Sulfate anion templation of macrocycles, capsules, interpenetrated and interlocked structures

This review examines the potential of anions, in particular sulfate, to template the formation of complex molecular architectures. Until recently, sulfate has been largely overlooked in this area and the examples described herein demonstrate this anion’s versatility in templating the formation of a diverse range of molecular systems including macrocycles, helixes, molecular capsules, interpenetrated and interlocked assemblies such as catenanes. In addition sulfate has been shown to template the formation of interpenetrated structures on a range of solid surfaces including gold, polystyrene beads and silicate nanoparticles, highlighting the potential of this anion in the fabrication of functional sensory devices exhibiting highly selective binding behaviour.

A general procedure for the derivation of principal domains of higher-order spectra

A general procedure to determine the principal domain (i.e., nonredundant region of computation) of any higher-order spectrum is presented, using the bispectrum as an example. The procedure is then applied to derive the principal domain of the trispectrum of a real-valued, stationary time series. These results are easily extended to compute the principal domains of other higher-order spectra

Vibration characteristics of concrete-steel composite floor structures

This paper discusses the vibration characteristics of a concrete-steel composite multi-panel floor structure; the use of these structures is becoming more common. These structures have many desirable properties but are prone to excessive and complex vibration, which is not currently well understood. Existing design codes and practice guides provide generic advice or simple techniques that cannot address the complex vibration in these types of low-frequency structures. The results of this study show the potential for an adverse dynamic response from higher and multi-modal excitation influenced by human-induced pattern loading, structural geometry, and activity frequency. Higher harmonics of the load frequency are able to excite higher modes in the composite floor structure in addition to its fundamental mode. The analytical techniques used in this paper can supplement the current limited code and practice guide provisions for mitigating the impact of human-induced vibrations in these floor structures.

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.

A review of optimization techniques used in the design of fibre composite structures for civil engineering applications

Fibre composite structures have become the most attractive candidate for civil engineering applications. Fibre reinforced plastic polymer (FRP) composite materials have been used in the rehabilitation and replacement of the old degrading traditional structures or build new structures. However, the lack of design standards for civil infrastructure limits their structural applications. The majority of the existing applications have been designed based on the research and guidelines provided by the fibre composite manufacturers or based on the designer’s experience. It has been a tendency that the final structure is generally over-designed. This paper provides a review on the available studies related to the design optimization of fibre composite structures used in civil engineering such as; plate, beam, box beam, sandwich panel, bridge girder, and bridge deck. Various optimization methods are presented and compared. In addition, the importance of using the appropriate optimization technique is discussed. An improved methodology, which considering experimental testing, numerical modelling, and design constrains, is proposed in the paper for design optimization of composite structures.

General characteristics of anticipated user experience (AUX) with interactive products

Providing a positive user experience (UX) has become the key differentiator for products to win a competition in mature markets. To ensure that a product will support enjoyable experiences for its users, assessment of UX should be conducted early during the design and development process. However, most UX frameworks and evaluation techniques focus on understanding and assessing user’s experience with functional prototypes or existing products. This situation delays UX assessment until the late phases of product development which may result in costly design modifications and less desirable products. A qualitative study was conducted to investigate anticipated user experience (AUX) to address this issue. Twenty pairs of participants were asked to imagine an interactive product, draw their product concept, and anticipate their interactions and experiences with it. The data was analyzed to identify general characteristics of AUX. We found that while positive AUX was mostly related to an imagined/desired product, negative AUX was mainly associated with existing products. It was evident that the pragmatic quality of product was fundamental, and significantly influenced user’s anticipated experiences. Furthermore, the hedonic quality of product received more focus in positive than negative AUX. The results also showed that context, user profile, experiential knowledge, and anticipated emotion could be reflected in AUX. The understanding of AUX will help product designers to better foresee the users’ underlying needs and to focus on the most important aspects of their positive experiences, which in turn facilitates the designers to ensure pleasurable UX from the start of the design process.

