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.

Stepping stones : teacher lesson plans : year 1

"ORIGO Stepping Stones gives mathematics teachers the best of both worlds by delivering lessons and teacher guides on a digital platform blended with the more traditional printed student journals." -- Publisher website

Comparative Studies Simplified in GPFlow

We present a novel, web-accessible scientific workflow system which makes large-scale comparative studies accessible without programming or excessive configuration requirements. GPFlow allows a workflow defined on single input values to be automatically lifted to operate over collections of input values and supports the formation and processing of collections of values without the need for explicit iteration constructs. We introduce a new model for collection processing based on key aggregation and slicing which guarantees processing integrity and facilitates automatic association of inputs, allowing scientific users to manage the combinatorial explosion of data values inherent in large scale comparative studies. The approach is demonstrated using a core task from comparative genomics, and builds upon our previous work in supporting combined interactive and batch operation, through a lightweight web-based user interface.

Human neural cell interactions with orientated electrospun nanofibers in vitro

Aim: Electrospun nanofibers represent potent guidance substrates for nervous tissue repair. Development of nanofiber-based scaffolds for CNS repair requires, as a first step, an understanding of appropriate neural cell type-substrate interactions. Materials & methods: Astrocyte–nanofiber interactions (e.g., adhesion, proliferation, process extension and migration) were studied by comparing human neural progenitor-derived astrocytes (hNP-ACs) and a human astrocytoma cell line (U373) with aligned polycaprolactone (PCL) nanofibers or blended (25% type I collagen/75% PCL) nanofibers. Neuron–nanofiber interactions were assessed using a differentiated human neuroblastoma cell line (SH-SY5Y). Results & discussion: U373 cells and hNP-AC showed similar process alignment and length when associated with PCL or Type I collagen/PCL nanofibers. Cell adhesion and migration by hNP-AC were clearly improved by functionalization of nanofiber surfaces with type I collagen. Functionalized nanofibers had no such effect on U373 cells. Another clear difference between the U373 cells and hNP-AC interactions with the nanofiber substrate was proliferation; the cell line demonstrating strong proliferation, whereas the hNP-AC line showed no proliferation on either type of nanofiber. Long axonal growth (up to 600 µm in length) of SH-SY5Y neurons followed the orientation of both types of nanofibers even though adhesion of the processes to the fibers was poor. Conclusion: The use of cell lines is of only limited predictive value when studying cell–substrate interactions but both morphology and alignment of human astrocytes were affected profoundly by nanofibers. Nanofiber surface functionalization with collagen significantly improved hNP-AC adhesion and migration. Alternative forms of functionalization may be required for optimal axon–nanofiber interactions.

Stop lecturing me, I want to learn

Re-evaluation of pedagogical practice is driving learning design at Queensland University of Technology. One objective is to support approaches to increase student engagement and attendance in physical and virtual learning spaces through opportunities for active and problem-based learning. This paper provides an overview and preliminary evaluation of the pilot of one of these initiatives, the Open Web Lecture (OWL), a new web-based student response application that seamlessly integrates a virtual learning environment within a physical learning space.

‘Please leave your mobile phone on’ : Social educational networking in a social society : Encouraging in-class engagement at QUT across physical and virtual learning environments

Though stadium style seating in large lecture theatres may suggest otherwise, effective teaching and learning is a not a spectator sport. A challenge in creating effective learning environments in both physical and virtual spaces is to provide optimal opportunity for student engagement in active learning. Queensland University of Technology (QUT) has developed the Open Web Lecture (OWL), a new web-based student response application, which seamlessly integrates a virtual learning environment within the physical learning space. The result is a blended learning experience; a fluid collaboration between academic and students connected to OWL via the University’s Wi-Fi using their own laptop or mobile web device. QUT is currently piloting the OWL application to encourage student engagement. OWL offers opportunities for participants to: • Post comments and questions • Reply to comments
 • "Like" comments
 • Poll students and review data • Review archived sessions. Many of these features instinctively appeal to student users of social networking media, yet avail the academic of control within the University network. Student privacy is respected through a system of preserving peer-peer anonymity, a functionality that seeks to address a traditional reluctance to speak up in large classes. The pilot is establishing OWL as an opportunity for engaging students in active learning opportunities by enabling • virtual learning in physical spaces for large group lectures, seminar groups, workshops and conferences • live collaborative technology connecting students and the academic via the wireless network using their own laptop or mobile device • an non- intimidating environment in which to ask questions • promotion of a sense of community • instant feedback • problem based learning. The student and academic response to OWL has been overwhelmingly positive, crediting OWL as an easy to use application, which creates effective learning opportunities though interactivity and immediate feedback. This poster and accompanying online presentation of the technology will demonstrate how OWL offers new possibilities for active learning in physical spaces by: • providing increased opportunity for student engagement • supporting a range of learners and learning activities • fostering blended learning experiences. The presentation will feature visual displays of the technology, its various interfaces and feedback including clips from interviews with students and academics participating in the early stages of the pilot.

