC substrates at low substrate temperatures. Using hybrid numerical simulations, the formation of Si QDs through a self-organization approach is investigated by taking into account two distinct cases of Si QD formation using the ionization energy approximation theory, which considers ionized in-fluxes containing Si3+ and Si1+ ions in the presence of a microscopic nonuniform electric field induced by a variable surface bias. The results show that the highest percentage of the surface coverage by 1 and 2 nm size-selected QDs was achieved using a bias of -20 V and ions in the lowest charge state, namely, Si1+ ions in a low substrate temperature range (227-327 °C). As low substrate temperatures (≤500 °C) are desirable from a technological point of view, because (i) low-temperature deposition techniques are compatible with current thin-film Si-based solar cell fabrication and (ii) high processing temperatures can frequently cause damage to other components in electronic devices and destroy the tandem structure of Si QD-based third-generation solar cells, our results are highly relevant to the development of the third-generation all-Si tandem photovoltaic solar cells.

Structural evolution of nanocrystalline silicon thin films synthesized in high-density, low-temperature reactive plasmas

Silicon thin films with a variable content of nanocrystalline phase were deposited on single-crystal silicon and glass substrates by inductively coupled plasma-assisted chemical vapor deposition using a silane precursor without any hydrogen dilution in the low substrate temperature range from 100 to 300 °C. The structural and optical properties of the deposited films are systematically investigated by Raman spectroscopy, x-ray diffraction, Fourier transform infrared absorption spectroscopy, UV/vis spectroscopy, scanning electron microscopy and high-resolution transmission electron microscopy. It is shown that the structure of the silicon thin films evolves from the purely amorphous phase to the nanocrystalline phase when the substrate temperature is increased from 100 to 150 °C. It is found that the variations of the crystalline fraction fc, bonded hydrogen content CH, optical bandgap ETauc, film microstructure and growth rate Rd are closely related to the substrate temperature. In particular, at a substrate temperature of 300 °C, the nanocrystalline Si thin films of our interest feature a high growth rate of 1.63nms-1, a low hydrogen content of 4.0at.%, a high crystalline fraction of 69.1%, a low optical bandgap of 1.55eV and an almost vertically aligned columnar structure with a mean grain size of approximately 10nm. It is also shown that the low-temperature synthesis of nanocrystalline Si thin films without any hydrogen dilution is attributed to the outstanding dissociation ability of the high-density inductively coupled plasmas and effective plasma-surface interactions during the growth process. Our results offer a highly effective yet simple and environmentally friendly technique to synthesize high-quality nanocrystalline Si films, vitally needed for the development of new-generation solar cells and other emerging nanotechnologies.

