Near-surface distributions of soil water and water repellency under three effluent irrigation schemes in a blue gum (Eucalyptus globulus) plantation

Water repellent soils are difficult to irrigate and susceptible to preferential flow, which enhances the potential for accelerated leaching to groundwater of hazardous substances. Over 5 Mha of Australian soil is water repellent, while treated municipal sewage is increasingly used for irrigation. Only if a critical water content is exceeded will repellent soils become wettable. To avoid excessive loss of water from the root zone via preferential flow paths, irrigation schemes should therefore aim to keep the soil wet enough to maintain soil wettability. Our objective was to monitor the near-surface water content and water repellency in a blue gum (Eucalyptus globulus) plantation irrigated with treated sewage. The plantation's sandy soil surface was strongly water repellent when dry. For 4 months, three rows of 15 blue gum trees each received no irrigation, three other rows received 50% of the estimated potential water use minus rainfall, and three more rows received 100%. During this period, 162 soil samples were obtained in three sampling rounds, and their water content (% dry mass) and degree of water repellency determined. Both high and low irrigation effectively wetted up the soil and eliminated water repellency after 2 (high) or 4 (low) months. A single-peaked distribution of water contents was observed in the soil samples, but the water repellency distribution was dichotomous, with 44% extremely water-repellent and 36% wettable. This is consistent with a threshold water content at which a soil sample changes from water repellent to wettable, with spatial variability of this threshold creating a much wider transition zone at the field scale. We characterized this transition zone by expressing the fraction of wettable samples as a function of water content, and demonstrated a way to estimate from this the wettable portion of a field from a number of water content measurements. To keep the plantation soil wettable, the water content must be maintained at a level at which a significant downward flux is likely, with the associated enhanced leaching. At water contents with negligible downward flux, the field is water repellent, and leaching through preferential flow paths is likely. Careful management is needed to resolve these conflicting requirements.

The effect of potential bias on the formation of ionic liquid generated surface films on Mg alloys

An electrochemical approach to the formation of a protective surface film on Mg alloys immersed in the ionic liquid (IL), trihexyl(tetradecyl)phosphonium–bis 2,4,4-trimethylpentylphosphinate, was investigated in this work. Initially, cyclic voltammetry was used with the Mg alloy being cycled from OCP to more anodic potentials. EIS data indicate that, under these circumstances, an optimum level of protection was achieved at intermediate potentials (e.g., 0 or 0.25 V versus Ag/AgCl). In the second part of this paper, a small constant bias was applied to the Mg alloy immersed in the IL for extended periods using a novel cell design. This electrochemical cell allowed us to monitor in situ surface film formation on the metal surface as well as the subsequent corrosion behaviour of the metal in a corrosive medium. This apparatus was used to investigate the evolution of the surface film on an AZ31 magnesium alloy under a potential bias (between ±100 mV versus open circuit) applied for over 24 h, and the film evolution was monitored using electrochemical impedance spectroscopy (EIS). A film resistance was determined from the EIS data and it was shown that this increased substantially during the first few hours (independent of the bias potential used) with a subsequent decrease upon longer exposure of the surface to the IL. Preliminary characterization of the film formed on the Mg alloy surface using ToF-SIMS indicates that a multilayer surface exists with a phosphorous rich outer layer and a native oxide/hydroxide film underlying this. The corrosion performance of a treated AZ31 specimen when exposed to 0.1 M NaCl aqueous solution showed considerable improvement, consistent with electrochemical data.

Identification of surface heterogeneity effects in cyclic voltammograms derived from analysis of an individually addressable gold array electrode

Voltammetric behavior at gold electrodes in aqueous media is known to be strongly dependent on electrode polishing and history. In this study, an electrode array consisting of 100 nominally identical and individually addressable gold disks electrodes, each with a radius of 127 µm, has been fabricated. The ability to analyze both individual electrode and total array performance enables microscopic aspects of the overall voltammetric response arising from variable levels of inhomogeneity in each electrode to be identified. The array configuration was initially employed with the reversible and hence relatively surface insensitive [Ru(NH₃)₆]^3+/2+ reaction and then with the more highly surface sensitive quasi-reversible [Fe(CN)₆]^3−/4− process. In both these cases, the reactants and products are solution soluble and, at a scan rate of 50 mV s⁻¹, each electrode in the array is assumed to behave independently, since no evidence of overlapping of the diffusion layers was detected. As would be expected, the variability of the individual electrodesʼ responses was significantly larger than found for the summed electrode behavior. In the case of cytochrome c voltammetry at a 4,4′-dipyridyl disulfide modified electrode, a far greater dependence on electrode history and electrode heterogeneity was detected. In this case, voltammograms derived from individual electrodes in the gold array electrode exhibit shape variations ranging from peak to sigmoidal. However, again the total response was always found to be well-defined. This voltammetry is consistent with a microscopic model of heterogeneity where some parts of each chemically modified electrode surface are electroactive while other parts are less active. The findings are consistent with the common existence of electrode heterogeneity in cyclic voltammetric responses at gold electrodes, that are normally difficult to detect, but fundamentally important, as electrode nonuniformity can give rise to subtle forms of kinetic and other forms of dispersion.

