N-Aryl stilbazolium dyes as sensitizers for solar cells

Eight new N-arylstilbazolium chromophores with electron donating –NR2 (R = Me or Ph) substituents have been synthesized via Knoevenagel condensations and isolated as their PF6− salts. These compounds have been characterized by using various techniques including 1H NMR and IR spectroscopies and electrospray mass spectrometry. UV–vis absorption spectra recorded in acetonitrile are dominated by intense, low energy π → π* intramolecular charge-transfer (ICT) bands, and replacing Me with Ph increases the ICT energies. Cyclic voltammetric studies show irreversible reduction processes, together with oxidation waves that are irreversible for R = Me, but reversible for R = Ph. Single crystal X-ray structures have been determined for three of the methyl ester-substituted stilbazolium salts and for the Cl− salts of their picolinium precursors. Time-dependent density functional theory calculations afford reasonable predictions of ICT energies, but greater rigour is necessary for –NPh2 derivatives. The four new acid-functionalized dyes give moderate sensitization efficiencies (ca. 0.2%) when using TiO2-based photoanodes, with relatively higher values for R = Ph vs Me, while larger efficiencies (up to 0.8%) are achieved with ZnO substrates.

Physical characteristics of small ions and their interaction with ultrafine particles in the urban environment

In recent years, the effect of ions and ultrafine particles on ambient air quality and human health has been well documented, however, knowledge about their sources, concentrations and interactions within different types of urban environments remains limited. This thesis presents the results of numerous field studies aimed at quantifying variations in ion concentration with distance from the source, as well as identifying the dynamics of the particle ionisation processes which lead to the formation of charged particles in the air. In order to select the most appropriate measurement instruments and locations for the studies, a literature review was also conducted on studies that reported ion and ultrafine particle emissions from different sources in a typical urban environment. The initial study involved laboratory experiments on the attachment of ions to aerosols, so as to gain a better understanding of the interaction between ions and particles. This study determined the efficiency of corona ions at charging and removing particles from the air, as a function of different particle number and ion concentrations. The results showed that particle number loss was directly proportional to particle charge concentration, and that higher small ion concentrations led to higher particle deposition rates in all size ranges investigated. Nanoparticles were also observed to decrease with increasing particle charge concentration, due to their higher Brownian mobility and subsequent attachment to charged particles. Given that corona discharge from high voltage powerlines is considered one of the major ion sources in urban areas, a detailed study was then conducted under three parallel overhead powerlines, with a steady wind blowing in a perpendicular direction to the lines. The results showed that large sections of the lines did not produce any corona at all, while strong positive emissions were observed from discrete components such as a particular set of spacers on one of the lines. Measurements were also conducted at eight upwind and downwind points perpendicular to the powerlines, spanning a total distance of about 160m. The maximum positive small and large ion concentrations, and DC electric field were observed at a point 20 m downwind from the lines, with median values of 4.4×103 cm-3, 1.3×103 cm-3 and 530 V m-1, respectively. It was estimated that, at this point, less than 7% of the total number of particles was charged. The electrical parameters decreased steadily with increasing downwind distance from the lines but remained significantly higher than background levels at the limit of the measurements. Moreover, vehicles are one of the most prevalent ion and particle emitting sources in urban environments, and therefore, experiments were also conducted behind a motor vehicle exhaust pipe and near busy motorways, with the aim of quantifying small ion and particle charge concentration, as well as their distribution as a function of distance from the source. The study found that approximately equal numbers of positive and negative ions were observed in the vehicle exhaust plume, as well as near motorways, of which heavy duty vehicles were believed to be the main contributor. In addition, cluster ion concentration was observed to decrease rapidly within the first 10-15 m from the road and ion-ion recombination and ion-aerosol attachment were the most likely cause of ion depletion, rather than dilution and turbulence related processes. In addition to the above-mentioned dominant ion sources, other sources also exist within urban environments where intensive human activities take place. In this part of the study, airborne concentrations of small ions, particles and net particle charge were measured at 32 different outdoor sites in and around Brisbane, Australia, which were classified into seven different groups as follows: park, woodland, city centre, residential, freeway, powerlines and power substation. Whilst the study confirmed that powerlines, power substations and freeways were the main ion sources in an urban environment, it also suggested that not all powerlines emitted ions, only those with discrete corona discharge points. In addition to the main ion sources, higher ion concentrations were also observed environments affected by vehicle traffic and human activities, such as the city centre and residential areas. A considerable number of ions were also observed in a woodland area and it is still unclear if they were emitted directly from the trees, or if they originated from some other local source. Overall, it was found that different types of environments had different types of ion sources, which could be classified as unipolar or bipolar particle sources, as well as ion sources that co-exist with particle sources. In general, fewer small ions were observed at sites with co-existing sources, however particle charge was often higher due to the effect of ion-particle attachment. In summary, this study quantified ion concentrations in typical urban environments, identified major charge sources in urban areas, and determined the spatial dispersion of ions as a function of distance from the source, as well as their controlling factors. The study also presented ion-aerosol attachment efficiencies under high ion concentration conditions, both in the laboratory and in real outdoor environments. The outcomes of these studies addressed the aims of this work and advanced understanding of the charge status of aerosols in the urban environment.

