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.

Everything is political

Everything is Political Ben Eltham, Kieran Lord, Jeff Brand, Truna. Chair: Daniel Golding Videogames don’t exist in isolation. They are part of artistic, cultural, and political spheres – even if some would much rather they weren’t. This panel takes a look at the way videogames are used as political tools and how we as developers and critics can better engage with that, and perhaps wrestle some of the conversation back into our hands.

Urban food futures : ICTs and opportunities

Food is a vital foundation of all human life. It is essential to a myriad of political, socio-cultural, economic and environmental practices throughout history. However, those practices of food production, consumption, and distribution have the potential to now go through immensely transformative shifts as network technologies become increasingly embedded in every domain of contemporary life. Information and communication technologies (ICTs) are one of the key foundations of global functionality and sustenance today and undoubtedly will continue to present new challenges and opportunities for the future. As such, this Symposium will bring together leading scholars across disciplines to address challenges and opportunities at the intersection of food and ICTs in everyday urban environment. In particular, the discussion will revolve around the question: What are the key roles that network technologies play in re-shaping the food systems at micro- to macroscopic level? The symposium will contribute a unique perspective on urban food futures through the lens of network society paradigm where ICTs enable innovations in production, organisation, and communication within society. Some of the topics addressed will include encouraging transparency in food commodity chains; value of cultural understanding and communication in global food sustainability; and technologies to social inclusion; all of which evoke and examine the question surrounding networked individuals as changes catalysts for urban food futures. The event will provide an avenue for new discussions and speculations on key issues surrounding urban food futures in the network era, with a particular focus on bottom-up micro actions that challenge the existing food systems towards a broader sociocultural, political, technological, and environmental transformations. One central area of concern is that current systems of food production, distribution, and consumption do not ensure food security for the future, but rather seriously threaten it. With the recent unprecedented scale of urban growth and rise of middle-class, the problem continues to intensify. This situation requires extensive distribution networks to feed urban residents, and therefore poses significant infrastructural challenges to both the public and private sectors. The symposium will also address the transferability of citizen empowerment that network technologies enable as demonstrated in various significant global political transformations from the bottom-up, such as the recent Egyptian Youth Revolution. Another key theme of the discussion will be the role of ICTs (and the practices that they mediate) in fostering transparency in commodity chains. The symposium will ask what differences these technologies can make on the practices of food consumption and production. After discussions, we will initiate an international network of food-thinkers and actors that will function as a platform for knowledge sharing and collaborations. The participants will be invited to engage in planning for the on-going future development of the network.

Trends in policies, programs and practices in the Australasian First Year Experience literature 2000-2010. The First Year in Higher Education Research Series on Evidence-based Practice. Number 1

This publication is the first in a series of scholarly reports on research-based practice related to the First Year Experience in Higher Education. This report synthesises evidence about practice-based initiatives and pragmatic approaches in Aotearoa (New Zealand) and Australia that aim to enhance the experience of commencing students in the higher education sector. Trends in policies, programs and practices ... examines the first year experience literature from 2000-2010. It acknowledges the uniqueness of the Australasian socio-political context and its influence on the interests and output of researchers. The review surveyed almost 400 empirical reports and conceptual discussions produced over the decade that dealt with the stakeholders, institutions and the higher education sector in Australasia. The literature is examined through two theoretical constructs or “lenses”: first, a set of first year curriculum design principles and second, the generational approach to describing the maturation of initiatives. These outcomes and suggested directions for further research provide the challenges and the opportunities for FYE adherents, both scholars and practitioners, to grapple with in the next decade.

The uses of satire : unorthodox news, cultural chaos and the interrogation of power

This article focuses on the satirical Australian show The Chaser’s War on Everything, and uses it to critically assess the potential political and social ramifications of what McNair (2006) has called ‘cultural chaos’. Drawing upon and analysing several examples from this particular program, alongside interviews with its production team and qualitative audience research, this article argues that this TV show’s engagement with politicians and political issues, in a way that departs from the conventions of traditional journalism, offers a significant opportunity for the interrogation of power. The program’s use of often bizarre and unexpected comedic confrontation allows it to present a perhaps more authentic image of political agents than is often cultivated in mainstream journalism. This suggests therefore that the shift from homogeneity to heterogeneity in the news media – which McNair (2006) sees as a key feature of cultural chaos – presents a significant challenge to those who wish to retain control over what the public sees and understands about the political world, and is a development which should be viewed in positive terms.

