Alex M. Lord

Branched Hydrocarbon Low Surface Energy Materials for Superhydrophobic Nanoparticle Derived Surfaces

We present a new class of superhydrophobic surfaces created from low-cost and easily synthesized aluminum oxide nanoparticles functionalized carboxylic acids having highly branched hydrocarbon (HC) chains. These branched chains are new low surface energy materials (LSEMs) which can replace environmentally hazardous and expensive fluorocarbons (FCs). Regardless of coating method and curing temperature, the resulting textured surfaces develop water contact angles (θ) of ∼155° and root-mean-square roughnesses (Rq) ≈ 85 nm, being comparable with equivalent FC functionalized surfaces (θ = 157° and Rq = 100 nm). The functionalized nanoparticles may be coated onto a variety of substrates to generate different superhydrophobic materials.

Factors that determine and limit the resistivity of high-quality individual ZnO nanowires

Knowing and controlling the resistivity of an individual nanowire (NW) is crucial for the production of new sensors and devices. For ZnO NWs this is poorly understood; a 10(8) variation in resistivity has previously been reported, making the production of reproducible devices almost impossible. Here, we provide accurate resistivity measurements of individual NWs, using a four-probe scanning tunnelling microscope (STM), revealing a dependence on the NW dimensions. To correctly interpret this behaviour, an atomic level transmission electron microscopy technique was employed to study the structural properties of the NWs in relation to three growth techniques: hydrothermal, catalytic and non-catalytic vapour phase. All NWs were found to be defect free and structurally equivalent; those grown with a metallic catalyst were free from Au contamination. The resistivity measurements showed a distinct increase with decreasing NW diameter, independent of growth technique. The increasing resistivity at small NW diameters was attributed to the dominance of surface states removing electrons from the bulk. However, a fundamental variance in resistivity (10(2)) was observed and attributed to changes in occupied surface state density, an effect which is not seen with other NW materials such as Si. This is examined by a model to predict the effect of surface state occupancy on the measured resistivity and is confirmed with measurements after passivating the ZnO surface. Our results provide an understanding of the primary influence of the reactive nature of the surface and its dramatic effect on the electrical properties of ZnO NWs.

pH-responsive octylamine coupling modification of carboxylated aluminium oxide surfaces

The formation of a pH-sensitive coupling layer, through both physisorption and chemisorption, provides a responsive surface that can be assembled and disassembled in relation to external stimuli. Contact angle measurements, X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and Fourier transform IR-attenuated reflectance spectroscopy (FTIR-ATR) have been used to characterize a series of bi-functionalized self-assembled monolayers (SAMs) grown on aluminium oxide wafers/nanoparticles and investigate the reaction nature of pH-responsive coupling layer (octylamine) with the SAMs. Contact angle, XPS, and AFM analyses indicate that the surface of native aluminium oxide was covered considerably as the contact angle of the surfaces decreased, carbon atomic % and roughness of the surfaces increased.

Nano-analyses of Wear Particles from Metal-on-Metal and Non-Metal-on-Metal Dual Modular Neck Hip Arthroplasty

Increased failure rates due to metallic wear particle-associated adverse local tissue reactions (ALTR) is a significant clinical problem in resurfacing and total hip arthroplasty. Retrieved periprosthetic tissue of 53 cases with corrosion/conventional metallic wear particles from 285 revision operations for ALTR was selected for nano-analyses. Three major classes of hip implants associated with ALTR, metal-on-metal hip resurfacing arthroplasty (MoM HRA) and large head total hip replacement (MoM LHTHA) and non-metal-on-metal dual modular neck total hip replacement (Non-MoM DMNTHA) were included. The size, shape, distribution, element composition, and crystal structure of the metal particles were analyzed by conventional histological examination and electron microscopy with analytic tools of 2D X-ray energy dispersive spectrometry and X-ray diffraction. Distinct differences in size, shape, and element composition of the metallic particles were detected in each implant class which correlate with the histological features of severity of ALTR and variability in implant performance.

Controlling the Electrical Transport Properties of Nanocontacts to Nanowires

The ability to control the properties of electrical contacts to nanostructures is essential to realize operational nanodevices. Here, we show that the electrical behavior of the nanocontacts between free-standing ZnO nanowires and the catalytic Au particle used for their growth can switch from Schottky to Ohmic depending on the size of the Au particles in relation to the cross-sectional width of the ZnO nanowires. We observe a distinct Schottky to Ohmic transition in transport behavior at an Au to nanowire diameter ratio of 0.6. The current-voltage electrical measurements performed with a multiprobe instrument are explained using 3-D self-consistent electrostatic and transport simulations revealing that tunneling at the contact edge is the dominant carrier transport mechanism for these nanoscale contacts. The results are applicable to other nanowire materials such as Si, GaAs, and InAs when the effects of surface charge and contact size are considered.