Optical and microscopic study of a polymer-nanotube mixture for organic photovoltaic applications

Organic solar cells based on bulk heterojunction between a conductive polymer and a carbon nanostructure offer potential advantages compared to conventional inorganic cells. Low cost, light weight, flexibility and high peak power per unit weight are all features that can be considered a reality for organic photovoltaics. Although polymer/carbon nanotubes solar cells have been proposed, only low power conversion efficiencies have been reached without addressing the mechanisms responsible for this poor performance. The purpose of this work is therefore to investigate the basic interaction between carbon nanotubes and poly(3-hexylthiophene) in order to demonstrate how this interaction affects the performance of photovoltaic devices. The outcomes of this study are the contributions made to the knowledge of the phenomena explaining the behaviour of electronic devices based on carbon nanotubes and poly(3-hexylthiophene). In this PhD, polymer thin films with the inclusion of uniformly distributed carbon nanotubes were deposited from solution and characterised. The bulk properties of the composites were studied with microscopy and spectroscopy techniques to provide evidence of higher degrees of polymer order when interacting with carbon nanotubes. Although bulk investigation techniques provided useful information about the interaction between the polymer and the nanotubes, clear evidence of the phenomena affecting the heterojunction formed between the two species was investigated at nanoscale. Identifying chirality-driven polymer assisted assembly on the carbon nanotube surface was one of the major achievements of this study. Moreover, the analysis of the electrical behaviour of the heterojunction between the polymer and the nanotube highlighted the charge transfer responsible for the low performance of photovoltaic devices. Polymer and carbon nanotube composite-based devices were fabricated and characterised in order to study their electronic properties. The carbon nanotube introduction in the polymer matrix evidenced a strong electrical conductivity enhancement but also a lower photoconductivity response. Moreover, the extension of pristine polymer device characterisation models to composites based devices evidenced the conduction mechanisms related to nanotubes. Finally, the introduction of carbon nanotubes in the polymer matrix was demonstrated to improve the pristine polymer solar cell performance and the spectral response even though the power conversion efficiency is still too low.

Structural behaviour and design of cold-formed steel wall systems under fire conditions

