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.

School education as social and economic governance : responsibilising communities through industry-school engagement

This article examines shifts in educational and social governance taking place in Queensland, Australia, through Industry School Engagement Strategy of Education Queensland and its Gateway Schools program. This significant educational initiative is set within the context of the social investment agenda first articulated in the education policy framework, Queensland State Education-2010. The article traces the historic extension of this governmental strategy through establishment of the Gateway Schools concept that brokers industry-school partnerships with global players in the Queensland economy. Industry sectors forming the partnerships include Minerals and Energy, Aerospace, Wine Tourism, Agribusiness, Manufacturing and Engineering, Building and Construction and ICT. We argue that this ‘post-bureaucratic’ model of schooling represents a new social settlement of neoliberal governance, in which educational outcomes align with economic objectives, and frame the conditions for community self-governance.

Building engaged, sustainable online communities : a case study of an adventure travel website

This paper will provide an overview of a join research initiative being developed by the Queensland University of Technology in conjunction with the Australian Smart Services Cooperative Research Centre in relation to the development and analysis of online communities. The intention of this project is to initially create an exciting and innovative web space around the concept of adventure travel and then to analyse the level of user engagement to uncover possible patterns and processes that could be used in the future development of other virtual online communities. Travel websites are not a new concept and there are many successful examples currently operating and generating profit. The intention of the QUT/Smart Services CRC project is to analyse the site metrics to determine the following: what specific conditions/parameters are required to foster a growing and engaged virtual community; when does the shift occur from external moderation to a more sustainable system of self-moderation within the online community; when do users begin to take ownership of a site and take an invested interested in the content and growth of an online community; and how to retain active contributors and high-impact power users on a long-term basis. With the travel website rapidly approaching release, this paper begins the process of reflection, outlining the process undertaken and the findings so far aggregated whilst also positioning the project within the greater context of current online user participation and user generated content research.

Extending client-centered support : counselors’ proposals to shift from email to telephone counseling

The availability and use of online counseling approaches has increased rapidly over the last decade. While research has suggested a range of potential affordances and limitations of online counseling modalities, very few studies have offered detailed examinations of how counselors and clients manage asynchronous email counseling exchanges. In this paper we examine email exchanges involving clients and counselors through Kids Helpline, a national Australian counseling service that offers free online, email and telephone counseling for young people up to the age of 25. We employ tools from the traditions of ethnomethodology and conversation analysis to analyze the ways in which counselors from Kids Helpline request that their clients call them, and hence change the modality of their counseling relationship, from email to telephone counseling. This paper shows the counselors’ three multi-layered approaches in these emails as they negotiate the potentially delicate task of requesting and persuading a client to change the trajectory of their counseling relationship from text to talk without placing that relationship in jeopardy.

Value management : an extension of quantity surveying services in Malaysia

Value Management (VM) initially started in early 1940s in the US manufacturing industry has increasingly becoming popular within the construction industry community internationally. It has been widely accepted as an important tool in the management of projects. The structured, systematic and multi-disciplinary approach in decision making process is a niche for VM in delivering better value for money project to the client investment. It would appear to be gaining some momentum as an essential management tool in the Malaysian construction sector especially in the quantity surveying practice. Quantity surveyors increasing involvement in VM provides an opportunity for the profession to re-model some of its traditional services in a more positive light and develop leading-edge skills and promote the profession. International practice has associated VM to be part of services offered in the quantity surveying practice; especially in UK has proven to be a natural progression of QS profession. The introduction of VM as early 1980’s in Malaysia combined with increasing demand for construction project to facilitate nation progress is shedding a positive light for quantity surveying profession to take lead in developing VM as one of their niche area. Therefore, the quantity surveying profession having the opportunity to take lead of this service which reflect their traditional attributes for providing the best value-for-money advise to the client. This paper shall discuss on the development of VM in Malaysia and the challenges VM face services in QS firm to remain ahead of their competitors.

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.

