Effect of dangling chains on the structure and physical properties of a tightly crosslinked poly(ethylene glycol) network

Major imperfections in crosslinked polymers include loose or dangling chain ends that lower the crosslink d., thereby reducing elastic recovery and increasing the solvent swelling. These imperfections are hard to detect, quantify and control when the network is initiated by free radical reactions. As an alternative approach, the sol-​gel synthesis of a model poly(ethylene glycol) (PEG-​2000) network is described using controlled amts. of bis- and mono-​triethoxy silyl Pr urethane PEG precursors to give silsesquioxane (SSQ, R-​SiO1.5) structures as crosslink junctions with a controlled no. of dangling chains. The effect of the no. of dangling chains on the structure and connectivity of the dried SSQ networks has been detd. by step-​crystn. differential scanning calorimetry. The role that micelle formation plays in controlling the sol-​gel PEG network connectivity has been studied by dynamic light scattering of the bis- and mono-​triethoxy silyl precursors and the networks have been characterized by 29Si solid state NMR, sol fraction and swelling measurements. These show that the dangling chains will increase the mesh size and water uptake. Compared to other end-​linked PEG hydrogels, the SSQ-​crosslinked networks show a low sol fraction and high connectivity, which reduces solvent swelling, degree of crystallinity and the crystal transition temp. The increased degree of freedom in segment movement on the addn. of dangling chains in the SSQ-​crosslinked network facilitates the packing process in crystn. of the dry network and, in the hydrogel, helps to accommodate more water mols. before reaching equil.

Dynamic capabilities and innovation in supply chains

Supply chain relationships between firms are increasingly important in terms of both competitiveness and developing dynamic capability to respond to rapid changes in the market. Innovation capacity both in firms and in supply chains is also integral to responding to dynamic markets and customer needs. This explorative research examines a sample of firms active in supply chain relationships in Australia, as a pilot study, to examine any linkages between firm dynamic capabilities and supply chains developing innovative capacity to meet competitive and market changes. Initial findings indicate that although firms focus on developing capabilities, particularly dynamic capabilities to innovate individually, these preliminary findings indicate little reliance on developing their supply chain innovation capacity. This study is the initial stage of more extensive research on this topic.

Extending knowledge management across the supply chains in the construction industry : knowledge sharing in construction supply chains

Supply chain management and knowledge management have emerged as two distinct business philosophies in the last decade. Both are making rapid inroads into the construction industry. The premise of this paper is that knowledge management would make it possible for all the trading partners in a supply chain to reap benefits. Current research in knowledge management in the construction industry is generally targeting those big organisations that are main contractors. This has restricted the scope of knowledge management, and limits the benefits to a few, rather than the whole industry. If the construction industry as a whole is to prosper and improve its productivity, strategies for knowledge management strategy at the industry level must be established. This paper argues the case for extending the scope of knowledge management across the full extent of the supply chain, and attempts to identify the benefits that may arise out of sharing knowledge across the supply chain.

Investigating the role of ICT in improving productivity in construction supply chains in Australian construction industry.

The Australian construction industry is a fragmented and profoundly competitive industry with high levels of subcontracting resulting in complex supply chain formations. Traditional methods and forms of communication are being proven as inefficient and losing their charm while participants face heavy volumes of communications that often occurs on a daily basis between trading partners in a supply chain on projects. Information Communication Technologies (ICT), due to their robustness and the ability to quickly disseminate data/information, have the capacity to address highlighted communication issues in a structured and an efficient manner. Timesavings produced by these can be directly translated in terms of productivity gain. This paper presents perceptions of subcontractors working in the construction industry in Melbourne Australia on the use of ICT obtained through an exploratory study.