An Introduction to Political Communication, 5th Edition

An Introduction to Political Communication introduces students to the complex relationship between politics, the media and democracy in the United Kingdom, United States and other contemporary societies. Brian McNair examines how politicians, trade unions, pressure groups, NGOs and terrorist organisations make use of the media. Individual chapters look at political media and their effects, the work of political advertising, marketing and public relations, and the communicative practices of organizations at all levels, from grass-root campaigning through to governments and international bodies. This fifth edition has been revised and updated to include: • the 2008 US presidential election, and the early years of Barack Obama’s term • the MPs’ expenses scandal in Britain, and the 2010 UK election campaign • the growing role of bloggers and online pundits such as Guido Fawkes in the political agenda setting process • the emergence of social media platforms such as Twitter, YouTube and Facebook, and their destabiising impact on the management of political crises all over the world, including the Iranian pro-reform protests of July 2009 and the Israeli atack on the anti-blockade flotilla of May 2010 • the growing power of Wikileaks and other online information sources to challenge state control of classified information

Deviant knowledge : criminology, politics and policy

The “political” dynamics and the details of conducting criminological research on a day-to-day basis are examined. The role of government and commercial contracts in contemporary criminological scholarship are explored, as well as the various obstacles that criminologists must negotiate during the completion of a research project. The criminological implications of the ways in which academic environments are changing under new managerialist philosophies are examined. The ways in which notions of “critique” have become subordinate to the politics of existing governing rationalities are also examined. Chapter 1 details the questions, contours, and methods of “deviant knowledge.” Chapter 2 discusses the contours of criminological knowledge, including early criminological developments, international reconstruction and developments in criminological research following World War II, the United Nations, and the rise of critical genres. Chapter 3 explores criminology, government, and public policy, including the policies of the Home Office of England and Wales; the National Institute of Justice in Washington, DC; and the Australian Institute of Criminology in Canberra. The politics and control of criminological knowledge are discussed in chapter 4, along with ethical and legal issues, gathering and accessing data, and publishing results of research. Chapter 5 describes the “War on Terror” and government intolerance and suppression of free speech. Chapter 6 examines the new modes of governance and the commercialization of criminological knowledge. Chapter 7 discusses intellectual independence and collective concern, and the value of critique. 3 appendices, 546 references, index

Parrhesia and democracy : Truthtelling, WikiLeaks and the Arab Spring

Parrhesia — the practice of truth-telling — was adapted to various ancient legal, political, philosophical and religious contexts. In this essay we focus on parrhesia in politics and its relevance for democracy, concentrating on the account given by Michel Foucault. We suggest that Foucault’s approach to parrhesia and democracy is valuable because of its stress on the analysis of governmental rationalities and the ethical comportment of citizens, rather than on the normative dimensions of democracy, as is more usual (but more sterile) in political thought. We take two modern examples of truth-telling’s role in democracy – the recent WikiLeaks scandal and the political struggles in Tunisia and Egypt – as a way of assessing the value of Foucault’s distinctive approach and the relevance of parrhesia for democracy today.

Local Hollywood: global film production and the Gold Coast

Hollywood films and television programs are watched by a global audience. While many of these productions are still made in southern California, the last twenty years have seen new production centres emerge in the US, Canada and other locations worldwide. Global Hollywood has been made possible by this growing number of Local Hollywoods: locations equipped with the requisite facilities, resources and labour, as well as the political will and tax incentives, to attract and retain high-budget, Hollywood-standard projects. This new book gives an unprecedented insight into how the Gold Coast became the first outpost of Hollywood in Australia. When a combination of forces drove Hollywood studios and producers to work outside California, the Gold Coast's unique blend of government tax support, innovative entrepreneurs and diverse natural settings made it a perfect choice to host Hollywood productions. 'Local Hollywood' makes an essential contribution to the field of film and media studies, as well as giving film buffs a behind-the-scenes tour of the film industry.

Criminology, Crime and Politics Before and After 9/11

Criminologists have mostly followed the criminal law in adopting an apolitical concept of crime. They paid limited attention to both political crime and the political power to criminalise. The article traces efforts to redress this since the 1960s. It nevertheless remained a minority concern, mostly of critical criminology. Yet crime has been politicised in various ways by other developments, also examined in the article. The events of 9/11 have crowned the emergence of crime as a strategic security issue posing a challenge to criminology to engage with politically inspired crime and its control.

Living and Working on the Cusp of Contradictions

In this article Jo Phoenix argues that the struggles practitioners face to have the complex welfare needs of sexually exploited young people recognised are likely to continue into the future. The argument is made by examining three profound tensions shaping the context which both young people and practitioners inhabit. These tensions are between the, broadly, protectionist agenda of policy development on sexual exploitation and: firstly, socio-cultural changes in respect of consumption, sex and identities; secondly political changes and punitive youth justice system expansionism; and, finally, the closed and moralist rhetoric justifying recent policy changes. In the final analysis, young people and practitioners get caught in these contradictions in ways that foreclose critical examination of policy development and recognition of the complexities of the issues involved.