Stepping Stones A world-Class Mathematics program for the Australian Curriculum Year 1 (Student Journal)

ORIGO Stepping Stones gives mathematics teachers the best of both worlds by delivering lessons and teacher guides on a digital platform blended with the more traditional printed student journals. This uniquely interactive program allows students to participate in exciting learning activites whilst still allowing the teacher to maintain control of learning outcomes. It is the first program in Australia to give teachers activities to differentiate instruction within each lesson and across school years. Written by a team of Australia's leading mathematics educators, this program integrates key research findings in a practical sequence of modules and lessons providing schools with a step-by-step approach to the new curriculum. Click links on the right to explore the program.

Stepping stones : teacher lesson plans : year 2

"ORIGO Stepping Stones gives mathematics teachers the best of both worlds by delivering lessons and teacher guides on a digital platform blended with the more traditional printed student journals." -- Publisher website

Stepping stones : student journal : year 2

"ORIGO Stepping Stones gives mathematics teachers the best of both worlds by delivering lessons and teacher guides on a digital platform blended with the more traditional printed student journals." -- Publisher website

Stepping stones : student guide : year 3

"ORIGO Stepping Stones gives mathematics teachers the best of both worlds by delivering lessons and teacher guides on a digital platform blended with the more traditional printed student journals." -- Publisher website

Stepping stones : student journal : year K

"ORIGO Stepping Stones gives mathematics teachers the best of both worlds by delivering lessons and teacher guides on a digital platform blended with the more traditional printed student journals." -- Publisher website

Stepping stones : teacher lesson plans : year K

"ORIGO Stepping Stones gives mathematics teachers the best of both worlds by delivering lessons and teacher guides on a digital platform blended with the more traditional printed student journals." -- Publisher website

Fundamentals of process integration

Technologies and languages for integrated processes are a relatively recent innovation. Over that period many divergent waves of innovation have transformed process integration. Like sockets and distributed objects, early workflow systems ordered programming interfaces that connected the process modelling layer to any middleware. BPM systems emerged later, connecting the modelling world to middleware through components. While BPM systems increased ease of use (modelling convenience), long-standing and complex interactions involving many process instances remained di±cult to model. Enterprise Service Buses (ESBs), followed, connecting process models to heterogeneous forms of middleware. ESBs, however, generally forced modellers to choose a particular underlying middleware and to stick to it, despite their ability to connect with many forms of middleware. Furthermore ESBs encourage process integrations to be modelled on their own, logically separate from the process model. This can lead to the inability to reason about long standing conversations at the process layer. Technologies and languages for process integration generally lack formality. This has led to arbitrariness in the underlying language building blocks. Conceptual holes exist in a range of technologies and languages for process integration and this can lead to customer dissatisfaction and failure to bring integration projects to reach their potential. Standards for process integration share similar fundamental flaws to languages and technologies. Standards are also in direct competition with other standards causing a lack of clarity. Thus the area of greatest risk in a BPM project remains process integration, despite major advancements in the technology base. This research examines some fundamental aspects of communication middleware and how these fundamental building blocks of integration can be brought to the process modelling layer in a technology agnostic manner. This way process modelling can be conceptually complete without becoming stuck in a particular middleware technology. Coloured Petri nets are used to define a formal semantics for the fundamental aspects of communication middleware. They provide the means to define and model the dynamic aspects of various integration middleware. Process integration patterns are used as a tool to codify common problems to be solved. Object Role Modelling is a formal modelling technique that was used to define the syntax of a proposed process integration language. This thesis provides several contributions to the field of process integration. It proposes a framework defining the key notions of integration middleware. This framework provides a conceptual foundation upon which a process integration language could be built. The thesis defines an architecture that allows various forms of middleware to be aggregated and reasoned about at the process layer. This thesis provides a comprehensive set of process integration patterns. These constitute a benchmark for the kinds of problems a process integration language must support. The thesis proposes a process integration modelling language and a partial implementation that is able to enact the language. A process integration pilot project in a German hospital is brie°y described at the end of the thesis. The pilot is based on ideas in this thesis.

Introduction to the First International Workshop on Empirical Research in Business Process Management (ER-BPM 2009)

Providing effective IT support for business processes has become crucial for enterprises to stay competitive. In response to this need numerous process support paradigms (e.g., workflow management, service flow management, case handling), process specification standards (e.g., WS-BPEL, BPML, BPMN), process tools (e.g., ARIS Toolset, Tibco Staffware, FLOWer), and supporting methods have emerged in recent years. Summarized under the term “Business Process Management” (BPM), these paradigms, standards, tools, and methods have become a success-critical instrument for improving process performance.