Fabrication and characterization of plasma polymer thin films from monoterpene alcohols for applications in organic electronics and biotechnology

After more than twenty years of basic and applied research, the use of nanotechnology in the design and manufacture of nanoscale materials is rapidly increasing, particularly in commercial applications that span from electronics across renewable energy areas, and biomedical devices. Novel polymers are attracting significant attention for they promise to provide a low−cost high−performance alternative to existing materials. Furthermore, these polymers have the potential to overcome limitations imposed by currently available materials thus enabling the development of new technologies and applications that are currently beyond our reach. This work focuses on the development of a range of new low−cost environmentally−friendly polymer materials for applications in areas of organic (flexible) electronics, optics, and biomaterials. The choice of the monomer reflects the environmentally−conscious focus of this project. Terpinen−4−ol is a major constituent of Australian grown Melaleuca alternifolia (tea tree) oil, attributed with the oil's antimicrobial and anti−inflammatory properties. Plasma polymerisation was chosen as a deposition technique for it requires minimal use of harmful chemicals and produces no hazardous by−products. Polymer thin films were fabricated under varied process conditions to attain materials with distinct physico−chemical, optoelectrical, biological and degradation characteristics. The resultant materials, named polyterpenol, were extensively characterised using a number of well−accepted and novel techniques, and their fundamental properties were defined. Polyterpenol films were demonstrated to be hydrocarbon rich, with variable content of oxygen moieties, primarily in the form of hydroxyl and carboxyl functionalities. The level of preservation of original monomer functionality was shown to be strongly dependent on the deposition energy, with higher applied power increasing the molecular fragmentation and substrate temperature. Polyterpenol water contact angle contact angle increased from 62.7° for the 10 W samples to 76.3° for the films deposited at 100 W. Polymers were determined to resist solubilisation by water, due to the extensive intermolecular and intramolecular hydrogen bonds present, and other solvents commonly employed in electronics and biomedical processing. Independent of deposition power, the surface topography of the polymers was shown to be smooth (Rq <0.5 nm), uniform and defect free. Hardness of polyterpenol coatings increased from 0.33 GPa for 10 W to 0.51 GPa for 100 W (at 500 μN load). Coatings deposited at higher input RF powers showed less mechanical deformation during nanoscratch testing, with no considerable damage, cracking or delamination observed. Independent of the substrate, the quality of film adhesion improved with RF power, suggesting these coatings are likely to be more stable and less susceptible to wear. Independent of fabrication conditions, polyterpenol thin films were optically transparent, with refractive index approximating that of glass. Refractive index increased slightly with deposition power, from 1.54 (10 W) to 1.56 (100 W) at 500 nm. The optical band gap values declined with increasing power, from 2.95 eV to 2.64 eV, placing the material within the range for semiconductors. Introduction of iodine impurity reduced the band gap of polyterpenol, from 2.8 eV to 1.64 eV, by extending the density of states more into the visible region of the electromagnetic spectrum. Doping decreased the transparency and increased the refractive index from 1.54 to 1.70 (at 500 nm). At optical frequencies, the real part of permittivity (k) was determined to be between 2.34 and 2.65, indicating a potential low-k material. These permittivity values were confirmed at microwave frequencies, where permittivity increased with input RF energy – from 2.32 to 2.53 (at 10 GHz ) and from 2.65 to 2.83 (at 20 GHz). At low frequencies, the dielectric constant was determined from current−voltage characteristics of Al−polyterpenol−Al devices. At frequencies below 100 kHz, the dielectric constant varied with RF power, from 3.86 to 4.42 at 1 kHz. For all samples, the resistivity was in order of 10⁸−10⁹ _m (at 6 V), confirming the insulating nature of polyterpenol material. In situ iodine doping was demonstrated to increase the conductivity of polyterpenol, from 5.05 × 10⁻⁸ S/cm to 1.20 × 10⁻⁶ S/cm (at 20 V). Exposed to ambient conditions over extended period of time, polyterpenol thin films were demonstrated to be optically, physically and chemically stable. The bulk of ageing occurred within first 150 h after deposition and was attributed to oxidation and volumetric relaxation. Thermal ageing studies indicated thermal stability increased for the films manufactured at higher RF powers, with degradation onset temperature associated with weight loss shifting from 150 ºC to 205 ºC for 10 W and 100 W polyterpenol, respectively. Annealing the films to 405 °C resulted in full dissociation of the polymer, with minimal residue. Given the outcomes of the fundamental characterisation, a number of potential applications for polyterpenol have been identified. Flexibility, tunable permittivity and loss tangent properties of polyterpenol suggest the material can be used as an insulating layer in plastic electronics. Implementation of polyterpenol as a surface modification of the gate insulator in pentacene-based Field Effect Transistor resulted in significant improvements, shifting the threshold voltage from + 20 V to –3 V, enhancing the effective mobility from 0.012 to 0.021 cm²/Vs, and improving the switching property of the device from 10⁷ to 10⁴. Polyterpenol was demonstrated to have a hole transport electron blocking property, with potential applications in many organic devices, such as organic light emitting diodes. Encapsulation of biomedical devices is also proposed, given that under favourable conditions, the original chemical and biological functionality of terpinen−4−ol molecule can be preserved. Films deposited at low RF power were shown to successfully prevent adhesion and retention of several important human pathogens, including P. aeruginosa, S. aureus, and S. epidermidis, whereas films deposited at higher RF power promoted bacterial cell adhesion and biofilm formation. Preliminary investigations into in vitro biocompatibility of polyterpenol demonstrated the coating to be non−toxic for several types of eukaryotic cells, including Balb/c mice macrophage and human monocyte type (HTP−1 non-adherent) cells. Applied to magnesium substrates, polyterpenol encapsulating layer significantly slowed down in vitro biodegradation of the metal, thus increasing the viability and growth of HTP−1 cells. Recently, applied to varied nanostructured titanium surfaces, polyterpenol thin films successfully reduced attachment, growth, and viability of P. aeruginosa and S. aureus.