Properties of lignin and poly(hydroxybutyrate) blends

The Queensland University of Technology (QUT) allows the presentation of a thesis for the Degree of Doctor of Philosophy in the format of published or submitted papers, where such papers have been published, accepted or submitted during the period of candidature. This thesis is composed of Seven published/submitted papers and one poster presentation, of which five have been published and the other two are under review. This project is financially supported by the QUTPRA Grant. The twenty-first century started with the resurrection of lignocellulosic biomass as a potential substitute for petrochemicals. Petrochemicals, which enjoyed the sustainable economic growth during the past century, have begun to reach or have reached their peak. The world energy situation is complicated by political uncertainty and by the environmental impact associated with petrochemical import and usage. In particular, greenhouse gasses and toxic emissions produced by petrochemicals have been implicated as a significant cause of climate changes. Lignocellulosic biomass (e.g. sugarcane biomass and bagasse), which potentially enjoys a more abundant, widely distributed, and cost-effective resource base, can play an indispensible role in the paradigm transition from fossil-based to carbohydrate-based economy. Poly(3-hydroxybutyrate), PHB has attracted much commercial interest as a plastic and biodegradable material because some its physical properties are similar to those of polypropylene (PP), even though the two polymers have quite different chemical structures. PHB exhibits a high degree of crystallinity, has a high melting point of approximately 180°C, and most importantly, unlike PP, PHB is rapidly biodegradable. Two major factors which currently inhibit the widespread use of PHB are its high cost and poor mechanical properties. The production costs of PHB are significantly higher than for plastics produced from petrochemical resources (e.g. PP costs $US1 kg-1, whereas PHB costs $US8 kg-1), and its stiff and brittle nature makes processing difficult and impedes its ability to handle high impact. Lignin, together with cellulose and hemicellulose, are the three main components of every lignocellulosic biomass. It is a natural polymer occurring in the plant cell wall. Lignin, after cellulose, is the most abundant polymer in nature. It is extracted mainly as a by-product in the pulp and paper industry. Although, traditionally lignin is burnt in industry for energy, it has a lot of value-add properties. Lignin, which to date has not been exploited, is an amorphous polymer with hydrophobic behaviour. These make it a good candidate for blending with PHB and technically, blending can be a viable solution for price and reduction and enhance production properties. Theoretically, lignin and PHB affect the physiochemical properties of each other when they become miscible in a composite. A comprehensive study on structural, thermal, rheological and environmental properties of lignin/PHB blends together with neat lignin and PHB is the targeted scope of this thesis. An introduction to this research, including a description of the research problem, a literature review and an account of the research progress linking the research papers is presented in Chapter 1. In this research, lignin was obtained from bagasse through extraction with sodium hydroxide. A novel two-step pH precipitation procedure was used to recover soda lignin with the purity of 96.3 wt% from the black liquor (i.e. the spent sodium hydroxide solution). The precipitation process is presented in Chapter 2. A sequential solvent extraction process was used to fractionate the soda lignin into three fractions. These fractions, together with the soda lignin, were characterised to determine elemental composition, purity, carbohydrate content, molecular weight, and functional group content. The thermal properties of the lignins were also determined. The results are presented and discussed in Chapter 2. On the basis of the type and quantity of functional groups, attempts were made to identify potential applications for each of the individual lignins. As an addendum to the general section on the development of composite materials of lignin, which includes Chapters 1 and 2, studies on the kinetics of bagasse thermal degradation are presented in Appendix 1. The work showed that distinct stages of mass losses depend on residual sucrose. As the development of value-added products from lignin will improve the economics of cellulosic ethanol, a review on lignin applications, which included lignin/PHB composites, is presented in Appendix 2. Chapters 3, 4 and 5 are dedicated to investigations of the properties of soda lignin/PHB composites. Chapter 3 reports on the thermal stability and miscibility of the blends. Although the addition of soda lignin shifts the onset of PHB decomposition to lower temperatures, the lignin/PHB blends are thermally more stable over a wider temperature range. The results from the thermal study also indicated that blends containing up to 40 wt% soda lignin were miscible. The Tg data for these blends fitted nicely to the Gordon-Taylor and Kwei models. Fourier transform infrared spectroscopy (FT-IR) evaluation showed that the miscibility of the blends was because of specific hydrogen bonding (and similar interactions) between reactive phenolic hydroxyl groups of lignin and the carbonyl group of PHB. The thermophysical and rheological properties of soda lignin/PHB blends are presented in Chapter 4. In this chapter, the kinetics of thermal degradation of the blends is studied using thermogravimetric analysis (TGA). This preliminary investigation is limited to the processing temperature of blend manufacturing. Of significance in the study, is the drop in the apparent energy of activation, Ea from 112 kJmol-1 for pure PHB to half that value for blends. This means that the addition of lignin to PHB reduces the thermal stability of PHB, and that the comparative reduced weight loss observed in the TGA data is associated with the slower rate of lignin degradation in the composite. The Tg of PHB, as well as its melting temperature, melting enthalpy, crystallinity and melting point decrease with increase in lignin content. Results from the rheological investigation showed that at low lignin content (.30 wt%), lignin acts as a plasticiser for PHB, while at high lignin content it acts as a filler. Chapter 5 is dedicated to the environmental study of soda lignin/PHB blends. The biodegradability of lignin/PHB blends is compared to that of PHB using the standard soil burial test. To obtain acceptable biodegradation data, samples were buried for 12 months under controlled conditions. Gravimetric analysis, TGA, optical microscopy, scanning electron microscopy (SEM), differential scanning calorimetry (DSC), FT-IR, and X-ray photoelectron spectroscopy (XPS) were used in the study. The results clearly demonstrated that lignin retards the biodegradation of PHB, and that the miscible blends were more resistant to degradation compared to the immiscible blends. To obtain an understanding between the structure of lignin and the properties of the blends, a methanol-soluble lignin, which contains 3× less phenolic hydroxyl group that its parent soda lignin used in preparing blends for the work reported in Chapters 3 and 4, was blended with PHB and the properties of the blends investigated. The results are reported in Chapter 6. At up to 40 wt% methanolsoluble lignin, the experimental data fitted the Gordon-Taylor and Kwei models, similar to the results obtained soda lignin-based blends. However, the values obtained for the interactive parameters for the methanol-soluble lignin blends were slightly lower than the blends obtained with soda lignin indicating weaker association between methanol-soluble lignin and PHB. FT-IR data confirmed that hydrogen bonding is the main interactive force between the reactive functional groups of lignin and the carbonyl group of PHB. In summary, the structural differences existing between the two lignins did not manifest itself in the properties of their blends.

