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 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.

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.)

Cellulosic ethanol from sugarcane bagasse in Australia : exploring industry feasibility through systems analysis, techno-economic assessment and pilot plant development

Overcoming many of the constraints to early stage investment in biofuels production from sugarcane bagasse in Australia requires an understanding of the complex technical, economic and systemic challenges associated with the transition of established sugar industry structures from single product agri-businesses to new diversified multi-product biorefineries. While positive investment decisions in new infrastructure requires technically feasible solutions and the attainment of project economic investment thresholds, many other systemic factors will influence the investment decision. These factors include the interrelationships between feedstock availability and energy use, competing product alternatives, technology acceptance and perceptions of project uncertainty and risk. This thesis explores the feasibility of a new cellulosic ethanol industry in Australia based on the large sugarcane fibre (bagasse) resource available. The research explores industry feasibility from multiple angles including the challenges of integrating ethanol production into an established sugarcane processing system, scoping the economic drivers and key variables relating to bioethanol projects and considering the impact of emerging technologies in improving industry feasibility. The opportunities available from pilot scale technology demonstration are also addressed. Systems analysis techniques are used to explore the interrelationships between the existing sugarcane industry and the developing cellulosic biofuels industry. This analysis has resulted in the development of a conceptual framework for a bagassebased cellulosic ethanol industry in Australia and uses this framework to assess the uncertainty in key project factors and investment risk. The analysis showed that the fundamental issue affecting investment in a cellulosic ethanol industry from sugarcane in Australia is the uncertainty in the future price of ethanol and government support that reduces the risks associated with early stage investment is likely to be necessary to promote commercialisation of this novel technology. Comprehensive techno-economic models have been developed and used to assess the potential quantum of ethanol production from sugarcane in Australia, to assess the feasibility of a soda-based biorefinery at the Racecourse Sugar Mill in Mackay, Queensland and to assess the feasibility of reducing the cost of production of fermentable sugars from the in-planta expression of cellulases in sugarcane in Australia. These assessments show that ethanol from sugarcane in Australia has the potential to make a significant contribution to reducing Australia’s transportation fuel requirements from fossil fuels and that economically viable projects exist depending upon assumptions relating to product price, ethanol taxation arrangements and greenhouse gas emission reduction incentives. The conceptual design and development of a novel pilot scale cellulosic ethanol research and development facility is also reported in this thesis. The establishment of this facility enables the technical and economic feasibility of new technologies to be assessed in a multi-partner, collaborative environment. As a key outcome of this work, this study has delivered a facility that will enable novel cellulosic ethanol technologies to be assessed in a low investment risk environment, reducing the potential risks associated with early stage investment in commercial projects and hence promoting more rapid technology uptake. While the study has focussed on an exploration of the feasibility of a commercial cellulosic ethanol industry from sugarcane in Australia, many of the same key issues will be of relevance to other sugarcane industries throughout the world seeking diversification of revenue through the implementation of novel cellulosic ethanol technologies.

Integrating electrical vehicles to demand side response scheme in Queensland Australia

Depleting fossil fuel resources and increased accumulation of greenhouse gas emissions are increasingly making electrical vehicles (EV) attractive option for the transportation sector. However uncontrolled random charging and discharging of EVs may aggravate the problems of an already stressed system during the peak demand and cause voltage problems during low demand. This paper develops a demand side response scheme for properly integrating EVs in the Electrical Network. The scheme enacted upon information on electricity market conditions regularly released by the Australian Energy Market Operator (AEMO) on the internet. The scheme adopts Internet relays and solid state switches to cycle charging and discharging of EVs. Due to the pending time-of-use and real-price programs, financial benefits will represent driving incentives to consumers to implement the scheme. A wide-scale dissemination of the scheme is expected to mitigate excessive peaks on the electrical network with all associated technical, economic and social benefits.

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.

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.

Information technology and business value in a global economy : do information technology investments pay off in a developing economy?

Understanding the business value of IT has mostly been studied in developed countries, but because most investment in developing countries is derived from external sources, the influence of that investment on business value is likely to be different. We test this notion using a two-layer model. We examine the impact of IT investments on firm processes, and the relationship of these processes to firm performance in a developing country. Our findings suggest that investment in different areas of IT positively relates to improvements in intermediate business processes and these intermediate business processes positively relate to the overall financial performance of firms in a developing country.

Renegades on the frontier of innovation: The shanzhai grassroots communities of Shenzhen in China's creative economy

Two Australian researchers specializing in China's creative industries examine recent developments in southern China commonly associated with the shanzhai phenomenon (e.g., production and sale of cheap local facsimiles of globally branded goods). While shanzhai is often condemned as the embodiment of China's "knock-off" industries, the authors argue that it might be more appropriately viewed as an instance of China's emerging creative economy and an example of rapid prototyping. The paper traces the evolution of shanzhai mobile phones and the materialization of the shanzhai ethos in popular culture. In arguing that shanzhai provides inputs into creative industries, the paper describes the fuzzy boundary between formal and informal culture and notes the interaction between three spheres of activity: official culture, the market, and grassroots culture.

The film studio: film production in the global economy

The Film Studio sheds new light on the evolution of global film production, highlighting the role of film studios worldwide. The authors explore the contemporary international production environment, alleging that global competition is best understood as an unequal and unstable partnership between the 'design interest' of footloose producers and the 'location interest' of local actors. Ben Goldsmith and Tom O'Regan identify various types of film studios and investigate the consequences for Hollywood, international film production, and the studio locations.

A comparative study of the number and mass of fine particles emitted with diesel fuel and marine gas oil (MGO)

The current investigation reports on diesel particulate matter emissions, with special interest in fine particles from the combustion of two base fuels. The base fuels selected were diesel fuel and marine gas oil (MGO). The experiments were conducted with a four-stroke, six-cylinder, direct injection diesel engine. The results showed that the fine particle number emissions measured by both SMPS and ELPI were higher with MGO compared to diesel fuel. It was observed that the fine particle number emissions with the two base fuels were quantitatively different but qualitatively similar. The gravimetric (mass basis) measurement also showed higher total particulate matter (TPM) emissions with the MGO. The smoke emissions, which were part of TPM, were also higher for the MGO. No significant changes in the mass flow rate of fuel and the brake-specific fuel consumption (BSFC) were observed between the two base fuels.