Poly(3-hexyl-thiophene) coil-wrapped single wall carbon nanotube investigated by scanning tunneling spectroscopy

Scanning Tunneling Spectroscopy was performed on a (15,0) single wall carbon nanotube partially wrapped by Poly(3-hexyl-thiophene). On the bare nanotube section, the local density of states is in good agreement with the theoretical model based on local density approximation and remarkably is not perturbed by the polymer wrapping. On the coiled section, a rectifying current-voltage characteristic has been observed along with the charge transfer from the polymer to the nanotube. The electron transfer from Poly(3-hexyl-thiophene) to metallic nanotube was previously theoretically proposed and contributes to the presence of the Schottky barrier at the interface responsible for the rectifying behavior.

Self-defence against terrorism in the post 9/11 world

In 1986 the then United States Secretary of State George Shultz asserted that: It is absurd to argue that international law prohibits us from capturing terrorists in international waters or airspace; from attacking them on the soil of other nations, even for the purpose of rescuing hostages; or from using force against states that support, train and harbor terrorists or guerrillas. At that time the United States’ claim of a right to use military force in self-defence against terrorism2 received little support from other states.3 The predominant view then was that terrorist attacks committed by private or non-state actors were a form of criminal activity to be combated through domestic and international criminal justice mechanisms. The notion that such terrorist acts should be treated as ‘armed attacks’ triggering a victim state’s right of self-defence was not accepted by the majority of states. To suggest, as Shultz had done, that a state not directly responsible for terrorist acts could have its territorial integrity violated by military action targeting terrorists located within that state, was a controversial proposition in 1986. However, some fifteen years later, when the United States and a coalition of allies launched a military campaign in Afghanistan following the 11 September 2001 (hereafter ‘9/11’) terrorist attacks, there was virtually unanimous international support for the use of force.

Removing barriers to protection at the exported border : visas, carrier sanctions, and international obligation

Asylum is being gradually denuded of the national institutional mechanisms (judicial, legislative and administrative) that provide the framework for a fair and effective asylum hearing. In this sense, there is an ongoing ‘denationalization’ or ‘deformalization’ of the asylum process. This chapter critically examines one of the linchpins of this trend: the erection of pre-entry measures at ports of embarkation in order to prevent asylum seekers from physically accessing the territory of the state. Pre-entry measures comprise the core requirement that foreigners possess an entry visa granting permission to enter the state of destination. Visa requirements are increasingly implemented by immigration officials posted abroad or by officials of transit countries pursuant to bilateral agreements (so-called ‘juxtaposed’ immigration controls). Private carriers, which are subject to sanctions if they bring persons to a country who do not have permission to enter, also engage in a form of de facto immigration control on behalf of states. These measures constitute a type of ‘externalized’ or ‘exported’ border that pushes the immigration boundaries of the state as far from its physical boundaries as possible. Pre-entry measures have a crippling impact on the ability of asylum seekers to access the territory of states to claim asylum. In effect, states have ‘externalized’ asylum by replacing the legal obligation on states to protect refugees arriving at ports of entry with what are perceived to be no more than moral obligations towards asylum seekers arriving at the external border of the state.