Hydrogen-bonding in the structures of the hydrated proton-transfer compounds of isonipecotamide with the isomeric indole-2 and indole-3-carboxylic acids

The structures of two hydrated proton-transfer compounds of 4-piperidinecarboxamide (isonipecotamide) with the isomeric heteroaromatic carboxylic acids indole-2-carboxylic acid and indole-3-carboxylic acid, namely 4-carbamoylpiperidinium indole-2-carboxylate dihydrate (1) and 4-carbamoylpiperidinium indole-3-carboxylate hemihydrate (2) have been determined at 200 K. Crystals of both 1 and 2 are monoclinic, space groups P21/c and P2/c respectively with Z = 4 in cells having dimensions a = 10.6811(4), b = 12.2017(4), c = 12.5456(5) Å, β = 96.000(4)o (1) and a = 15.5140(4), b = 10.2908(3), c = 9.7047(3) Å, β = 97.060(3)o (2). Hydrogen-bonding in 1 involves a primary cyclic interaction involving complementary cation amide N-H…O(carboxyl) anion and anion hetero N-H…O(amide) cation hydrogen bonds [graph set R22(9)]. Secondary associations involving also the water molecules of solvation give a two-dimensional network structure which includes weak water O-H…π interactions. In the three-dimensional hydrogen-bonded structure of 2, there are classic centrosymmetric cyclic head-to-head hydrogen-bonded amide-amide interactions [graph set R22(8)] as well as lateral cyclic amide-O linked amide-amide extensions [graph set R24(8)]. The anions and the water molecule, which lies on a twofold rotation axis, are involved in secondary extensions.

An evaluation of the sustainability of agreements reached through mediations conducted by the dispute resolution centres of the Department of Justice and Attorney General, Queensland between 1999 to 2003

