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.

Comparative study on green building supportive policies of pacific-rim countries most vulnerable to climate change

- Problem Climate change is affecting the world in numerous ways such as increased temperatures, sea level rise, and increased droughts and floods. Governments worldwide, especially in the most vulnerable countries, are urged to seek better solutions for sustainable development. The construction industry and buildings have enormous impacts on humans and the environment, meaning green building must be one of the solutions. Government involvement is widely considered as one of the essential and most effective ways to promote green building and drive the construction market towards sustainability. This paper will review green building policy of the Pacific-Rim countries that are most vulnerable to climate change according to the recent Standard and Poor’s ranking, including: Cambodia, Vietnam, Fiji, Philippines, Papua New Guinea and Indonesia. Methodology: This paper will review policy related publications including journal and conference papers, portal websites of governments, legislation documents and reports of international organisations. It will focus on the policies and governmental instruments that support the adoption of green building practices. - Findings All six governments have launched climate change adaptation policies, showing a great concern regarding the damages caused by the phenomenon. All countries except Papua New Guinea have promulgated energy efficiency policy and programs which indirectly promote the adoption of green building practices. The comparison study shows that Philippines and Indonesia motivate the adoption of renewable energy generation, energy efficiency and green building through either financial or advocacy instruments, while other four countries tend to implement regulatory tools to mandate energy conservation. Through comparison, Cambodia and Vietnam – the two countries providing vision to develop green building - can learn from Philippines and Indonesia’s policy and instruments. - Research limitations Language differences between the countries and limit of formal sources may pose difficulties in searching for information. While much English language literature exists, sources from Cambodia, Philippines and Indonesia are less accessible. - Takeaway for practice As the paper provides more understanding about the supportive policy of those countries, it will introduce more opportunities for green property developers to invest in construction markets of those Pacific-Rim countries. - Originality There is little research reviewing green building supportive policies of developing and less-wealthy countries that are forecasted to be most vulnerable and most impacted by climate change. The originality of this paper lies in its investigation on how those countries intend to respond to this phenomenon and whether and to what extent they support the green building market by using policy tools.

Biofuels from food processing wastes

Food processing industry generates substantial high organic wastes along with high energy uses. The recovery of food processing wastes as renewable energy sources represents a sustainable option for the substitution of fossil energy, contributing to the transition of food sector towards a low-carbon economy. This article reviews the latest research progress on biofuel production using food processing wastes. While extensive work on laboratory and pilot-scale biosystems for energy production has been reported, this work presents a review of advances in metabolic pathways, key technical issues and bioengineering outcomes in biofuel production from food processing wastes. Research challenges and further prospects associated with the knowledge advances and technology development of biofuel production are discussed.

Editorial of "International Journal of Critical Indigenous Studies Volume 5, Number 1, 2012"

The first two articles of this edition of the journal testify to the lengthening reach of the discipline of Critical Indigenous Studies that is, remarkably, still in its nascence. Emiel Martens examines the development of Maori filmmaking since the 1980s and takes the opportunity to explore this Indigenous cinema in the context of developments in the New Zealand film industry generally. Shifting from cultural production to renewable energy, Steven M. Hoffman and Thibault Martin remind us that in the effort to satiate the demands for energy, it is often Indigenous peoples who bear adverse consequences. Using a social capital framework, the authors examine the impact of the development of hydroelectric power upon a displaced Aboriginal community and conclude that displacement has resulted in an erosion of cohesive social bonds that once ensured a sustainable way of life.

Integration and optimization of pressure retarded osmosis with reverse osmosis for power generation and high efficiency desalination

Salinity gradient power is proposed as a source of renewable energy when two solutions of different salinity are mixed. In particular, Pressure Retarded Osmosis (PRO) coupled with a Reverse Osmosis process (RO) has been previously suggested for power generation, using RO brine as the draw solution. However, integration of PRO with RO may have further value for increasing the extent of water recovery in a desalination process. Consequently, this study was designed to model the impact of various system parameters to better understand how to design and operate practical PRO-RO units. The impact of feed salinity and recovery rate for the RO process on the concentration of draw solution, feed pressure, and membrane area of the PRO process was evaluated. The PRO system was designed to operate at maximum power density of . Model results showed that the PRO power density generated intensified with increasing seawater salinity and RO recovery rate. For an RO process operating at 52% recovery rate and 35 g/L feed salinity, a maximum power density of 24 W/m2 was achieved using 4.5 M NaCl draw solution. When seawater salinity increased to 45 g/L and the RO recovery rate was 46%, the PRO power density increased to 28 W/m2 using 5 M NaCl draw solution. The PRO system was able to increase the recovery rate of the RO by up to 18% depending on seawater salinity and RO recovery rate. This result suggested a potential advantage of coupling PRO process with RO system to increase the recovery rate of the desalination process and reduce brine discharge.

Sugarcane-Based Biofuels and Bioproducts

Sugarcane has garnered much interest for its potential as a viable renewable energy crop. While the use of sugar juice for ethanol production has been in practice for years, a new focus on using the fibrous co-product known as bagasse for producing renewable fuels and bio-based chemicals is growing in interest. The success of these efforts, and the development of new varieties of energy canes, could greatly increase the use of sugarcane and sugarcane biomass for fuels while enhancing industry sustainability and competitiveness. Sugarcane-Based Biofuels and Bioproducts examines the development of a suite of established and developing biofuels and other renewable products derived from sugarcane and sugarcane-based co-products, such as bagasse. Chapters provide broad-ranging coverage of sugarcane biology, biotechnological advances, and breakthroughs in production and processing techniques. This text brings together essential information regarding the development and utilization of new fuels and bioproducts derived from sugarcane. Authored by experts in the field, Sugarcane-Based Biofuels and Bioproducts is an invaluable resource for researchers studying biofuels, sugarcane, and plant biotechnology as well as sugar and biofuels industry personnel.