Hysteresis and mode transitions in a low-frequency inductively coupled plasma

The performance of the 500 KHz planar-coil inductively coupled plasma source was studied. The global electrical characteristics of the discharge, distributions of the induced electromagnetic fields, plasma density, potential, and electron temperature were investigated. Achieved high plasma density and low electron temperature implied that the studied plasma source was promising for industrial applications.

The effects of ambient temperature on cerebrovascular mortality: An epidemiologic study in four climatic zones in China

Background Little evidence is available about the association between temperature and cerebrovascular mortality in China. This study aims to examine the effects of ambient temperature on cerebrovascular mortality in different climatic zones in China. Method We obtained daily data on weather conditions, air pollution and cerebrovascular deaths from five cities (Beijing, Tianjin, Shanghai, Wuhan, and Guangzhou) in China during 2004-2008. We examined city-specific associations between ambient temperature and the cerebrovascular mortality, while adjusting for season, long-term trends, day of the week, relative humidity and air pollution. We examined cold effects using a 1°C decrease in temperature below a city-specific threshold, and hot effects using a 1°C increase in temperature above a city-specific threshold. We used a meta-analysis to summarize the cold and hot effects across the five cities. Results Beijing and Tianjin (with low mean temperature) had lower thresholds than Shanghai, Wuhan and Guangzhou (with high mean temperature). In Beijing, Tianjin, Wuhan and Guangzhou cold effects were delayed, while in Shanghai there was no or short induction. Hot effects were acute in all five cities. The cold effects lasted longer than hot effects. The hot effects were followed by mortality displacement. The pooled relative risk associated with a 1°C decrease in temperature below thresholds (cold effect) was 1.037 (95% confidence interval (CI): 1.020, 1.053). The pooled relative risk associated with a 1°C increase in temperature above thresholds (hot effect) was 1.014 (95% CI: 0.979, 1.050). Conclusion Cold temperatures are significantly associated with cerebrovascular mortality in China, while hot effect is not significant. People in colder climate cities were sensitive to hot temperatures, while people in warmer climate cities were vulnerable to cold temperature.

Fabrication of Fe-doped WO3 films for NO2 sensing at lower operating temperature

Fe-doped tungsten oxide thin films with different concentrations (0 to 2.6 at%) were synthesized on glass and alumina substrates at room temperature using DC reactive sputtering and subsequently annealed at 300oC for 1 hour in air. The alumina substrate has pre-printed interdigitated Pt-electrodes for gas sensing measurements. The effects of Fe-doping on the film structure and morphology, electronic and optical properties for gas sensing were investigated. The grain size of the different films on the alumina and Pt regions of the substrate vary only slightly between 43-57 nm with median size of about 50 nm. Raman spectra showed that the integrated intensity of W=O to O–W–O bands increases with increasing Fe concentrations and this indicated an increase in the number of defects. From XPS the different concentrations of the Fe-doped films were 0.03 at%, 1.33 at% and 2.6 at%. All the films deposited on glass substrate have shown similar visible transmittance (about 70%) but the optical band gap of the pure film decreased form 3.30 eV to 3.15 eV after doping with 2.6 at% Fe. The Fe-doped WO3 film with the highest Fe concentration (2.6 at% Fe) has shown an enhanced gas sensing properties to NO2 at relatively lower operating temperature (150oC) and this can be attributed to the decrease in the optical band gap and an increase in the number of defects compared to the pure WO3 film.