Labour rights as human rights : workers' safety at work in Australian-based supply chains

The increase of buyer-driven supply chains, outsourcing and other forms of non-traditional employment has resulted in challenges for labour market regulation. One business model which has created substantial regulatory challenges is supply chains. The supply chain model involves retailers purchasing products from brand corporations who then outsource the manufacturing of the work to traders who contract with factories or outworkers who actually manufacture the clothing and textiles. This business model results in time and cost pressures being pushed down the supply chain which has resulted in sweatshops where workers systematically have their labour rights violated. Literally millions of workers work in dangerous workplaces where thousands are killed or permanently disabled every year. This thesis has analysed possible regulatory responses to provide workers a right to safety and health in supply chains which provide products for Australian retailers. This thesis will use a human rights standard to determine whether Australia is discharging its human rights obligations in its approach to combating domestic and foreign labour abuses. It is beyond this thesis to analyse Occupational Health and Safety (OHS) laws in every jurisdiction. Accordingly, this thesis will focus upon Australian domestic laws and laws in one of Australia’s major trading partners, the Peoples’ Republic of China (China). It is hypothesised that Australia is currently breaching its human rights obligations through failing to adequately regulate employees’ safety at work in Australian-based supply chains. To prove this hypothesis, this thesis will adopt a three- phase approach to analysing Australia’s regulatory responses. Phase 1 will identify the standard by which Australia’s regulatory approach to employees’ health and safety in supply chains can be judged. This phase will focus on analysing how workers’ rights to safety as a human right imposes a moral obligation on Australia to take reasonablely practicable steps regulate Australian-based supply chains. This will form a human rights standard against which Australia’s conduct can be judged. Phase 2 focuses upon the current regulatory environment. If existing regulatory vehicles adequately protect the health and safety of employees, then Australia will have discharged its obligations through simply maintaining the status quo. Australia currently regulates OHS through a combination of ‘hard law’ and ‘soft law’ regulatory vehicles. The first part of phase 2 analyses the effectiveness of traditional OHS laws in Australia and in China. The final part of phase 2 then analyses the effectiveness of the major soft law vehicle ‘Corporate Social Responsibility’ (CSR). The fact that employees are working in unsafe working conditions does not mean Australia is breaching its human rights obligations. Australia is only required to take reasonably practicable steps to ensure human rights are realized. Phase 3 identifies four regulatory vehicles to determine whether they would assist Australia in discharging its human rights obligations. Phase 3 then analyses whether Australia could unilaterally introduce supply chain regulation to regulate domestic and extraterritorial supply chains. Phase 3 also analyses three public international law regulatory vehicles. This chapter considers the ability of the United Nations Global Compact, the ILO’s Better Factory Project and a bilateral agreement to improve the detection and enforcement of workers’ right to safety and health.

Highly efficient, stoichiometric radical exchange reactions using isoindoline profluorescent nitroxides

Exchange reactions between the isoindoline profluorescent nitroxide 1,1,3,3-tetramethyldibenzo[e,g]isoindolin-2-yloxyl (TMDBIO) and a TEMPO capped polystyrene were carried out. High conversions to the desired products were achieved using only stoichiometric ratios of nitroxide relative to polymer. The scope of this study was expanded by exploiting a di-nitroxide 9,10-bis(5-[1,1,3,3-tetramethylisoindolin-2-yloxy])anthracene (BTMIOA) as a connector between two polymer chains forming PS–nitroxide–PS systems.

Inexact uniformization method for computing transient distributions of Markov chains

The uniformization method (also known as randomization) is a numerically stable algorithm for computing transient distributions of a continuous time Markov chain. When the solution is needed after a long run or when the convergence is slow, the uniformization method involves a large number of matrix-vector products. Despite this, the method remains very popular due to its ease of implementation and its reliability in many practical circumstances. Because calculating the matrix-vector product is the most time-consuming part of the method, overall efficiency in solving large-scale problems can be significantly enhanced if the matrix-vector product is made more economical. In this paper, we incorporate a new relaxation strategy into the uniformization method to compute the matrix-vector products only approximately. We analyze the error introduced by these inexact matrix-vector products and discuss strategies for refining the accuracy of the relaxation while reducing the execution cost. Numerical experiments drawn from computer systems and biological systems are given to show that significant computational savings are achieved in practical applications.

Patterning of tailored polycarbonate based non-chemically amplified resists using extreme ultraviolet lithography

A series of high-performance polycarbonates have been prepared with glass-transition temperatures and decomposition temperatures that are tunable by varying the repeat-unit chemical structure. Patterning of the polymers with extreme UV lithography has been achieved by taking advantage of direct photoinduced chain scission of the polymer chains, which results in a molecular-weight based solubility switch. After selective development of the irradiated regions of the polymers, feature sizes as small as 28.6 nm have been printed and the importance of resist-developer interactions for maximizing image quality has been demonstrated.