In recent times, light gauge steel framed (LSF) structures, such as cold-formed steel wall systems, are increasingly used, but without a full understanding of their fire performance. Traditionally the fire resistance rating of these load-bearing LSF wall systems is based on approximate prescriptive methods developed based on limited fire tests. Very often they are limited to standard wall configurations used by the industry. Increased fire rating is provided simply by adding more plasterboards to these walls. This is not an acceptable situation as it not only inhibits innovation and structural and cost efficiencies but also casts doubt over the fire safety of these wall systems. Hence a detailed fire research study into the performance of LSF wall systems was undertaken using full scale fire tests and extensive numerical studies. A new composite wall panel developed at QUT was also considered in this study, where the insulation was used externally between the plasterboards on both sides of the steel wall frame instead of locating it in the cavity. Three full scale fire tests of LSF wall systems built using the new composite panel system were undertaken at a higher load ratio using a gas furnace designed to deliver heat in accordance with the standard time temperature curve in AS 1530.4 (SA, 2005). Fire tests included the measurements of load-deformation characteristics of LSF walls until failure as well as associated time-temperature measurements across the thickness and along the length of all the specimens. Tests of LSF walls under axial compression load have shown the improvement to their fire performance and fire resistance rating when the new composite panel was used. Hence this research recommends the use of the new composite panel system for cold-formed LSF walls. The numerical study was undertaken using a finite element program ABAQUS. The finite element analyses were conducted under both steady state and transient state conditions using the measured hot and cold flange temperature distributions from the fire tests. The elevated temperature reduction factors for mechanical properties were based on the equations proposed by Dolamune Kankanamge and Mahendran (2011). These finite element models were first validated by comparing their results with experimental test results from this study and Kolarkar (2010). The developed finite element models were able to predict the failure times within 5 minutes. The validated model was then used in a detailed numerical study into the strength of cold-formed thin-walled steel channels used in both the conventional and the new composite panel systems to increase the understanding of their behaviour under nonuniform elevated temperature conditions and to develop fire design rules. The measured time-temperature distributions obtained from the fire tests were used. Since the fire tests showed that the plasterboards provided sufficient lateral restraint until the failure of LSF wall panels, this assumption was also used in the analyses and was further validated by comparison with experimental results. Hence in this study of LSF wall studs, only the flexural buckling about the major axis and local buckling were considered. A new fire design method was proposed using AS/NZS 4600 (SA, 2005), NAS (AISI, 2007) and Eurocode 3 Part 1.3 (ECS, 2006). The importance of considering thermal bowing, magnified thermal bowing and neutral axis shift in the fire design was also investigated. A spread sheet based design tool was developed based on the above design codes to predict the failure load ratio versus time and temperature for varying LSF wall configurations including insulations. Idealised time-temperature profiles were developed based on the measured temperature values of the studs. This was used in a detailed numerical study to fully understand the structural behaviour of LSF wall panels. Appropriate equations were proposed to find the critical temperatures for different composite panels, varying in steel thickness, steel grade and screw spacing for any load ratio. Hence useful and simple design rules were proposed based on the current cold-formed steel structures and fire design standards, and their accuracy and advantages were discussed. The results were also used to validate the fire design rules developed based on AS/NZS 4600 (SA, 2005) and Eurocode Part 1.3 (ECS, 2006). This demonstrated the significant improvements to the design method when compared to the currently used prescriptive design methods for LSF wall systems under fire conditions. In summary, this research has developed comprehensive experimental and numerical thermal and structural performance data for both the conventional and the proposed new load bearing LSF wall systems under standard fire conditions. Finite element models were developed to predict the failure times of LSF walls accurately. Idealized hot flange temperature profiles were developed for non-insulated, cavity and externally insulated load bearing wall systems. Suitable fire design rules and spread sheet based design tools were developed based on the existing standards to predict the ultimate failure load, failure times and failure temperatures of LSF wall studs. Simplified equations were proposed to find the critical temperatures for varying wall panel configurations and load ratios. The results from this research are useful to both structural and fire engineers and researchers. Most importantly, this research has significantly improved the knowledge and understanding of cold-formed LSF loadbearing walls under standard fire conditions.