Conidia of the insect pathogenic fungus, Metarhizium anisopliae, fail to adhere to mosquito larval cuticle

Adhesion of conidia of the insect pathogenic fungus, Metarhizium anisopliae, to the arthropod host cuticle initially involves hydrophobic forces followed by consolidation facilitated by the action of extracellular enzymes and secretion of mucilage. Gene expression analysis and atomic force microscopy were used to directly quantify recognition and adhesion between single conidia of M. anisopliae and the cuticle of the aquatic larval stage of Aedes aegypti and a representative terrestrial host, Tenebrio molitor. Gene expression data indicated recognition by the pathogen of both hosts; however, the forces for adhesion to the mosquito were approximately five times lower than those observed for Tenebrio. Although weak forces were recorded in response to Aedes, Metarhizium was unable to consolidate firm attachment. An analysis of the cuticular composition revealed an absence of long-chain hydrocarbons in Aedes larvae which are thought to be required for fungal development on host cuticle. This study provides, to our knowledge, the first evidence that Metarhizium does not form firm attachment to Ae. aegypti larvae in situ, therefore preventing the normal route of invasion and pathogenesis from occuring.

ZnO nanowires with Au contacts characterised in the as-grown real device configuration using a local multi-probe method

We demonstrate here a method using a multi-probe UHV instrument to isolate and measure individual metal contacts controllably fabricated on the tips of free standing ZnO nanowires (NWs). The measurements show Au can form reliable Ohmic and rectifying contacts by exercising control over the surface properties. In the as-grown state the Au contacts display low-resistance characteristics which are determined by the adsorbed species and defects on the NW surface. Subjecting the NWs to an oxidising agent (H2O2) increases the surface potential barrier creating more rectifying contacts. These developments are crucial for controllable NW array devices.

Forming reproducible non-lithographic nanocontacts to assess the effect of contact compressive strain in nanomaterials

The application of electrical nanoprobes to measure and characterize nanomaterials has become widely spread. However, the formation of quality electrical contacts using metallic probes on nanostructures has not been directly assessed. We investigate here the electrical behaviour of non-lithographically formed contacts to ZnO nanowires (NWs) and develop a method to reproducibly form Ohmic contacts for accurate electrical measurement of the nanostructures. The contacting method used in this work relies on an electrical feedback mechanism to determine the point of contact to the individual NWs, ensuring minimal compressive strain at the contact. This developed method is compared with the standard tip deflection contacting technique and shows a significant improvement in reproducibility. The effect of excessive compressive strain at the contact was investigated, with a change from rectifying to ohmic I–V behaviour observed as compressive strain at the contact was increased, leading to irreversible changes to the electrical properties of the NW. This work provides an ideal method for forming reproducible non-lithographic nanocontacts to a multitude of nanomaterials.

An Investigation of pH Mediated Extraction and Precipitation of Phosphorus from Sludge Using Microfiltration: Processing and Costs

Membrane filtration of wastewater sludge is a feasible technology for the recovery of sustainable nutrients in bacteria and particle-free solutions. Diafiltration and acidification strategies were investigated for the recovery of phosphorus (P) from trout farm sludge. Extraction costs were determined using a pilot-scale unit. pH of 2.7 was found to maximize the extraction of P (and metals) and highest concentrations were achieved by acidic leaching of the sludge sediment. Levels of P, Ca, Fe, Mg, and K recovered in soluble fractions were 418 mg/L, 6730 mg/L, 66.8 mg/L, 29 mg/L, and 34.1 mg/L, respectively. Operational costs associated with acidification and power consumption were estimated to be 0.018 kWh/L permeate or 0.037 kWh/g P obtained. The extraction of P by membrane filtration was mainly dependent on pH and cost was considerably lower than that for P-based fertilizers. Owing to the high concentration of Ca and P in the permeate fractions, 99% of the soluble P was precipitated from solution at pH 8. Elemental analysis and FTIR of the precipitate obtained indicated to be carbonated calcium-deficient hydroxyapatite.

Modifying the Interface Edge to Control the Electrical Transport Properties of Nanocontacts to Nanowires

Selecting the electrical properties of nanomaterials is essential if their potential as manufacturable devices is to be reached. Here, we show that the addition or removal of native semiconductor material at the edge of a nanocontact can be used to determine the electrical transport properties of metal-nanowire interfaces. While the transport properties of as-grown Au nanocatalyst contacts to semiconductor nanowires are well-studied, there are few techniques that have been explored to modify the electrical behavior. In this work, we use an iterative analytical process that directly correlates multiprobe transport measurements with subsequent aberration-corrected scanning transmission electron microscopy to study the effects of chemical processes that create structural changes at the contact interface edge. A strong metal-support interaction that encapsulates the Au nanocontacts over time, adding ZnO material to the edge region, gives rise to ohmic transport behavior due to the enhanced quantum-mechanical tunneling path. Removal of the extraneous material at the Au-nanowire interface eliminates the edge-tunneling path, producing a range of transport behavior that is dependent on the final interface quality. These results demonstrate chemically driven processes that can be factored into nanowire-device design to select the final properties.