Book review : Olivier Corten, The Law Against War

Olivier Corten’s The Law Against War is a comprehensive, meticulously-researched study of contemporary international law governing the use of armed force in international relations. As a translated and updated version of a 2008 book published in French, it offers valuable insights into the positivist methodology that underpins much of the European scholarship of international law. Corten undertakes a rigorous analysis of state practice from 1945 onwards, with a view to clarifying the current meaning and scope of international law’s prohibition on the use of force. His central argument is that the majority of states remain attached to a strict interpretation of this rule. For Corten, state practice indicates that the doctrines of anticipatory self-defence, pre-emptive force and humanitarian intervention have no basis in contemporary international law. His overall position accords with a traditional, restrictive view of the circumstances in which states are permitted to use force...

Organized crime in Oceania

Oceania has a relatively low level of crime prevalence yet in the smaller and under-developed PICs we have shown that transnational crime has become increasingly common. A risk contained but potentially dangerous if state failure or fragility undermines law enforcement capacities. We predict that as the pace of globalization quickens and the demand for raw materials and resources grows some parts of the Pacific will be prone to criminal enterprises run by both indigenous and foreign crime groups. Australia and New Zealand will remain attractors of illicit goods notably ATS but will in turn be source countries for diminishing fish stock such as beche de mere and abalone as well forest timber. Finally the role of states such as Australia and New Zealand in helping to maintain law enforcement capacities throughout the region will be crucial if organized crime in Oceania is to be kept in check while demand for illicit resources grow.

Transnational organized crime in Oceania

Oceania has a relatively low level of crime prevalence yet in the smaller and under-developed PICs we have shown that transnational crime has become increasingly common. A risk contained but potentially dangerous if state failure or fragility undermines law enforcement capacities. We predict that as the pace of globalization quickens and the demand for raw materials and resources grows some parts of the Pacific will be prone to criminal enterprises run by both indigenous and foreign crime groups. Australia and New Zealand will remain attractors of illicit goods notably ATS but will in turn be source countries for diminishing fish stock such as beche de mere and abalone as well forest timber. Finally the role of states such as Australia and New Zealand in helping to maintain law enforcement capacities throughout the region will be crucial if organized crime in Oceania is to be kept in check while demand for illicit resources grow.

Introduction

This book explores the impacts of global economic, political and cultural shifts on various international legal frameworks and legal norms. The economic growth of states throughout Asia, South and Central America and Africa is having a profound effect on the dynamics of international relations, with a resulting impact on the operation and development of international law. This book examines the influence of emerging economies on international legal rules, institutions and processes. It describes recent and predicted changes in economic, political and cultural powers, flowing from the growth of emerging economies such as China, India, Brazil, South Africa and Russia, and analyses the influence of these changes on various legal frameworks and norms. Expert contributors drawn from a variety of fields, including international law, politics, environmental law, human rights, economics and finance, provide a broad analysis of the nature of the shifting global dynamic in its historical and contemporary contexts, and a range of perspectives on the impact of these changes as they relate to specific regimes and issues, including climate change regulation, collective security, indigenous rights, the rights of women and girls, environmental protection and foreign aid and development. The book provides a fresh and comprehensive analysis of an issue with extensive implications for international law and politics.

Metal hexaborides with Sc, Ti or Mn

Comparison of well-determined single crystal data for stoichiometric, or near-stoichiometric, metal hexaborides con-firm previously identified lattice parameter trends using powder diffraction. Trends for both divalent and trivalent forms suggest that potential new forms for synthesis include Sc and Mn hexaborides. Density Functional Theory (DFT) calculations for KB6, CaB6, YB6, LaB6, boron octahedral clusters and Sc and Mn forms, show that the shapes of bonding orbitals are defined by the boron framework. Inclusion of metal into the boron framework induces a reduction in energy ranging from 1 eV to 6 eV increasing with ionic charge. For metals with d1 character, such a shift in energy brings a doubly degenerate band section along the G-M reciprocal space direction within the conduction bands tangential to the Fermi surface. ScB6 band structure and density of states calculations show directional and gap characteristics similar to those of YB6 and LaB6. These calculations for ScB6 suggest it may be possible to realize superconductivity in this compound if synthesized.