Cluster-based Intrusion Detection (CBID) architecture for mobile ad hoc networks

The ad hoc networks are vulnerable to attacks due to distributed nature and lack of infrastructure. Intrusion detection systems (IDS) provide audit and monitoring capabilities that offer the local security to a node and help to perceive the specific trust level of other nodes. The clustering protocols can be taken as an additional advantage in these processing constrained networks to collaboratively detect intrusions with less power usage and minimal overhead. Existing clustering protocols are not suitable for intrusion detection purposes, because they are linked with the routes. The route establishment and route renewal affects the clusters and as a consequence, the processing and traffic overhead increases due to instability of clusters. The ad hoc networks are battery and power constraint, and therefore a trusted monitoring node should be available to detect and respond against intrusions in time. This can be achieved only if the clusters are stable for a long period of time. If the clusters are regularly changed due to routes, the intrusion detection will not prove to be effective. Therefore, a generalized clustering algorithm has been proposed that can run on top of any routing protocol and can monitor the intrusions constantly irrespective of the routes. The proposed simplified clustering scheme has been used to detect intrusions, resulting in high detection rates and low processing and memory overhead irrespective of the routes, connections, traffic types and mobility of nodes in the network. Clustering is also useful to detect intrusions collaboratively since an individual node can neither detect the malicious node alone nor it can take action against that node on its own.

Thermally evaporated tungsten oxide (WO3) thin films for gas sensing applications

In this thesis, the author proposed and developed gas sensors made of nanostructured WO3 thin film by a thermal evaporation technique. This technique gives control over film thickness, grain size and purity. The device fabrication, nanostructured material synthesis, characterization and gas sensing performance have been undertaken. Three different types of nanostructured thin films, namely, pure WO3 thin films, iron-doped WO3 thin films by co-evaporation and Fe-implanted WO3 thin films have been synthesized. All the thin films have a film thickness of 300 nm. The physical, chemical and electronic properties of these films have been optimized by annealing heat treatment at 300ºC and 400ºC for 2 hours in air. Various analytical techniques were employed to characterize these films. Atomic Force Microscopy and Transmission Electron Microscopy revealed a very small grain size of the order 5-10 nm in as-deposited WO3 films, and annealing at 300ºC or 400ºC did not result in any significant change in grain size. X-ray diffraction (XRD) analysis revealed a highly amorphous structure of as-deposited films. Annealing at 300ºC for 2 hours in air did not improve crystallinity in these films. However, annealing at 400ºC for 2 hours in air significantly improved the crystallinity in pure and iron-doped WO3 thin films, whereas it only slightly improved the crystallinity of iron-implanted WO3 thin film as a result of implantation. Rutherford backscattered spectroscopy revealed an iron content of 0.5 at.% and 5.5 at.% in iron-doped and iron-implanted WO3 thin films, respectively. The RBS results have been confirmed using energy dispersive x-ray spectroscopy (EDX) during analysis of the films using transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) revealed significant lowering of W 4f7/2 binding energy in all films annealed at 400ºC as compared with the as-deposited and 300ºC annealed films. Lowering of W 4f7/2 is due to increase in number of oxygen vacancies in the films and is considered highly beneficial for gas sensing. Raman analysis revealed that 400ºC annealed films except the iron-implanted film are highly crystalline with significant number of O-W-O bonds, which was consistent with the XRD results. Additionally, XRD, XPS and Raman analyses showed no evidence of secondary peaks corresponding to compounds of iron due to iron doping or implantation. This provided an understanding that iron was incorporated in the host WO3 matrix rather than as a separate dispersed compound or as catalyst on the surface. WO3 thin film based gas sensors are known to operate efficiently in the temperature range 200ºC-500 ºC. In the present study, by optimizing the physical, chemical and electronic properties through heat treatment and doping, an optimum response to H2, ethanol and CO has been achieved at a low operating temperature of 150ºC. Pure WO3 thin film annealed at 400ºC showed the highest sensitivity towards H2 at 150ºC due to its very small grain size and porosity, coupled with high number of oxygen vacancies, whereas Fe-doped WO3 film annealed at 400ºC showed the highest sensitivity to ethanol at an operating temperature of 150ºC due to its crystallinity, increased number of oxygen vacancies and higher degree of crystal distortions attributed to Fe addition. Pure WO3 films are known to be insensitive to CO, but iron-doped WO3 thin film annealed at 300ºC and 400ºC showed an optimum response to CO at an operating temperature of 150ºC. This result is attributed to lattice distortions produced in WO3 host matrix as a result of iron incorporation as substitutional impurity. However, iron-implanted WO3 thin films did not show any promising response towards the tested gases as the film structure has been damaged due to implantation, and annealing at 300ºC or 400ºC was not sufficient to induce crystallinity in these films. This study has demonstrated enhanced sensing properties of WO3 thin film sensors towards CO at lower operating temperature, which was achieved by optimizing the physical, chemical and electronic properties of the WO3 film through Fe doping and annealing. This study can be further extended to systematically investigate the effects of different Fe concentrations (0.5 at.% to 10 at.%) on the sensing performance of WO3 thin film gas sensors towards CO.