Reconfiguration or innovation in supply chains?

This research explores supply chain competitiveness and dynamic capabilities. It examines a pilot group of Australian supply chain organisations to understand the importance of dynamic capability in building innovation capacity for competitive advantage, and the concept of adopting a strategic approach to supply chain relationship building. A supply chain is after all a group of intra and interorganisational relationships delivering demand to end-users. This exploratory study confirms a positive relationship between the variables indicating both a strategic intent to develop relational capability, and very strong predictive linkages between the importance placed on developing supply chain dynamic capability and achieving supply chain innovation capacity as a competitive advantage.

Photoclickable surfaces for profluorescent covalent polymer coatings

The nitrile imine-mediated tetrazole-ene cycloaddition reaction (NITEC) is introduced as a powerful and versatile conjugation tool to covalently ligate macromolecules onto variable (bio)surfaces. The NITEC approach is initiated by UV irradiation and proceeds rapidly at ambient temperature yielding a highly fluorescent linkage. Initially, the formation of block copolymers by the NITEC methodology is studied to evidence its efficacy as a macromolecular conjugation tool. The grafting of polymers onto inorganic (silicon) and bioorganic (cellulose) surfaces is subsequently carried out employing the optimized reaction conditions obtained from the macromolecular ligation experiments and evidenced by surface characterization techniques, including X-ray photoelectron spectroscopy and FT-IR microscopy. In addition, the patterned immobilization of variable polymer chains onto profluorescent cellulose is achieved through a simple masking process during the irradiation. Photoinduced nitrile imine-alkene 1,3-dipolar cycloaddition (NITEC) is employed to covalently bind well-defined polymers onto silicon oxide or cellulose. A diaryl tetrazole-functionalized molecule is grafted via silanization or amidification, respectively. Under UV light, a reactive nitrile imine rapidly forms and reacts with maleimide-functionalized polymers yielding a fluorescent linkage. Via a masking method, polymeric fluorescent patterns are achieved.

(Ultra)fast catalyst-free macromolecular conjugation in aqueous environment at ambient temperature

Tailor-made water-soluble macromolecules, including a glycopolymer, obtained by living/controlled RAFT-mediated polymerization are demonstrated to react in water with diene-functionalized poly(ethylene glycol)s without pre- or post-functionalization steps or the need for a catalyst at ambient temperature. As previously observed in organic solvents, hetero-Diels-Alder (HDA) conjugations reached quantitative conversion within minutes when cyclopentadienyl moieties were involved. However, while catalysts and elevated temperatures were previously necessary for open-chain diene conjugation, additive-free HDA cycloadditions occur in water within a few hours at ambient temperature. Experimental evidence for efficient conjugations is provided via unambiguous ESI-MS, UV/vis, NMR, and SEC data.

Safety culture in supply chains : 'Customer is king'

Despite the presence of many regulations governing the operation of heavy vehicles and supply chains in Australia, the truck driving sector continues to have the highest incidence of fatal injuries compared to all other industries. The working environment has been the focus of attention by safety researchers during the past few decades, with particular consideration been given to the concept ‘safety culture’ and how to maintain, modify and advance responses to occupational risk. One important aspect of the heavy industry which sets it apart is the existence of cultural or sub-cultural influences at an industry wide and occupation-specific level rather than organisational level. This paper reports on the findings of stakeholder’s perceptions of the influences of power and control, and culture on industry safety. In-depth structured interviews were conducted during 2011 with Australian industry stakeholders (n=31). The questioning surrounded decision-making processes with regards to identifying risks, self-monitoring and reducing risky activities; as well as how power-affected relationships may influence the operational performance of supply chains and impacts on driver safety. One of the most significant findings from these interviews relates to the notion of power. The perception that the ‘Customer is King’ was widely viewed, with the majority of stakeholders believing that there exists a ‘master slave mentality’ in the industry. There appears to be great frustration in the industry as to the apparent immunity of customers (particularly retail supply chains) to their responsibilities. There was also a strong perception that the customer holds the balance of power by covertly employing remuneration-related incentives and pressures. Smaller trucking companies are perceived as being more vulnerable to the pressure of customer expectations.