An analogy between the double slit experiment and document ranking

In the last years several works have investigated a formal model for Information Retrieval (IR) based on the mathematical formalism underlying quantum theory. These works have mainly exploited geometric and logical–algebraic features of the quantum formalism, for example entanglement, superposition of states, collapse into basis states, lattice relationships. In this poster I present an analogy between a typical IR scenario and the double slit experiment. This experiment exhibits the presence of interference phenomena between events in a quantum system, causing the Kolmogorovian law of total probability to fail. The analogy allows to put forward the routes for the application of quantum probability theory in IR. However, several questions need still to be addressed; they will be the subject of my PhD research

Recursive pathways to marginal likelihood estimation with prior-sensitivity analysis

We investigate the utility to computational Bayesian analyses of a particular family of recursive marginal likelihood estimators characterized by the (equivalent) algorithms known as "biased sampling" or "reverse logistic regression" in the statistics literature and "the density of states" in physics. Through a pair of numerical examples (including mixture modeling of the well-known galaxy dataset) we highlight the remarkable diversity of sampling schemes amenable to such recursive normalization, as well as the notable efficiency of the resulting pseudo-mixture distributions for gauging prior-sensitivity in the Bayesian model selection context. Our key theoretical contributions are to introduce a novel heuristic ("thermodynamic integration via importance sampling") for qualifying the role of the bridging sequence in this procedure, and to reveal various connections between these recursive estimators and the nested sampling technique.

Coherent phonon decay and the boron isotope effect for MgB2

Ab-initio DFT calculations for the phonon dispersion (PD) and the Phonon Density Of States (PDOS) of the two isotopic forms (10B and 11B) of MgB2 demonstrate that use of a reduced symmetry super-lattice provides an improved approximation to the dynamical, phonon-distorted P6/mmm crystal structure. Construction of phonon frequency plots using calculated values for these isotopic forms gives linear trends with integer multiples of a base frequency that change in slope in a manner consistent with the isotope effect (IE). Spectral parameters inferred from this method are similar to that determined experimentally for the pure isotopic forms of MgB2. Comparison with AlB2 demonstrates that a coherent phonon decay down to acoustic modes is not possible for this metal. Coherent acoustic phonon decay may be an important contributor to superconductivity for MgB2.

Fred’s Flow (Canada) and Murphy Well (Australia) : thick komatiitic lava flows with contrasting compositions, emplacement mechanisms and water contents

Two Archaean komatiitic flows, Fred’s Flow in Canada and the Murphy Well Flow in Australia, have similar thicknesses (120 and 160 m) but very different compositions and internal structures. Their contrasting differentiation profiles are keys to determine the cooling and crystallization mechanisms that operated during the eruption of Archaean ultramafic lavas. Fred’s Flow is the type example of a thick komatiitic basalt flow. It is strongly differentiated and consists of a succession of layers with contrasting textures and compositions. The layering is readily explained by the accumulation of olivine and pyroxene in a lower cumulate layer and by evolution of the liquid composition during downward growth of spinifex-textured rocks within the upper crust. The magmas that erupted to form Fred’s Flow had variable compositions, ranging from 12 to 20 wt% MgO, and phenocryst contents from 0 to 20 vol%. The flow was emplaced by two pulses. A first ~20-m-thick pulse was followed by another more voluminous but less magnesian pulse that inflated the flow to its present 120 m thickness. Following the second pulse, the flow crystallized in a closed system and differentiated into cumulates containing 30–38 wt% MgO and a residual gabbroic layer with only 6 wt% MgO. The Murphy Well Flow, in contrast, has a remarkably uniform composition throughout. It comprises a 20-m-thick upper layer of fine-grained dendritic olivine and 2–5 vol% amygdales, a 110–120 m intermediate layer of olivine porphyry and a 20–30 m basal layer of olivine orthocumulate. Throughout the flow, MgO contents vary little, from only 30 to 33 wt%, except for the slightly more magnesian basal layer (38–40 wt%). The uniform composition of the flow and dendritic olivine habits in the upper 20 m point to rapid cooling of a highly magnesian liquid with a composition like that of the bulk of the flow. Under equilibrium conditions, this liquid should have crystallized olivine with the composition Fo94.9, but the most magnesian composition measured by electron microprobe in samples from the flow is Fo92.9. To explain these features, we propose that the parental liquid contained around 32 wt% MgO and 3 wt% H2O. This liquid degassed during the eruption, creating a supercooled liquid that solidified quickly and crystallized olivine with non-equilibrium textures and compositions.