Contemporary State Terrorism: Theory and Practice

This volume aims to 'bring the state back into terrorism studies' and fill the notable gap that currently exists in our understanding of the ways in which states employ terrorism as a political strategy of internal governance or foreign policy. Within this broader context, the volume has a number of specific aims. First, it aims to make the argument that state terrorism is a valid and analytically useful concept which can do much to illuminate our understanding of state repression and governance, and illustrate the varieties of actors, modalities, aims, forms, and outcomes of this form of contemporary political violence. Secondly, by discussing a rich and diverse set of empirical case studies of contemporary state terrorism this volume explores and tests theoretical notions, generates new questions and provides a resource for further research. Thirdly, it contributes to a critical-normative approach to the study of terrorism more broadly and challenges dominant approaches and perspectives which assume that states, particularly Western states, are primarily victims and not perpetrators of terrorism. Given the scarceness of current and past research on state terrorism, this volume will make a genuine contribution to the wider field, particularly in terms of ongoing efforts to generate more critical approaches to the study of political terrorism. This book will be of much interest to students of critical terrorism studies, critical security studies, terrorism and political violence and political theory in general.

Archimedes, aid/watch, constitutional levers and where we now stand

Significant reform of the laws regulating charities is under way in Australia. The reforms cover almost every facet of the relationship between charities and government and the process has brought to the surface different assumptions about the role of charities in society, their entitlement to fiscal and other privileges and the scope and nature of regulation that can or should be imposed on the charities. This paper explores these broader issues in the context of the Aid/Watch case, involving an organisation used by citizens to challenge the State. Such organisations occupy contested space as to what does and does not constitute a charity. Accordingly the case provides a useful perspective from which to consider the broader issues in the relationship between government and charity. This paper seeks to build on the contribution made by other academics, by exploring the constitutional significance of political purposes and drawing from philosophy to provide context and meaning to potentially significant aspects of the judgment that might be missed when it is analysed only in terms of legal precedent through the narrow lens of the existing four heads of charity. Revenue implications for taxation of charities and political parties are also considered and it is suggested that in practice, if not in theory, the fence between them has come down.

The neglected dimension of community liveability : impact on social connectedness and active ageing in higher density accommodation

