David S. McPhail

Surface termination and subsurface restructuring of perovskite-based solid oxide electrode materials

We study the outer atomic surfaces of a series of perovskite-based ceramics using low energy ion scattering spectroscopy. After high temperature treatment, segregated A-site (or acceptor substituent) cations dominate the outer surfaces with no B-site cations detected. We also find evidence of an associated B-cation enriched region below the surface.

On the role of intermixed phases in organic photovoltaic blends

Recently, an intermixed phase has been identified within organic photovoltaic (OPV) bulk heterojunction (BHJ) systems that can exist in addition to relatively phase-pure regions, highlighting the need for a refined picture of the solid-state microstructure of donor–acceptor blends and for gaining further understanding of the exact nature and role such intermixed phases play in such devices. Here we manipulate the microstructure of polymer–fullerene systems via processing means and the selection of the molecular weight of the donor polymer. This manipulation is used as a tool to vary the fraction of intermixed phase present and its effects on the structure and subsequently the opto-electronic processes. We find clear relationships between the state of mixing and amount of exciton quenching and number of polarons generated per absorbed photon. Furthermore, we observe that blend systems incorporating higher molecular weight polymer result in a greater yield of dissociated polarons, likely due to the increase of the intermixed fraction.

The Stability of Silver Nanoparticles in a Model of Pulmonary Surfactant

The growing use of silver nanoparticles (AgNPs) in consumer products has raised concerns about their potential impact on the environment and human health. Whether AgNPs dissolve and release Ag(+) ions, or coarsen to form large aggregates, is critical in determining their potential toxicity. In this work, the stability of AgNPs in dipalmitoylphosphatidylcholine (DPPC), the major component of pulmonary surfactant, was investigated as a function of pH. Spherical, citrate-capped AgNPs with average diameters of 14 ± 1.6 nm (n = 200) were prepared by a chemical bath reduction. The kinetics of Ag(+) ion release was strongly pH-dependent. After 14 days of incubation in sodium perchlorate (NaClO4) or perchloric acid (HClO4) solutions, the total fraction of AgNPs dissolved varied from ∼10% at pH 3, to ∼2% at pH 5, with negligible dissolution at pH 7. A decrease in pH from 7 to 3 also promoted particle aggregation and coarsening. DPPC (100 mg·L(-1)) delayed the release of Ag(+) ions, but did not significantly alter the total amount of Ag(+) released after two weeks. In addition, DPPC improved the dispersion of the AgNPs and inhibited aggregation and coarsening. TEM images revealed that the AgNPs were coated with a DPPC layer serving as a semipermeable layer. Hence, lung lining fluid, particularly DPPC, can modify the aggregation state and kinetics of Ag(+) ion release of inhaled AgNPs in the lung. These observations have important implications for predicting the potential reactivity of AgNPs in the lung and the environment.

The lattice locations of silicon atoms in delta‐doped layers in GaAs

We have used secondary ion mass spectrometry, local vibrational mode infrared absorption, and electrical characterization to study the incorporation of Si delta‐doped planes in GaAs grown by molecular beam epitaxy at 400 °C, in the concentration range 0.01–0.5 monolayers. A correspondence is observed between the density of SiGa donors, the free electron concentration and the total Si coverage, up to a coverage of ∼1013 cm−2; however, above this value, the electron density falls, while [SiGa] remains constant up to a coverage of ∼1014 cm−2, and then falls below the detection limit at 0.5 monolayer coverage. These effects have been interpreted in terms of a model which takes account of Si migration and aggregation on the delta‐doped plane during deposition.

Amorphous Molybdenum Sulfide on Graphene–Carbon Nanotube Hybrids as Highly Active Hydrogen Evolution Reaction Catalysts

In this study, we report on the deposition of amorphous molybdenum sulfide (MoSx, with x ≈ 3) on a high specific surface area conductive support of Graphene-Carbon Nanotube hybrids (GCNT) as the Hydrogen Evolution Reaction (HER) catalysts. We found that the high surface area GCNT electrode could support the deposition of MoSx at much higher loadings compared with simple porous carbon paper or flat graphite paper. The morphological study showed that MoSx was successfully deposited on and was in good contact with the GCNT support. Other physical characterization techniques suggested the amorphous nature of the deposited MoSx. With a typical catalyst loading of 3 mg cm(-2), an overpotential of 141 mV was required to obtain a current density of 10 mA cm(-2). A Tafel slope of 41 mV decade(-1) was demonstrated. Both measures placed the MoSx-deposited GCNT electrode among the best performing molybdenum sulfide-based HER catalysts reported to date. The electrode showed a good stability with only a 25 mV increase in overpotential required for a current density of 10 mA cm(-2), after undergoing 500 potential sweeps with vigorous bubbling present. The current density obtained at -0.5 V vs SHE (Standard Hydrogen Electrode potential) decreased less than 10% after the stability test. The deposition of MoSx on high specific surface area conductive electrodes demonstrated to be an efficient method to maximize the catalytic performance toward HER.