In 1990 the Dispute Resolution Centres Act, 1990 (Qld) (the Act) was passed by the Queensland Parliament. In the second reading speech for the Dispute Resolution Centres Bill on May 1990 the Hon Dean Wells stated that the proposed legislation would make mediation services available “in a non-coercive, voluntary forum where, with the help of trained mediators, the disputants will be assisted towards their own solutions to their disputes, thereby ensuring that the result is acceptable to the parties” (Hansard, 1990, 1718). It was recognised at that time that a method for resolving disputes was necessary for which “the conventional court system is not always equipped to provide lasting resolution” (Hansard, 1990, 1717). In particular, the lasting resolution of “disputes between people in continuing relationships” was seen as made possible through the new legislation; for example, “domestic disputes, disputes between employees, and neighbourhood disputes relating to such issues as overhanging tree branches, dividing fences, barking dogs, smoke, noise and other nuisances are occurring continually in the community” (Hansard, 1990, 1717). The key features of the proposed form of mediation in the Act were articulated as follows: “attendance of both parties at mediation sessions is voluntary; a party may withdraw at any time; mediation sessions will be conducted with as little formality and technicality as possible; the rules of evidence will not apply; any agreement reached is not enforceable in any court; although it could be made so if the parties chose to proceed that way; and the provisions of the Act do not affect any rights or remedies that a party to a dispute has apart from the Act” (Hansard, 1990, 1718). Since the introduction of the Act, the Alternative Dispute Resolution Branch of the Queensland Department of Justice and Attorney General has offered mediation services through, first the Community Justice Program (CJP), and then the Dispute Resolution Centres (DRCs) for a range of family, neighbourhood, workplace and community disputes. These services have mirrored those available through similar government agencies in other states such as the Community Justice Centres of NSW and the Victorian Dispute Resolution Centres. Since 1990, mediation has become one of the fastest growing forms of alternative dispute resolution (ADR). Sourdin has commented that "In addition to the growth in court-based and community-based dispute resolution schemes, ADR has been institutionalised and has grown within Australia and overseas” (2005, 14). In Australia, in particular, the development of ADR service provision “has been assisted by the creation and growth of professional organisations such as the Leading Edge Alternative Dispute Resolvers (LEADR), the Australian Commercial Dispute Centres (ACDC), Australian Disputes Resolution Association (ADRA), Conflict Resolution Network, and the Institute of Arbitrators and Mediators Australia (IAMA)” (Sourdin, 2005, 14). The increased emphasis on the use of ADR within education contexts (particularly secondary and tertiary contexts) has “also led to an increasing acceptance and understanding of (ADR) processes” (Sourdin, 2005, 14). Proponents of the mediation process, in particular, argue that much of its success derives from the inherent flexibility and creativity of the agreements reached through the mediation process and that it is a relatively low cost option in many cases (Menkel-Meadow, 1997, 417). It is also accepted that one of the main reasons for the success of mediation can be attributed to the high level of participation by the parties involved and thus creating a sense of ownership of, and commitment to, the terms of the agreement (Boulle, 2005, 65). These characteristics are associated with some of the core values of mediation, particularly as practised in community-based models as found at the DRCs. These core values include voluntary participation, party self-determination and party empowerment (Boulle, 2005, 65). For this reason mediation is argued as being an effective approach to resolving disputes, that creates a lasting resolution of the issues. Evaluation of the mediation process, particularly in the context of the growth of ADR, has been an important aspect of the development of the process (Sourdin, 2008). Writing in 2005 for example, Boulle, states that “although there is a constant refrain for more research into mediation practice, there has been a not insignificant amount of mediation measurement, both in Australia and overseas” (Boulle, 2005, 575). The positive claims of mediation have been supported to a significant degree by evaluations of the efficiency and effectiveness of the process. A common indicator of the effectiveness of mediation is the settlement rate achieved. High settlement rates for mediated disputes have been found for Australia (Altobelli, 2003) and internationally (Alexander, 2003). Boulle notes that mediation agreement rates claimed by service providers range from 55% to 92% (Boulle, 2005, 590). The annual reports for the Alternative Dispute Resolution Branch of the Queensland Department of Justice and Attorney-General considered prior to the commencement of this study indicated generally achievement of an approximate settlement figure of 86% by the Queensland Dispute Resolution Centres. More recently, the 2008-2009 annual report states that of the 2291 civil dispute mediated in 2007-2008, 86% reached an agreement. Further, of the 2693 civil disputes mediated in 2008-2009, 73% reached an agreement. These results are noted in the report as indicating “the effectiveness of mediation in resolving disputes” and as reflecting “the high level of agreement achieved for voluntary mediations” (Annual Report, 2008-2009, online). Whilst the settlement rates for the DRCs are strong, parties are rarely contacted for long term follow-up to assess whether agreements reached during mediation lasted to the satisfaction of each party. It has certainly been the case that the Dispute Resolution Centres of Queensland have not been resourced to conduct long-term follow-up assessments of mediation agreements. As Wade notes, "it is very difficult to compare "success" rates” and whilst “politicians want the comparison studies (they) usually do not want the delay and expense of accurate studies" (1998, 114). To date, therefore, it is fair to say that the efficiency of the mediation process has been evaluated but not necessarily its effectiveness. Rather, the practice at the Queensland DRCs has been to evaluate the quality of mediation service provision and of the practice of the mediation process. This has occurred, for example, through follow-up surveys of parties' satisfaction rates with the mediation service. In most other respects it is fair to say that the Centres have relied on the high settlement rates of the mediation process as a sign of the effectiveness of mediation (Annual Reports 1991 - 2010). Research of the mediation literature conducted for the purpose of this thesis has also indicated that there is little evaluative literature that provides an in-depth analysis and assessment of the longevity of mediated agreements. Instead evaluative studies of mediation tend to assess how mediation is conducted, or compare mediation with other conflict resolution options, or assess the agreement rate of mediations, including parties' levels of satisfaction with the service provision of the dispute resolution service provider (Boulle, 2005, Chapter 16).