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.

The right to be green: using human rights law to achieve environmental protection

The relationship between the environment and human rights has long been recognised. It is now largely accepted that a ‘good’ environment is a necessary precondition for the enjoyment of a wide range of human rights, including the right to health, the right to an adequate standard of living, and even the right to life. It has even been suggested that as humans we all possess a right to live in an environment of a certain standard, based on the intrinsic value of the natural world to all human beings. In this context much has been written regarding the important role that the environment plays in human lives. This paper looks at the flip-side of this discussion, and examines what human rights can do for the environment. It is argued that, while there are valid criticisms for linking environmental protection too strongly to human needs, there is nonetheless much to be gained from using human rights law as a framework to achieve environmental protection.

The role of human rights in environmental governance : the challenge of climate change

The role of human rights in environmental governance is increasingly gaining attention. This is particularly the case in relation to the challenge of climate change, where there is growing recognition of a real threat to human rights. This chapter argues in favour of greater reference to human rights principles in environmental governance. It refers to the experiences of Torres Strait Islanders to demonstrate the impact of climate change on human rights, and the many benefits which can be gained from a greater consideration of human rights norms in the development of strategies to combat climate change. The chapter also argues that a human rights perspective can help address the underlying injustice of climate change: that it is the people who have contributed least to the problem who will bear the heaviest burden of its effects.

Human rights and environmental wrongs : achieving environmental justice through human rights law

The links between the environment and human rights are well established internationally. It is accepted that environmental problems impact on individuals’ and communities’ enjoyment of rights which are guaranteed to them under international human rights law. Environmental issues also impact on governments’ capacity to protect and fulfil the rights of their citizens. In addition to these links between the environment and human rights, it is argued that human rights principles offer a strategy for addressing environmental injustice. The justice implications of environmental problems are well documented, with many examples where pollution, deforestation or other degradation disproportionately impacts upon poorer neighbourhoods or areas populated by minority groups. On the international level, there are environmental injustices which exist between developed and developing states. Further, there are also potential injustices for future generations. This paper investigates the role of human rights principles in addressing these instances of environmental injustice, and argues that the framework of human rights norms provides an approach to environmental governance which can help to minimise injustice and promote the interests of those groups who are most adversely affected. Further, it suggests that the human rights enforcement mechanisms which exist at international law could be utilised to lend more weight to claims for more equitable environmental policies.

Social benchmarking to improve river ecosystems

To complement physical measures or indices of river health a social benchmarking instrument has been developed to measure community dispositions and behaviour regarding river health. This instrument seeks to achieve three outcomes. First, to provide a benchmark of the social condition of communities’ attitudes, values, understanding and behaviours in relation to river health; second, to provide information for developing management and educational priorities; and third, to provide an assessment of the long-term effectiveness of community education and engagement activities in achieving changes in attitudes, understanding and behaviours in relation to river health. In this paper the development of the social benchmarking instrument is described and results are presented from the first state-wide benchmark study in Victoria, Australia, in which the social dimensions of river health, community behaviours related to rivers, and community understanding of human impacts on rivers were assessed.

The role of property law in environmental management

Market-based environmental regulation is becoming increasingly common within international and national frameworks. In order for market-based regimes to attract sufficient levels of stakeholder engagement, participants within such schemes require an incentive to participate and furthermore need to feel a sense of security about investing in such processes. A sense of security is associated with property-based interests. This article explores the property-related issues connected with the operation of environmental markets. Relevant property-related considerations include examining the significant role that market-based regulation is playing in connection with the environment; examining the links between property rights and markets; exploring the legal definition of property; analysing the rights and powers associated with environmental interests in land; advancing theory on the need for landholder responsibilities in relation to land and examining the legal mechanisms used to recognise environmental property rights, including the registration thereof.

The role of gender and framing in shaping community activists' perceptions of environmental risks

campaign to oppose projects proposed in their local community. The social constructionist perspective advocates that these motivations are driven by activists’ interpretation of reality, such that activists will assign multiple meanings to and frame environmental issues in a way that reflects their view of reality. Past research suggest that these are also influenced by patterns of shared meaning and interpretation that develop over time in protest movements that shape activists’ perceptions of the environmental risks and impacts associated with construction activity. This paper explores the role of gender distinctions in shaping perceptions of environmental risk and how this affects their framing of the environmental, social, cultural/ historical impacts associated with a construction project. Using Snow and Benford’s (1988) 3-prong analytical tool for framing: diagnostic framing, prognostic framing and motivational framing, this paper presents findings from the content analysis of in-depth interviews of 24 activists protesting against a highly controversial housing project in the greater Sydney metropolitan area. The research adopts a single case study approach, and is particularly significant as it investigates an extensive and on-going community-based protest campaign (dating back almost 20 years) that has generated the longest standing 24-hour community picket in Australia.

An approximate Bayesian computation approach for estimating parameters of complex environmental processes in a cellular automata

Modelling an environmental process involves creating a model structure and parameterising the model with appropriate values to accurately represent the process. Determining accurate parameter values for environmental systems can be challenging. Existing methods for parameter estimation typically make assumptions regarding the form of the Likelihood, and will often ignore any uncertainty around estimated values. This can be problematic, however, particularly in complex problems where Likelihoods may be intractable. In this paper we demonstrate an Approximate Bayesian Computational method for the estimation of parameters of a stochastic CA. We use as an example a CA constructed to simulate a range expansion such as might occur after a biological invasion, making parameter estimates using only count data such as could be gathered from field observations. We demonstrate ABC is a highly useful method for parameter estimation, with accurate estimates of parameters that are important for the management of invasive species such as the intrinsic rate of increase and the point in a landscape where a species has invaded. We also show that the method is capable of estimating the probability of long distance dispersal, a characteristic of biological invasions that is very influential in determining spread rates but has until now proved difficult to estimate accurately.