Cotton-wool-like bioactive glasses for bone regeneration

Inorganic sol-gel solutions were electrospun to produce the first bioactive three-dimensional (3-D) scaffolds for bone tissue regeneration with a structure like cotton-wool (or cotton candy). This flexible 3-D fibrous structure is ideal for packing into complex defects. It also has large inter-fiber spaces to promote vascularization, penetration of cells and transport of nutrients throughout the scaffold. The 3-D fibrous structure was obtained by electrospinning, where the applied electric field and the instabilities exert tremendous force on the spinning jet, which is required to be viscoelastic to prevent jet break up. Previously, polymer binding agents were used with inorganic solutions to produce electrospun composite two-dimensional fibermats, requiring calcination to remove the polymer. This study presents novel reaction and processing conditions for producing a viscoelastic inorganic sol-gel solution that results in fibers by the entanglement of the intermolecularly overlapped nanosilica species in the solution, eliminating the need for a binder. Three-dimensional cotton-wool-like structures were only produced when solutions containing calcium nitrate were used, suggesting that the charge of the Ca(2+) ions had a significant effect. The resulting bioactive silica fibers had a narrow diameter range of 0.5-2μm and were nanoporous. A hydroxycarbonate apatite layer was formed on the fibers within the first 12h of soaking in simulated body fluid. MC3T3-E1 preosteoblast cells cultured on the fibers showed no adverse cytotoxic effect and they were observed to attach to and spread in the material.

Structural changes and conductance thresholds in metal-free intrinsic SiOx resistive random access memory

We present an investigation of structural changes in silicon-rich silicon oxide metal-insulator-metal resistive RAM devices. The observed unipolar switching, which is intrinsic to the bulk oxide material and does not involve movement of metal ions, correlates with changes in the structure of the oxide. We use atomic force microscopy, conductive atomic force microscopy, x-ray photoelectron spectroscopy, and secondary ion mass spectroscopy to examine the structural changes occurring as a result of switching. We confirm that protrusions formed at the surface of samples during switching are bubbles, which are likely to be related to the outdiffusion of oxygen. This supports existing models for valence-change based resistive switching in oxides. In addition, we describe parallel linear and nonlinear conduction pathways and suggest that the conductance quantum, G0, is a natural boundary between the high and low resistance states of our devices.

Bioactivity in silica/poly(γ-glutamic acid) sol–gel hybrids through calcium chelation

Bioactive glasses and inorganic/organic hybrids have great potential as biomedical implant materials. Sol-gel hybrids with interpenetrating networks of silica and biodegradable polymers can combine the bioactive properties of a glass with the toughness of a polymer. However, traditional calcium sources such as calcium nitrate and calcium chloride are unsuitable for hybrids. In this study calcium was incorporated by chelation to the polymer component. The calcium salt form of poly(γ-glutamic acid) (γCaPGA) was synthesized for use as both a calcium source and as the biodegradable toughening component of the hybrids. Hybrids of 40wt.% γCaPGA were successfully formed and had fine scale integration of Ca and Si ions, according to secondary ion mass spectrometry imaging, indicating a homogeneous distribution of organic and inorganic components. (29)Si magic angle spinning nuclear magnetic resonance data demonstrated that the network connectivity was unaltered with changing polymer molecular weight, as there was no perturbation to the overall Si speciation and silica network formation. Upon immersion in simulated body fluid a hydroxycarbonate apatite surface layer formed on the hybrids within 1week. The polymer molecular weight (Mw 30-120kDa) affected the mechanical properties of the resulting hybrids, but all hybrids had large strains to failure, >26%, and compressive strengths, in excess of 300MPa. The large strain to failure values showed that γCaPGA hybrids exhibited non-brittle behaviour whilst also incorporating calcium. Thus calcium incorporation by chelation to the polymer component is justified as a novel approach in hybrids for biomedical materials.

Highly flexible silica/chitosan hybrid scaffolds with oriented pores for tissue regeneration

Inorganic/organic sol-gel hybrids have nanoscale co-networks of organic and inorganic components that give them the unique potential of tailored mechanical properties and controlled biodegradation in tissue engineering applications. Here, silica/chitosan hybrid scaffolds with oriented structures were fabricated through the sol-gel method with a unidirectional freeze casting process. 3-Glycidoxypropyl trimethoxysilane (GPTMS) was used to obtain covalent inorganic/organic coupling. Process variables were investigated such as cooling rate, GPTMS and inorganic content, which can be used to tailor the mechanical properties and hybrid chemical coupling. Structural characterization and dissolution tests confirmed the covalent cross-linking of the chitosan and the silica network in hybrids. The scaffolds had a directional lamellar structure along the freezing direction and a cellular morphology perpendicular to the freezing direction. Compression testing showed that the scaffolds with 60 wt% organic were flexible and elastomeric perpendicular to the freezing direction whilst behaving in an elastic-brittle fashion parallel to the freezing direction. The compressive strengths are about one order of magnitude higher in the latter direction reaching values of the order of 160 kPa. This behaviour provides potential for clinicians to be able to squeeze the materials to fit tissue defect sites while providing some mechanical support from the other direction.

A topographical assessment and comparison of conservation cleaning treatments

Abstract The development of laser cleaning as a conservation treatment has imposed a need for the evaluation and assessment of other cleaning techniques. The use of more traditional methods like abrasive cleaning, steam cleaning and chemical cleaning has relied so far on visual assessment, unlike much of the research applied to laser cleaning. A conscientious use of these cleaning methods requires their assessment as well as the need for a comparison based on a common methodology. A topographical assessment of laser cleaning, abrasive cleaning, steam cleaning and chemical cleaning (using hydrofluoric acid, ammonium carbonate and EDTA) is presented. Topographical variations induced on marble, oolitic limestone and architectural terracotta surfaces are assessed by means of light interferometry, showing the potential of this non-contact and non-destructive technique for surface studies in conservation. The comparison between cleaning treatments is based upon key parameters associated with cleaning surfaces. The aesthetic impact of these treatments is verified by means of optical microscopy and quantified by colour measurement. Chemical analysis of the cleaned surface (EDS) is performed to investigate the removal of surface pollutants and the presence of residues. Finally, petrographical analysis was used to investigate the removal of pollutant layers and its effect on surface texture.