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.

Organized crime : policing illegal business entrepreneurialism

Organized crime in the twenty-first century is a knowledge war that poses an incalculable global threat to the world economy and harm to society - the economic and social costs are estimated at upwards of L20 billion a year for the UK alone (SOCA 2006/7). Organized Crime: Policing Illegal Business Entrepreneurialism offers a unique approach to the tackling of this area by exploring how it works through the conceptual framework of a business enterprise. Structured in three parts, the book progresses systematically through key areas and concepts integral to dealing effectively with the myriad contemporary forms of organised crime and provides insights on where, how and when to disrupt and dismantle a criminal business activity through current policing practices and policies. From the initial set up of a crime business through to the long term forecasting for growth and profitability, the authors dissect and analyse the different phases of the business enterprise and propose a 'Knowledge-Managed Policing' (KMP) approach to criminal entrepreneurialism. Combining conceptual and practical issues, this is a must-have reference for all police professionals, policing academics and government policy makers who are interested in a Strategy-led, Intelligence supported, Knowledge-Managed approach to policing illegal business entrepreneurialism.

The moral economy of social media

In this chapter we take a high-level view of social media, focusing not on specific applications, domains, websites, or technologies, but instead our interest is in the forms of engagement that social media engender. This is not to suggest that all social media are the same, or even that everyone’s experience with any particular medium or technology is the same. However, we argue common issues arise that characterize social media in a broad sense, and provide a different analytic perspective than we would gain from looking at particular systems or applications. We do not take the perspective that social life merely happens “within” such systems, nor that social life “shapes” such systems, but rather these systems provide a site for the production of social and cultural reality – that media are always already social and the engagement with, in, and through media of all sorts is a thoroughly social phenomenon. Accordingly, in this chapter, we examine two phenomena concurrently: social life seen through the lens of social media, and social media seen through the lens of social life. In particular, we want to understand the ways that a set of broad phenomena concerning forms of participation in social life is articulated in the domain of social media. As a conceptual entry-point, we use the notion of the “moral economy” as a means to open up the domain of inquiry. We first discuss the notion of the “moral economy” as it has been used by a number of social theorists, and then identify a particular set of conceptual concerns that we suggest link it to the phenomena of social networking in general. We then discuss a series of examples drawn from a range of studies to elaborate and ground this conceptual framework in empirical data. This leads us to a broader consideration of audiences and publics in social media that, we suggest, holds important lessons for how we treat social media analytically.

Understanding business process models : the costs and benefits of structuredness

Previous research has put forward a number of properties of business process models that have an impact on their understandability. Two such properties are compactness and(block-)structuredness. What has not been sufficiently appreciated at this point is that these desirable properties may be at odds with one another. This paper presents the results of a two-pronged study aimed at exploring the trade-off between compactness and structuredness of process models. The first prong of the study is a comparative analysis of the complexity of a set of unstructured process models from industrial practice and of their corresponding structured versions. The second prong is an experiment wherein a cohort of students was exposed to semantically equivalent unstructured and structured process models. The key finding is that structuredness is not an absolute desideratum vis-a-vis for process model understandability. Instead, subtle trade-offs between structuredness and other model properties are at play.

Digital economy future directions

Advances in information and communication technologies have brought about an information revolution, leading to fundamental changes in the way information is collected or generated, shared and distributed. The internet and digital technologies are re-shaping research, innovation and creativity. Economic research has highlighted the importance of information flows and the availability of information for access and re-use. Information is crucial to the efficiency of markets and enhanced information flows promote creativity, innovation and productivity. There is a rapidly expanding body of literature which supports the economic and social benefits of enabling access to and re-use of public sector information.1 (Note that a substantial research project associated with QUT’s Intellectual Property: Knowledge, Culture and Economy (IPKCE) Research Program is engaged in a comprehensive study and analysis of the literature on the economics of access to public sector information.)