Predicting single-layer technetium dichalcogenides (TcX2, X = S, Se) with promising applications in photovoltaics and photocatalysis

One of the least known compounds among transition metal dichalcogenides (TMDCs) is the layered triclinic technetium dichalcogenides (TcX2, X = S, Se). In this work, we systematically study the structural, mechanical, electronic, and optical properties of TcS2 and TcSe2 monolayers based on density functional theory (DFT). We find that TcS2 and TcSe2 can be easily exfoliated in a monolayer form because their formation and cleavage energy are analogous to those of other experimentally realized TMDCs monolayer. By using a hybrid DFT functional, the TcS2 and TcSe2 monolayers are calculated to be indirect semiconductors with band gaps of 1.91 and 1.69 eV, respectively. However, bilayer TcS2 exhibits direct-bandgap character, and both TcS2 and TcSe2 monolayers can be tuned from semiconductor to metal under effective tensile/compressive strains. Calculations of visible light absorption indicate that 2D TcS2 and TcSe2 generally possess better capability of harvesting sunlight compared to single-layer MoS2 and ReSe2, implying their potential as excellent light-absorbers. Most interestingly, we have discovered that the TcSe2 monolayer is an excellent photocatalyst for splitting water into hydrogen due to the perfect fit of band edge positions with respect to the water reduction and oxidation potentials. Our predictions expand the two-dimensional (2D) family of TMDCs, and the remarkable electronic/optical properties of monolayer TcS2 and TcSe2 will place them among the most promising 2D TMDCs for renewable energy application in the future.

Analytical modelling of integrated solar drying system

The drying of fruit and vegetables is a subject of great importance. Dried fruit and vegetables have gained commercial importance, and their growth on a commercial scale has become an important sector of the agricultural industry. However, food drying is one of the most energy intensive processes of the major industrial process and accounts for up to 15 % of all industrial energy usage. Due to increasingly high electricity prices and environmental concern, a dryer using traditional energy sources is not a feasible option anymore. Therefore, an alternative/renewable energy source is needed. In this regard, an integrated solar drying system that includes highly efficient double-pass counter flow v-groove solar collector, conical-shaped rock-bed thermal storage, auxiliary heater, the centrifugal fan and the drying chamber has been designed and constructed. Mathematical model for all the individual components as well as an integrated model combining all components of the drying system has been developed. Mathematical equations were solved using MATLAB program. This paper presents the analytical model and key finding of the simulation.

Development of an efficiency equation for solar evaporator- collectors

Considering the growing energy needs and concern for environmental degradation, clean and inexhaustible energy sources, e.g solar energy are receiving greater attention for various applications. The use of solar energy systems for low temperature applications reduces the burden on conventional fossil fuels and has little or no harmful effects on the environment. The performance of a solar system depends to a great extent on the collector used for the conversion of solar radiant energy to thermal energy. A solar evaporatorcollector (SEC) is basically an unglazed flat plate collector where refrigerant, like R134a, is used as the working fluid. As the operating temperature of SEC is very low, it collects energy both from solar irradiation and ambient energy leading to a much higher efficiency than the conventional collectors. The capability of SEC to utilize ambient energy also enables the system to operate at night. Therefore it is not appropriate to use for the evaluation of performance of SEC by conventional efficiency equation where ambient energy and condensation is not considered as energy input in addition to irradiation. In the National University of Singapore, several Solar Assisted Heat Pump (SAHP) systems were built for the evaluation of performance under the metrological condition of Singapore for thermal applications of desalination and SEC was the main component to harness renewable energy. In this paper, the design and performance of SEC are explored. Furthermore, an attempt is made to develop an efficiency equation for SEC and maximum efficiency attained 98% under the meteorological condition of Singapore.

Single atom (Pd/Pt) supported on graphitic carbon nitride as efficient photocatalyst for visible-light reduction of carbon dioxide

Reducing carbon dioxide (CO2) to hydrocarbon fuel with solar energy is significant for high-density solar energy storage and carbon balance. In this work, single palladium/platinum (Pd/Pt) atoms supported on graphitic carbon nitride (g-C3N4), i.e. Pd/g-C3N4 and Pt/g-C3N4, acting as photocatalysts for CO2 reduction were investigated by density function theory (DFT) calcu-lations for the first time. During CO2 reduction, the individual metal atoms function as the active sites, while g-C3N4 provides the source of hydrogen (H*) from hydrogen evolution reaction. The complete, as-designed photocatalysts exhibit excellent activity in CO2 reduction. HCOOH is the preferred product of CO2 reduction on the Pd/g-C3N4 catalyst with a rate-determining barrier of 0.66 eV, while the Pt/g-C3N4 catalyst prefers to reduce CO2 to CH4 with a rate-determining barrier of 1.16 eV. In addition, depositing atom catalysts on g-C3N4 significantly enhances the visible light absorption, rendering them ideal for visible light reduction of CO2. Our findings open a new avenue of CO2 reduction for renewable energy supply.