No longer Singaporean : visibilising the everyday contestations of identities

In the past decade or so, the citizens of Singapore have been vigorously urged by the state to turn their cultural and linguistic affinities with China to economic advantage. At the same time, the city-state has opened its doors to selected, skilled migrants from Asia including many of those from mainland and Greater China. These concurrent emphases have coincided with the trend and growing numbers of Singaporeans heading overseas for one reason or another. Through a reflexive journey sparked by a recent visit, I argue in this paper that the resultant change in the makeup of its population produces tensions that may well have important repercussions for a nation that is constitutionally multiethnic though pragmatically meritocratic. However, because these frictions find form only in everyday, pedestrian practices, they are often dismissed or ignored. It is my contention that as the stage on which innocuous, creeping shifts in social identities are enacted, finessed and (re)embedded into social imaginaries, these everyday contestations of identities need to studied for indications of what is at stake.

Investigating the performance of automatic new topic identification across multiple datasets 1

Recent studies on automatic new topic identification in Web search engine user sessions demonstrated that neural networks are successful in automatic new topic identification. However most of this work applied their new topic identification algorithms on data logs from a single search engine. In this study, we investigate whether the application of neural networks for automatic new topic identification are more successful on some search engines than others. Sample data logs from the Norwegian search engine FAST (currently owned by Overture) and Excite are used in this study. Findings of this study suggest that query logs with more topic shifts tend to provide more successful results on shift-based performance measures, whereas logs with more topic continuations tend to provide better results on continuation-based performance measures.

The resource boom's underbelly : criminological impacts of mining development

Australia is currently in the midst of a major resources boom. Resultant growing demands for labour in regional and remote areas have accelerated the recruitment of non resident workers, mostly contractors, who work extended block rosters of 12-hour shifts and are accommodated in work camps, often adjacent to established mining towns. Serious social impacts of these practices, including violence and crime, have generally escaped industry, government and academic scrutiny. This paper highlights some of these impacts on affected regional communities and workers and argues that post-industrial mining regimes serve to mask and privatize these harms and risks, shifting them on to workers, families and communities.

Representational change and strategy use in children's number line estimation during the first years of primary school

Background: The objective of this study was to scrutinize number line estimation behaviors displayed by children in mathematics classrooms during the first three years of schooling. We extend existing research by not only mapping potential logarithmic-linear shifts but also provide a new perspective by studying in detail the estimation strategies of individual target digits within a number range familiar to children. Methods: Typically developing children (n = 67) from Years 1 – 3 completed a number-to-position numerical estimation task (0-20 number line). Estimation behaviors were first analyzed via logarithmic and linear regression modeling. Subsequently, using an analysis of variance we compared the estimation accuracy of each digit, thus identifying target digits that were estimated with the assistance of arithmetic strategy. Results: Our results further confirm a developmental logarithmic-linear shift when utilizing regression modeling; however, uniquely we have identified that children employ variable strategies when completing numerical estimation, with levels of strategy advancing with development. Conclusion: In terms of the existing cognitive research, this strategy factor highlights the limitations of any regression modeling approach, or alternatively, it could underpin the developmental time course of the logarithmic-linear shift. Future studies need to systematically investigate this relationship and also consider the implications for educational practice.

Tracking the defining moments of crisis process and practice

Crisis holds the potential for profound change in organizations and industries. The past 50 years of crisis management highlight key shifts in crisis practice, creating opportunities for multiple theories and research tracks. Defining crises such as Tylenol, Exxon Valdez, and September 11 terrorist attacks have influenced or challenged the principles of best practice of crisis communication in public relations. This study traces the development of crisis process and practice by identifying shifts in crisis research and models and mapping these against key management theories and practices. The findings define three crisis domains: crisis planning, building and testing predictive models, and mapping and measuring external environmental influences. These crisis domains mirror but lag the evolution of management theory, suggesting challenges for researchers to reshape the research agenda to close the gap and lead the next stage of development in the field of crisis communication for effective organizational outcomes.