The impact of infrastructure charges on new housing costs : an international comparison

Sourcing funding for the provision of new urban infrastructure has been a policy dilemma for governments around the world for decades. This is particularly relevant in high growth areas where new services are required to support swelling populations. Existing communities resist the introduction of new taxes to fund such infrastructure, hence the introduction of charges to the developer has flourished. The Australian infrastructure funding policy dilemmas are reflective of similar matters to some extent in the United Kingdom, and to a greater extent the United States of America. In these countries, infrastructure cost recovery policies have been in place since the 1940’s and 1970’s respectively. There is an extensive body of theoretical and empirical literature that discusses the passing on (to home buyers) or passing back (to the englobo land seller) of these increased infrastructure charges, and the corresponding impact on housing cost and supply. The purpose of this research is to examine the international evidence that suggests infrastructure charges contribute to increased house prices as well as reduced land supply. The paper concludes that whilst the theoretical work is largely consistent, the empirical research to date is inconclusive and further research is required into these impacts in Australia.

Land buyers likely to foot reform costs

Article in Courier Mail. Friday July 22, 2011.

Legal Profession Act 2007 s 319 - Whether costs agreement made after trial valid and enforceable - whether agreement had retrospective operation

The decision in QCOAL Pty Ltd v Cliffs Australia Coal Pty Ltd [2010] QSC 479 involved an examination of a number of issues relating to the assessment of costs under the Legal Profession Act 2007 (Qld). The decision highlights a range of issues which, in slightly different circumstances, may have deprived the successful party of the right to recover costs by reference to the costs agreement.

Interim bills and costs assessment : was the application in or out of time?

This article examines the decision in Turner v Mitchells Solicitors [2011] QDC 61 and the issue whether an application for assessment of costs under an interim bill at the time of a final bill is subject to the usual 12-month restriction.

Developing support for micro-entrepreneurs in a developing economy in Africa

The purpose of this paper is to explore the means of building the capacity of those who are running an organisation designed to support and resource start-ups and growing micro enterprises among some of the world’s poorest urban poor. The project is based in Beira, Mozambique, one of the poorest countries in the world. The result of this study is the development of a model for providing ongoing, inexpensive, effective, capacity building in developing economies. The model also provides a base for the further development of strategies to provide better support to micro entrepreneurs in poor developing economies.

An object oriented road asset information model

Preservation and enhancement of transportation infrastructure is critical to continuous economic development in Australia. Of particular importance are the road assets infrastructure, due to their high costs of setting up and their social and economic impact on the national economy. Continuous availability of road assets, however, is contingent upon their effective design, condition monitoring, maintenance, and renovation and upgrading. However, in order to achieve this data exchange, integration, and interoperability is required across municipal boundaries. On the other hand, there are no agreed reference frameworks that consistently describe road infrastructure assets. As a consequence, specifications and technical solutions being chosen to manage road assets do not provide adequate detail and quality of information to support asset lifecycle management processes and decisions taken are based on perception not reality. This paper presents a road asset information model, which works as reference framework to, link other kinds of information with asset information; integrate different data suppliers; and provide a foundation for service driven integrated information framework for community infrastructure and asset management.

A conceptual model of capability learning for the 21st century knowledge economy

This chapter proposes a conceptual model for optimal development of needed capabilities for the contemporary knowledge economy. We commence by outlining key capability requirements of the 21st century knowledge economy, distinguishing these from those suited to the earlier stages of the knowledge economy. We then discuss the extent to which higher education currently caters to these requirements and then put forward a new model for effective knowledge economy capability learning. The core of this model is the development of an adaptive and adaptable career identity, which is created through a reflective process of career self-management, drawing upon data from the self and the world of work. In turn, career identity drives the individual’s process of skill and knowledge acquisition, including deep disciplinary knowledge. The professional capability learning thus acquired includes disciplinary skill and knowledge sets, generic skills, and also skills for the knowledge economy, including disciplinary agility, social network capability, and enterprise skills. In the final part of this chapter, we envision higher education systems that embrace the model, and suggest steps that could be taken toward making the development of knowledge economy capabilities an integral part of the university experience.

Place and Space: Community in the Internet Economy and What This Will Mean for Property

By 2020 Australia‟s National Digital Economy Strategy aims to increase household online participation and engage 12 per cent of all employees in teleworking arrangements. Achieving these goals is generally perceived as positive due to the reduced impact on the natural environment from less use of transport. However, this also will enable greater flexibility as to where people live and thus will impact upon the maintenance and formation of communities and on property use. This paper commences by clarifying what is Australia‟s internet economy before highlighting the impact of the internet on community formation and maintenance. The paper concludes by identifying what the achievement of these goals will mean for property use in the future.