Corporate profit and impression management in developing markets

In this study, we examine how organisations in Fiji communicate or legitimise their profit. We base the need for understanding this phenomenon on the following premise. Organisations are part of a wider society, and in competition for scarce resources. Organisations obtain the rights to consume resources upon conception, but must continually legitimise their rights of existence and the need to access the resources. Legitimacy is the ability to continue to justify one’s authority to exist in a society. Organisations rights to resources are contractual, and have a moral obligation to act in a responsible manner and justify their outcomes, actions, and activities to external stakeholders. Such justifications would be an attempt at legitimizing their existence by some form of impression management. Impression management refers to the process by which individuals attempt to influence the impression of others (Melo et al. 2009). In corporate reporting, impression management occurs when management selects, display, and presents that information in a manner that distorts readers’ perceptions of corporate achievements (Neu 1991; Patten 2002), and is managed best through disclosures (O’Donovan 2002). In developing economies, there is significant Government protection that creates near-monopoly sectors and industries. The rendered protection permits organisations to provide essential services to the community at reasonable costs. Organisations in these sectors and industries have an ominous need to legitimise their position and actions. The bond between the organisations and the society is much stronger, making organisations devote more effort in communicating their activities. Protection permits organisations to make reasonable profits to sustain their operations. Society may not accept abnormal profits from operational efficiencies. Profit is fundamental to the society’s perception of an organisation, amplifying the need for the firm to justify a level of profit. Abnormal profit for organisations construes bad news, and organisations would make relevant disclosures to manage stakeholder impressions on profit (Patten 2002). Organisations can manage impressions by disclosing information in a particular way. That is, organisations would want to put the impression that the abnormal profit is justified and the society will obtain its benefits in future. Such form of impression management requires unambiguous disclosure of information. The readability of corporate disclosures is an important indicator of organisational abnormal profit-related legitimacy efforts in developing economies.

Computational design of cyclic nitroxides as efficient redox mediators for dye-sensitized solar cells

Cyclic nitroxide radicals represent promising alternatives to the iodine-based redox mediator commonly used in dye-sensitized solar cells (DSSCs). To date DSSCs with nitroxide-based redox mediators have achieved energy conversion efficiencies of just over 5 % but efficiencies of over 15 % might be achievable, given an appropriate mediator. The efficacy of the mediator depends upon two main factors: it must reversibly undergo one-electron oxidation and it must possess an oxidation potential in a range of 0.600-0.850 V (vs. a standard hydrogen electrode (SHE) in acetonitrile at 25 °C). Herein, we have examined the effect that structural modifications have on the value of the oxidation potential of cyclic nitroxides as well as the reversibility of the oxidation process. These included alterations to the N-containing skeleton (pyrrolidine, piperidine, isoindoline, azaphenalene, etc.), as well as the introduction of different substituents (alkyl-, methoxy-, amino-, carboxy-, etc.) to the ring. Standard oxidation potentials were calculated using high-level ab initio methodology that was demonstrated to be very accurate (with a mean absolute deviation from experimental values of only 16 mV). An optimal value of 1.45 for the electrostatic scaling factor for UAKS radii in acetonitrile solution was obtained. Established trends in the values of oxidation potentials were used to guide molecular design of stable nitroxides with desired E° ox and a number of compounds were suggested for potential use as enhanced redox mediators in DSSCs. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Numerical solution of stress intensity factors of multiple cracks in great number with eigen COD boundary integral equations

Based on the eigen crack opening displacement (COD) boundary integral equations, a newly developed computational approach is proposed for the analysis of multiple crack problems. The eigen COD particularly refers to a crack in an infinite domain under fictitious traction acting on the crack surface. With the concept of eigen COD, the multiple cracks in great number can be solved by using the conventional displacement discontinuity boundary integral equations in an iterative fashion with a small size of system matrix. The interactions among cracks are dealt with by two parts according to the distances of cracks to the current crack. The strong effects of cracks in adjacent group are treated with the aid of the local Eshelby matrix derived from the traction BIEs in discrete form. While the relatively week effects of cracks in far-field group are treated in the iteration procedures. Numerical examples are provided for the stress intensity factors of multiple cracks, up to several thousands in number, with the proposed approach. By comparing with the analytical solutions in the literature as well as solutions of the dual boundary integral equations, the effectiveness and the efficiencies of the proposed approach are verified.