Conductometric gas sensors based on nanostructured WO3 thin films

Nanostructured WO3 thin films have been prepared by thermal evaporation to detect hydrogen at low temperatures. The influence of heat treatment on the physical, chemical and electronic properties of these films has been investigated. The films were annealed at 400oC for 2 hours in air. AFM and TEM analysis revealed that the as-deposited WO3 film is high amorphous and made up of cluster of particles. Annealing at 400oC for 2 hours in air resulted in very fine grain size of the order of 5 nm and porous structure. GIXRD and Raman analysis revealed that annealing improved the crystallinity of WO3 film. Gas sensors based on annealed WO3 films have shown a high response towards various concentrations (10-10000 ppm) H2 at an operating temperature of 150oC. The improved sensing performance at low operating temperature is due to the optimum physical, chemical and electronic properties achieved in the WO3 film through annealing.

Re-melting of Bi-2212/Ag laminated tapes by partial melting process

Bi-2212 tapes are prepared by a combination of dip-coating and partial melt processing. We investigate the effect of re-melting of those tapes by partial melting followed by slow cooling on the structure and superconducting properties. Microstructural studies of re-melted samples show that they have the same overall composition as partially melted tapes. However, the fractional volumes of the secondary phases differ and the amounts and distribution of the secondary phases have a significant effect on the critical current. Critical current of Bi-2212/Ag tapes strongly depends on the maximum processing temperature. Initial J(c)'s of the tapes, which are partially melted, then slowly solidified at optimum conditions and finally post-annealed in an inert atmosphere, are up to 10.4 x 10(3) A/cm(2). It is found that the maximum processing temperature at initial partial melting has an influence on the optimum re-heat treatment conditions for the tapes. Re-melted tapes processed at optimum conditions recover superconducting properties after post-annealing in an inert atmosphere: the J(c) values of the tapes are about 80-110% of initial J(c)'s of those tapes.

A comparative study of different porous amorphous silica minerals supported TiO2 catalysts

Three porous amorphous silica minerals, including diatomite, opal and porous precipitated SiO2wereadopted to prepare supported TiO2catalysts by hydrolysis–deposition method. The prepared compoundmaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fouriertransform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Through morphology and physical chemistry properties of the resultingTiO2/amorphous SiO2catalysts, it was proposed that the nature of silica supports could affect the particlesize and the crystal form of TiO2and then further influence the photocatalytic property of TiO2/amorphousSiO2catalysts. The catalytic properties of these porous amorphous silica supported photocatalysts(TiO2/SiO2) were investigated by UV-assisted degradation of Rhodamine B (RhB). Compared with pureTiO2(P25) and the other two TiO2/amorphous SiO2catalysts, TiO2/diatomite photocatalyst exhibits bet-ter catalytic performance at different calcined temperatures, the decoloration rate of which can be upto over 85% even at a relatively low calcined temperature. The TiO2/diatomite photocatalyst possessesmixed-phase TiO2with relatively smaller particles size, which might be responsible for higher photo-catalytic activity. Moreover, the stable and much inerter porous microstructure of diatomite could beanother key factor in improving its activity.

A detailed investigation of nominally 2-D radical-farming scramjet combustion

This paper reports on an investigation of the flow/chemistry coupling inside a nominally two-dimensional inlet-fuelled scramjet configuration. The experiments were conducted at a freestream Mach number of 7.3 and a total flow enthalpy of 4.3MJ/kg corresponding to a Mach 9.7 flight condition. The phenomenon of radical-farming has been studied in detail using two-dimensional OH* chemiluminescence imaging and emission spectroscopy. High signal levels of excited OH (OH*) were detected behind the first shock reflections inside the combustion chamber upstream of any measurable pressure rise from combustion, which occurred towards the rear of the combustor. The production of OH in the first hot pocket initiates the ignition process and then accelerates the combustion process in the next downstream hot pocket. This was confirmed by numerical simulations of premixed hydrogen/air flow through the scramjet. Chemical kinetics analyses reveal that the ignition process is governed by the interaction between various reaction groups leading to a chainbranching explosion for low mean temperature and pressure combustion flowfields.