Transferring knowledge through peer-reviewed assessment : the creation of a community of practice and the threats to its survival

While it is generally accepted in the learning and teaching literature that assessment is the single biggest influence on how students approach their learning, assessment methods within higher education are generally conservative and inflexible. Constrained by policy and accreditation requirements and the need for the explicit articulation of assessment standards for public accountability purposes, assessment tasks can fail to engage students or reflect the tasks students will face in the world of practice. Innovative assessment design can simultaneously deliver program objectives and active learning through a knowledge transfer process which increases student participation. This social constructivist view highlights that acquiring an understanding of assessment processes, criteria and standards needs active student participation. Within this context, a peer-assessed, weekly, assessment task was introduced in the first “serious” accounting subject offered as part of an undergraduate degree. The positive outcomes of this assessment innovation was that student failure rates declined 15%, tutorial participation increased fourfold, tutorial engagement increased six-fold and there was a 100% approval rating for the retention of the assessment task. In contributing to the core conference theme of “seismic” shifts within higher education, in stark contrast to the positive student response, staff-related issues of assessment conservatism and the necessity of meeting increasing research commitments, threatened the assessment task’s survival. These opposing forces to change have the potential to weaken the ability of higher education assessment arrangements to adequately serve either a new generation of students or the sector's community stakeholders.

A brief history of haemotopoietic stem cell Ex vivo expansion

Haematopoiesis is the process by which a hierarchy of mature and progenitor blood cells are formed. These cell populations are all derived from multipotent haematopoietic stem cells (HSC), which reside in the bone marrow ‘niche’ of adult humans. Over the lifetime of a healthy individual, this HSC population replenishes between 1010-1011 blood cells on a daily basis. Dysregulation of this system can lead to a number of haematopoietic diseases, including aplastic anaemias and leukaemias, which result in, or require for disease resolution, bone marrow cell depletion. In 1956, E. Donnall Thomas demonstrated that haematopoiesis could be restored by transplanting bone marrow-derived cells from one man into his identical twin brother, who was suffering from advanced leukaemia. His success drew significant interest in academic research and medicine communities, and 12 years later, the first successful allogeneic transplant was performed. To this day, HSCs remain the most studied and characterised stem cell population. In fact, HSCs are the only stem cell population routinely utilised in the clinic. As such, HSCs function as a model system both for the biological investigation of stem cells, as well as for their clinical application. Herein, we briefly review HSC transplantation, strategies for the ex vivo cultivation of HSCs, recent clinical outcomes, and their impact on the future direction of HSC transplantation therapy.

Transferring knowledge through peer-reviewed assessment : the creation of a community of practice and the threats to its survival

While it is generally accepted in the learning and teaching literature that assessment is the single biggest influence on how students approach their learning, assessment methods within higher education are generally conservative and inflexible. Constrained by policy and accreditation requirements and the need for the explicit articulation of assessment standards for public accountability purposes, assessment tasks can fail to engage students or reflect the tasks students will face in the world of practice. Innovative assessment design can simultaneously deliver program objectives and active learning through a knowledge transfer process which increases student participation. This social constructivist view highlights that acquiring an understanding of assessment processes, criteria and standards needs active student participation. Within this context, a peer-assessed, weekly, assessment task was introduced in the first “serious” accounting subject offered as part of an undergraduate degree. The positive outcomes of this assessment innovation was that student failure rates declined 15%, tutorial participation increased fourfold, tutorial engagement increased six-fold and there was a 100% approval rating for the retention of the assessment task. In contributing to the core conference theme of “seismic” shifts within higher education, in stark contrast to the positive student response, staff-related issues of assessment conservatism and the necessity of meeting increasing research commitments, threatened the assessment task’s survival. These opposing forces to change have the potential to weaken the ability of higher education assessment arrangements to adequately serve either a new generation of students or the sector's community stakeholders.

When the shoe doesn't quite fit: Regulating large commercial airports with expanding roles

Airports, whether publicly or privately owned or operated fill both public and private roles. They need to act as public infrastructure providers and as businesses which cover their operating costs. That leads to special governance concerns with respect to consumers and competitors which are only beginning to be addressed. These challenges are highlighted both by shifts in ownership status and by the expansion of roles performed by airports as passenger and cargo volumes continue to increase and as nearby urban areas expand outward towards airports. We survey five ways in which the regulatory shoe doesn‟t quite fit the needs. Our findings suggest that, while ad hoc measures limit political tension, new governance measures are needed.