A decision support system for sustainable urban development : the integrated land use and transportation indexing model

Broad, early definitions of sustainable development have caused confusion and hesitation among local authorities and planning professionals. This confusion has arisen because loosely defined principles of sustainable development have been employed when setting policies and planning projects, and when gauging the efficiencies of these policies in the light of designated sustainability goals. The question of how this theory-rhetoric-practice gap can be filled is the main focus of this chapter. It examines the triple bottom line approach–one of the sustainability accounting approaches widely employed by governmental organisations–and the applicability of this approach to sustainable urban development. The chapter introduces the ‘Integrated Land Use and Transportation Indexing Model’ that incorporates triple bottom line considerations with environmental impact assessment techniques via a geographic, information systemsbased decision support system. This model helps decision-makers in selecting policy options according to their economic, environmental and social impacts. Its main purpose is to provide valuable knowledge about the spatial dimensions of sustainable development, and to provide fine detail outputs on the possible impacts of urban development proposals on sustainability levels. In order to embrace sustainable urban development policy considerations, the model is sensitive to the relationship between urban form, travel patterns and socio-economic attributes. Finally, the model is useful in picturing the holistic state of urban settings in terms of their sustainability levels, and in assessing the degree of compatibility of selected scenarios with the desired sustainable urban future.

Candidate radial-inflow turbines and high-density working fluids for geothermal power systems

Optimisation of Organic Rankine Cycle (ORCs) for binary-cycle geothermal applications could play a major role in determining the competitiveness of low to moderate temperature geothermal resources. Part of this optimisation process is matching cycles to a given resource such that power output can be maximised. Two major and largely interrelated components of the cycle are the working fluid and the turbine. Both components need careful consideration: the selection of working fluid and appropriate operating conditions as well as optimisation of the turbine design for those conditions will determine the amount of power that can be extracted from a resource. In this paper, we present the rationale for the use of radial-inflow turbines for ORC applications and the preliminary design of several radial-inflow machines based on a number of promising ORC systems that use five different working fluids: R134a, R143a, R236fa, R245fa and n-Pentane. Preliminary meanline analysis lead to the generation of turbine designs for the various cycles with similar efficiencies (77%) but large differences in dimensions (139–289 mm rotor diameter). The highest performing cycle, based on R134a, was found to produce 33% more net power from a 150 °C resource flowing at 10 kg/s than the lowest performing cycle, based on n-Pentane.

Candidate radial-inflow turbines and high-density working fluids for geothermal power systems

Optimisation of Organic Rankine Cycles (ORCs) for binary-cycle geothermal applications could play a major role in the competitiveness of low to moderate temperature geothermal resources. Part of this optimisation process is matching cycles to a given resource such that power output can be maximised. Two major and largely interrelated components of the cycle are the working fluid and the turbine. Both components need careful consideration. Due to the temperature differences in geothermal resources a one-size-fits-all approach to surface power infrastructure is not appropriate. Furthermore, the traditional use of steam as a working fluid does not seem practical due to the low temperatures of many resources. A variety of organic fluids with low boiling points may be utilised as ORC working fluids in binary power cycle loops. Due to differences in thermodynamic properties, certain fluids are able to extract more heat from a given resource than others over certain temperature and pressure ranges. This enables the tailoring of power cycle infrastructure to best match the geothermal resource through careful selection of the working fluid and turbine design optimisation to yield the optimum overall cycle performance. This paper presents the rationale for the use of radial-inflow turbines for ORC applications and the preliminary design of several radial-inflow turbines based on a selection of promising ORC cycles using five different high-density working fluids: R134a, R143a, R236fa, R245fa and n-Pentane at sub- or trans-critical conditions. Numerous studies published compare a variety of working fluids for various ORC configurations. However, there is little information specifically pertaining to the design and implementation of ORCs using realistic radial turbine designs in terms of pressure ratios, inlet pressure, rotor size and rotational speed. Preliminary 1D analysis leads to the generation of turbine designs for the various cycles with similar efficiencies (77%) but large differences in dimensions (139289 mm rotor diameter). The highest performing cycle (R134a) was found to produce 33% more net power from a 150°C resource flowing at 10 kg/s than the lowest performing cycle (n-Pentane).