Time-independent charge carrier mobility in a model polymer:fullerene organic solar cell

The technique of photo-CELIV (charge extraction by linearly increasing voltage) is one of the more straightforward and popular approaches to measure the faster carrier mobility in measurement geometries that are relevant for operational solar cells and other optoelectronic devices. It has been used to demonstrate a time-dependent photocarrier mobility in pristine polymers, attributed to energetic relaxation within the density of states. Conversely, in solar cell blends, the presence or absence of such energetic relaxation on transport timescales remains under debate. We developed a complete numerical model and performed photo-CELIV experiments on the model high efficiency organic solar cell blend poly[3,6-dithiophene-2-yl-2,5-di(2-octyldodecyl)-pyrrolo[3,4-c]pyrrole-1,4-dione-alt-naphthalene] (PDPP-TNT):[6,6]-phenyl-C71-butyric-acid-methyl-ester (PC70BM). In the studied solar cells a constant, time-independent mobility on the scale relevant to charge extraction was observed, where thermalisation of photocarriers occurs on time scales much shorter than the transit time. Therefore, photocarrier relaxation effects are insignificant for charge transport in these efficient photovoltaic devices.

Lock the gate: Fracking, investor-state dispute settlement, and the Trans-Pacific Partnership

There has been much debate about the relationship between international trade, the environment, biodiversity protection, and climate change.The Obama Administration has pushed such issues into sharp relief, with its advocacy for sweeping international trade agreements, such as the Trans-Pacific Partnership and the Trans-Atlantic Trade and Investment Partnership. There has been much public concern about the impact of the mega-trade deals upon the protection of the environment. In particular, there has been a debate about whether the Trans-Pacific Partnership will promote dirty fracking. Will the Trans-Pacific Partnership transform the Pacific Rim into a Gasland?There has been a particular focus upon investor-state dispute settlement being used by unconventional mining companies. Investor-state dispute settlement is a mechanism which enables foreign investors to seek compensation from national governments at international arbitration tribunals. In her prescient 2009 book, The Expropriation of Environmental Governance, Kyla Tienhaara foresaw the rise of investor-state dispute resolution of environmental matters. She observed:'Over the last decade there has been an explosive increase of cases investment arbitration. This is significant in terms of not only the number of disputes that have arisen and the number of states that have been involved, but also the novel types of dispute that have emerged. Rather than solely involving straightforward incidences of nationalization or breach of contract, modern disputes often revolve around public policy measures and implicate sensitive issues such as access to drinking water, development on sacred indigenous sites and the protection of biodiversity.'In her study, Kyla Tienhaara observed that investment agreements, foreign investment contracts and investment arbitration had significant implications for the protection for the protection of the environment. She concluded that arbitrators have made it clear that they can, and will, award compensation to investors that claim to have been harmed by environmental regulation. She also found that some of the cases suggest that the mere threat of arbitration is sufficient to chill environmental policy development. Tienhaara was equally concerned by the possibility that a government may use the threat of arbitration as an excuse or cover for its failure to improve environmental regulation. In her view, it is evident that arbitrators have expropriated certain fundamental aspects of environmental governance from states. Tienhaara held: As a result, environmental regulation has become riskier, more expensive, and less democratic, especially in developing countries. This article provides a comparative analysis of the battles over fracking, investment, trade, and the environment in a number of key jurisdictions including the United States, Canada, Australia, and New Zealand. Part 1 focuses upon the United States. Part 2 examines the dispute between the Lone Pine Resources Inc. and the Government of Canada over a fracking moratorium in Quebec. Part 3 charts the rise of the Lock the Gate Alliance in Australia, and its demands for a moratorium in respect of coal seam gas and unconventional mining. Part 4 focuses upon parallel developments in New Zealand. This article concludes that Pacific Rim countries should withdraw from investor-state dispute settlement procedures, because of the threat posed to environmental regulation in respect of air, land, and water.