Purpose This thesis is about liveability, place and ageing in the high density urban landscape of Brisbane, Australia. As with other major developed cities around the globe, Brisbane has adopted policies to increase urban residential densities to meet the main liveability and sustainability aim of decreasing car dependence and therefore pollution, as well as to minimise the loss of greenfield areas and habitats to developers. This objective hinges on urban neighbourhoods/communities being liveable places, which residents do not have to leave for everyday living. Community/neighbourhood liveability is an essential ingredient in healthy ageing in place and has a substantial impact upon the safety, independence and well-being of older adults. It is generally accepted that ageing in place is optimal for both older people and the state. The optimality of ageing in place generally assumes that there is a particular quality to environments or standard of liveability in which people successfully age in place. The aim of this thesis was to examine if there are particular environmental qualities or aspects of liveability that test optimality and to better understand the key liveability factors that contribute to successful ageing in place. Method A strength of this thesis is that it draws on two separate studies to address the research question of what makes high density liveable for older people. In Chapter 3, the two methods are identified and differentiated as Method 1 (used in Paper 1) and Method 2 (used in Papers 2, 3, 4 and 5). Method 1 involved qualitative interviews with 24 inner city high density Brisbane residents. The major strength of this thesis is the innovative methodology outlined in the thesis as Method 2. Method 2 involved a case study approach employing qualitative and quantitative methods. Qualitative data was collected using semi-structured, in-depth interviews and time-use diaries completed by participants during the week of tracking. The quantitative data was gathered using Global Positioning Systems for tracking and Geographical Information Systems for mapping and analysis of participants’ activities. The combination of quantitative and qualitative analysis captured both participants’ subjective perceptions of their neighbourhoods and their patterns of movement. This enhanced understanding of how neighbourhoods and communities function and of the various liveability dimensions that contribute to active ageing and ageing in place for older people living in high density environments. Both studies’ participants were inner-city high density residents of Brisbane. The study based on Method 1 drew on a wider age demographic than the study based on Method 2. Findings The five papers presented in this thesis by publication indicate a complex inter-relationship of the factors that make a place liveable. The first three papers identify what is comparable and different between the physical and social factors of high density communities/neighbourhoods. The last two papers explore relationships between social engagement and broader community variables such as infrastructure and the physical built environments that are risk or protective factors relevant to community liveability, active ageing and ageing in place in high density. The research highlights the importance of creating and/or maintaining a barrier-free environment and liveable community for ageing adults. Together, the papers promote liveability, social engagement and active ageing in high density neighbourhoods by identifying factors that constitute liveability and strategies that foster active ageing and ageing in place, social connections and well-being. Recommendations There is a strong need to offer more support for active ageing and ageing in place. While the data analyses of this research provide insight into the lived experience of high density residents, further research is warranted. Further qualitative and quantitative research is needed to explore in more depth, the urban experience and opinions of older people living in urban environments. In particular, more empirical research and theory-building is needed in order to expand understanding of the particular environmental qualities that enable successful ageing in place in our cities and to guide efforts aimed at meeting this objective. The results suggest that encouraging the presence of more inner city retail outlets, particularly services that are utilised frequently in people’s daily lives such as supermarkets, medical services and pharmacies, would potentially help ensure residents fully engage in their local community. The connectivity of streets, footpaths and their role in facilitating the reaching of destinations are well understood as an important dimension of liveability. To encourage uptake of sustainable transport, the built environment must provide easy, accessible connections between buildings, walkways, cycle paths and public transport nodes. Wider streets, given that they take more time to cross than narrow streets, tend to .compromise safety - especially for older people. Similarly, the width of footpaths, the level of buffering, the presence of trees, lighting, seating and design of and distance between pedestrian crossings significantly affects the pedestrian experience for older people and impacts upon their choice of transportation. High density neighbourhoods also require greater levels of street fixtures and furniture for everyday life to make places more useable and comfortable for regular use. The importance of making the public realm useful and habitable for older people cannot be over-emphasised. Originality/value While older people are attracted to high density settings, there has been little empirical evidence linking liveability satisfaction with older people’s use of urban neighbourhoods. The current study examined the relationships between community/neighbourhood liveability, place and ageing to better understand the implications for those adults who age in place. The five papers presented in this thesis add to the understanding of what high density liveable age-friendly communities/ neighbourhoods are and what makes them so for older Australians. Neighbourhood liveability for older people is about being able to age in place and remain active. Issues of ageing in Australia and other areas of the developed world will become more critical in the coming decades. Creating livable communities for all ages calls for partnerships across all levels of government agencies and among different sectors within communities. The increasing percentage of older people in the community will have increasing political influence and it will be a foolish government who ignores the needs of an older society.

From slum to suburbia : examining a spectrum of planned and unplanned urban morphology in humid sub-tropical regions of the world

The current rapid urban growth throughout the world manifests in various ways and historically cities have grown, similarly, alternately or simultaneously between planned extensions and organic informal settlements (Mumford, 1989). Within cities different urban morphological regions can reveal different contexts of economic growth and/or periods of dramatic social/technological change (Whitehand, 2001, 105). Morpho-typological study of alternate contexts can present alternative models and contribute to the present discourse which questions traditional paradigms of urban planning and design (Todes et al, 2010). In this study a series of cities are examined as a preliminary exploration into the urban morphology of cities in ‘humid subtropical’ climates. From an initial set of twenty, six cities were selected: Sao Paulo, Brazil; Jacksonville, USA; Maputo, Mozambique; Kanpur, India; Hong Kong, China; and Brisbane, Australia. The urban form was analysed from satellite imagery at a constant scale. Urban morphological regions (types) were identified as those demonstrating particular consistant characteristics of form (density, typology and pattern) different to their surroundings when examined at a constant scale. This analysis was correlated against existing data and literature discussing the proliferation of two types of urban development, ‘informal settlement’ (defined here as self-organised communities identifiable but not always synonymous with ‘slums’) and ‘suburbia’ (defined here as master planned communities of generally detached houses prevalent in western society) - the extreme ends of a hypothetical spectrum from ‘planned’ to ‘spontaneous’ urban development. Preliminary results show some cities contain a wide variety of urban form ranging from the highly organic ‘self-organised’ type to the highly planned ‘master planned community’ (in the case of Sao Paulo) while others tend to fall at one end of the planning spectrum or the other (more planned in the cases of Brisbane and Jacksonville; and both highly planned and highly organic in the case of Maputo). Further research will examine the social, economical and political drivers and controls which lead to this diversity or homogeneity of urban form and speculates on the role of self-organisation as a process for the adaptation of urban form.