The exemplification of governance principles within state asset management laws and policies : the case of Indonesia

Efficient state asset management is crucial for governments as they facilitate the fulfillment of their public functions, which include the provision of essential services and other public administration support. In recent times economies internationally and particularly in South east Asia, have displayed increased recognition of the importance of efficiencies across state asset management law, policies and practice. This has been exemplified by a surge in notable instances of reform in state asset management. A prominent theme in this phenomenon is the consideration of governance principles within the re-conceptualization of state asset management law and related policy, with many countries recognizing variability in the quality of asset governance and opportunities for profit as being critical factors. This issue is very current in Indonesia where a major reform process in this area has been confirmed by the establishment of a new Directorate of State Asset Management. The incumbent Director-General of State Asset Management has confirmed a re-emphasis on adherence to governance principles within applicable state asset management law and policy reform. This paper reviews aspects of the challenge of reviewing and reforming Indonesian practice within state asset management law and policy specifically related to public housing, public buildings, parklands, and vacant land. A critical issue in beginning this review is how Indonesia currently conceptualizes the notion of asset governance and how this meaning is embodied in recent changes in law and policy and importantly in options for future change. This paper discusses the potential complexities uniquely Indonesian characteristics such as decentralisation and regional autonomy regime, political history, and bureaucratic culture.

Multi-level knowledge transfer in software development outsourcing projects : the agency theory view

In recent years, software development outsourcing has become even more complex. Outsourcing partner have begun‘re- outsourcing’ components of their projects to other outsourcing companies to minimize cost and gain efficiencies, creating a multi-level hierarchy of outsourcing. This research in progress paper presents preliminary findings of a study designed to understand knowledge transfer effectiveness of multi-level software development outsourcing projects. We conceptualize the SD-outsourcing entities using the Agency Theory. This study conceptualizes, operationalises and validates the concept of Knowledge Transfer as a three-phase multidimensional formative index of 1) Domain knowledge, 2) Communication behaviors, and 3) Clarity of requirements. Data analysis identified substantial, significant differences between the Principal and the Agent on two of the three constructs. Using Agency Theory, supported by preliminary findings, the paper also provides prescriptive guidelines of reducing the friction between the Principal and the Agent in multi-level software outsourcing.

Approaches to the Synthesis of a Water-soluble Carboxy Nitroxide

The robust and diversely useful isoindoline nitroxide, 5-carboxy-1,1,3,3-tetramethylisoindolin-2-yloxyl (1; CTMIO), has previously been synthesised in low-to-moderate yields from phthalic anhydride (3). Recent interest in its biological potential as a potent antioxidant and in other areas has seen an increased demand for its production. Herein, three new synthetic routes to CTMIO are presented and their efficiencies assessed. Two routes, via the nitrile 9 and the formyl compound 11, derive from 5-bromo-1,1,3,3-tetramethylisoindoline (6). The third approach starts from the readily accessible starting material, 4-methylphthalic anhydride (12), and proceeds by a methylarene oxidation with potassium permanganate. The three new approaches yield CTMIO in comparable overall yields (16–18 %); however, the synthetic efficiency is most improved when employing the nitrile intermediate 9.

Insights into the nature of the coupling interactions between uracil corrosion inhibitors and copper : a DFT and molecular dynamics study

In this study, the nature of the coupling interactions between copper and uracil as well as its several derivatives has been systematically investigated employing the atoms in molecules (AIM) theory and energy decomposition analyses. The whole interaction process has been investigated through the analyses of the radial distribution functions of the Cu⋯X (X = S and O) contact on the basis of the ab initio molecular dynamics. No direct relationship between the adsorption strengths and inhibition efficiencies of the inhibitors has been observed. Additionally, the possibility of the methyl-substituted dithiouracil species to act as copper corrosion inhibitors has been tested.