Philosophy, behaviour disorders, and the school

The recent exponential rise in the number of behaviour disorders has been the focus of a wide range of commentaries, ranging from the pedagogic and the administrative, to the sociological, and even the legal. This book will be the first to apply, in a systematic and thorough manner, the ideas of the foundational discipline of philosophy. A number of philosophical tools are applied here, tools arising through the medium of the traditional philosophical debates, such as those concerning governance, truth, logic, ethics, free-will, law and language. Each forms a separate chapter, but together they constitute a comprehensive, rigorous and original insight into what is now an important set of concerns for all those interested in the governance of children. The intention is threefold: first, to demonstrate the utility, accessibility and effectiveness of philosophical ideas within this important academic area. Philosophy does not have to be regarded an arcane and esoteric discipline, with only limited contemporary application, far from it. Second, the book offers a new set of approaches and ideas for both researchers and practitioners within education, a field is in danger of continually using the same ideas, to endlessly repeat the same conclusions. Third, the book offers a viable alternative to the dominant psychological model which increasingly employs pathology as its central rationale for conduct. The book would not only be of interest to mainstream educators, and to those students and academics interested in philosophy, and more specifically, the application of philosophical ideas to educational issues, it would also be an appropriate text for courses on education and difference, and due to the breadth of the philosophical issues addressed, courses on applied philosophy.

Risky strategic behaviour : unintended consequences of good intentions in the homelessness service system

The delivery of human services occurs through a complex and often volatile system characterised by both competing and cooperating efforts. A recent strategic intention of government has been to integrate disparate service providers and programs into a more effective and efficient system using competitive funding regimes. A program of amalgamation has also been forecast and promoted as a further mechanism by which to link up smaller agencies thus creating economy and efficiency in the scale and scope of their service modes. Despite the current reliance on competitive funding models and amalgamation as the preferred ways forward for the sector little is known about their integrative capacity including their ability to predict outcomes and their consequences : the ‘unknown unknowns’. Drawing on an extensive data set of human services integration initiatives in Queensland, Australia, this paper examines the impact of government policy and service models and the risks arising from the tensions between competition and accountability on the one hand and the established good will and trust on the other. It is argued that unresolved, these tensions can lead to a weakening of the social infrastructure and make the system more vulnerable to inherent systemic risks. The paper finds that government’s efforts to externalise risk to the non-government sector leads to fragmentation of the service system and fractured collaborative capability. These unintended outcomes themselves have the unintended consequence of leaving governments disconnected from the service system and unable to provide the leadership role and direction necessary for sustained integration. Moreover, facilitating such a leadership role is undermined by behaviours that are directly contrary to collective integration models.

Individual user behaviour modelling for effective web recommendation

With the growth of the Web, E-commerce activities are also becoming popular. Product recommendation is an effective way of marketing a product to potential customers. Based on a user’s previous searches, most recommendation methods employ two dimensional models to find relevant items. Such items are then recommended to a user. Further too many irrelevant recommendations worsen the information overload problem for a user. This happens because such models based on vectors and matrices are unable to find the latent relationships that exist between users and searches. Identifying user behaviour is a complex process, and usually involves comparing searches made by him. In most of the cases traditional vector and matrix based methods are used to find prominent features as searched by a user. In this research we employ tensors to find relevant features as searched by users. Such relevant features are then used for making recommendations. Evaluation on real datasets show the effectiveness of such recommendations over vector and matrix based methods.

A suspicious behaviour detection using a context space model for smart surveillance systems

Video surveillance systems using Closed Circuit Television (CCTV) cameras, is one of the fastest growing areas in the field of security technologies. However, the existing video surveillance systems are still not at a stage where they can be used for crime prevention. The systems rely heavily on human observers and are therefore limited by factors such as fatigue and monitoring capabilities over long periods of time. This work attempts to address these problems by proposing an automatic suspicious behaviour detection which utilises contextual information. The utilisation of contextual information is done via three main components: a context space model, a data stream clustering algorithm, and an inference algorithm. The utilisation of contextual information is still limited in the domain of suspicious behaviour detection. Furthermore, it is nearly impossible to correctly understand human behaviour without considering the context where it is observed. This work presents experiments using video feeds taken from CAVIAR dataset and a camera mounted on one of the buildings Z-Block) at the Queensland University of Technology, Australia. From these experiments, it is shown that by exploiting contextual information, the proposed system is able to make more accurate detections, especially of those behaviours which are only suspicious in some contexts while being normal in the others. Moreover, this information gives critical feedback to the system designers to refine the system.

A natural model for architecture

In John Frazer's seminal book An Evolutionary Architecture (1995), from which this essay is extracted, a fundamental approach is established for have natural systems can unfold mechanisms for negotiating the complex design space inherent in architectural systems. In this essay, which forms a critical part of the book, Frazer draws both correlations and distinctions from natural processes as emulated in design processes and form as active manifestations within natural systems. Form is seen as an evolving agent generated via the rules of descriptive genetic coding, functioning as a part of a metabolic environment. Frazer's process-model establishes the realm in which computation must manoeuvre to produce a valid solution space, including the operations of self-organisation, complexity and emergent behaviour. Addressing design as an authored practice, he extends the transference of 'creativity' from the explicit impression into form, to the investment of though, organisation and strategy in the computational processes which produce form. Frazer's text concentrates astutely on the practising of the evolutionary paradigm, the output of which postulates an architecture born of the relationships to dynamic environmental and socio-economic contexts, and realised through morphogenetic materialisation.