First-principles based force-field for the interaction of proteins with Au(100)(5 x 1): an extension of GolP-CHARMM

Noncovalent recognition between peptides and inorganic materials is an established phenomenon. Key to exploiting these interactions in a wide range of materials self-assembly applications would be to harness the facet-selective control of peptide binding onto these materials. Fundamental understanding of what drives facet-selectivity in peptide binding is developing, but as yet is not sufficient to enable design of predictable facet-specific sequences. Computational simulation of the aqueous peptide-gold interface, commonly used to understand the mechanisms driving adsorption at an atomic level, has thus far neglected the role that surface reconstruction might play in facet specificity. Here the polarizable GolP-CHARMM suite of force fields is extended to include the reconstructed Au(100) surface. The force field, compatible with the bio-organic force field CHARMM, is parametrized using first-principles data. Our extended force field is tailored to reproduce the heterogeneity of weak chemisorbing N and S species to specific locations in the Au(100)(5 × 1) surface identified from the first-principles calculations. We apply our new model to predict and compare the three-dimensional structure of liquid water at Au(111), Au(100)(1 × 1), and Au(100)(5 × 1) interfaces. Using molecular dynamics simulations, we predict an increased likelihood for water-mediated peptide adsorption at the aqueous-Au(100)(1 × 1) interface compared with the Au(100)(5 × 1) interface. Therefore, our findings suggest that peptide binding can discriminate between the native and reconstructed Au(100) interfaces and that the role of reconstruction on binding at the Au(100) interface should not be neglected. © 2013 American Chemical Society.

Characterization and optimization to improve uneven surface on MEMS bridge fabrication

This paper presents an optimized fabrication method for developing a freestanding bridge for RF MEMS switches. In this method, the sacrificial layer is patterned and hard baked a 220°C for 3min, after filling the gap between the slots of the coplanar waveguide. Measurement results by AFM and SEM demonstrate that this technique significantly improves the planarity of the sacrificial layer, reducing the uneven surface to less than 20nm, and the homogeneity of the Aluminum thickness across the bridge. Moreover, a mixture of O2, Ar and CF4 was used and optimized for dry releasing of the bridge. A large membrane (200×100μm2) was released without any surface bending. Therefore, this method not only simplifies the fabrication process, but also improves the surface flatness and edge smoothness of the bridge. This fabrication method is fully compatible with standard silicon IC technology.

Self-assembly of monolayered lipid membranes for surface-coating of a nanoconfined Bombyx mori silk fibroin film

Regenerated Bombyx mori (B. mori) silk fibroin is a type of widely used biomaterial. The β-sheet structure of it after methanol treatment provides water-insolubility and mechanical stability while on the other side leads to a hydrophobic surface which is less preferred by biological systems. In this work we prepare a novel type of nanoconfined silk fibroin film with a thickness below 100 nm. The film has a flat while hydrophobic surface because of its β-sheet structure due to the z-direction confinement during formation. Different types of lipid monolayers, DOPC, DPPC and MO, are assembled on the silk film surface. The lipid coating, especially the DPPC membrane, provides a much smoother and more hydrophilic surface due to the gel phase tails of the lipids, in comparison with the DOPC and MO ones which are in a liquid phase and have a much stronger interfacial association between silk film surface and lipid tails. Such a lipid coating preserves the biocompatibility and cellular affinity of the silk film which promises potential applications as surface coatings for materials for biological use.

Self-cleaning, superhydrophobic cotton fabrics with excellent washing durability, solvent resistance and chemical stability prepared from an SU-8 derived surface coating

Superhydrophobic cotton fabrics with a very low contact angle hysteresis were prepared using a single-pot coating solution comprising SU-8 (a negative photoresist), a fluorinated alkyl silane and silica nanoparticles. The fabric was treated using a dip-coating technique and subsequently cured under UV light. The coated fabric showed excellent superhydrophobicity with a water contact angle as high as 163° and a sliding angle as low as 2°. The coating was durable enough to withstand 100 laundry cycles. It also had excellent stability against long immersion times in organic solvents, and acid and base solutions.

The effect of treatment time on the ionic liquid surface film formation: promising surface coating for Mg alloy AZ31

Mg alloys are attractive materials for medical devices. The main limitation is that they are prone to corrosion. A low toxicity surface coating that enables uniform, controlled corrosion at a desired rate (this usually means it must offer barrier functions for a limited time period) is desirable. Phosphate-based ionic liquids (ILs) are known to induce a coating that can reduce the corrosion rate of Mg alloys, Furthermore, some ILs are known to be biocompatible and therefore, controlling the corrosion behaviour of an Mg alloy and its surface biocompatibility can be achieved through adding an appropriate low toxic IL surface layer to the substrate. In this study, we have evaluated the cytotoxicity of three phosphate-based ILs to primary human coronary artery endothelial cells. Among them, tributyl(methyl)-phosphonium diphenylphosphate (P1,4,4,4dpp) shows the lowest cytotoxicity. Therefore, further work was aimed at developing an appropriate treatment method to produce a homogeneous and passive surface coating based on P1,4,4,4dpp IL, with the focus on investigating the effect of treatment time. The results showed that that the formation of IL coating on AZ31 has proceeded progressively, and treatment time plays an important role. An IL treatment at 100 °C with an extended treatment time of 5 h significantly enhanced corrosion resistance of the AZ31 alloy in simulated body fluid. Additionally, the corrosion morphology was uniform and there was no evidence of "localized pitting corrosion" observed. Such a performance makes this ionic liquid coating as a potential surface coating biodegradable Mg-based implants.