Plasma-deposited Ge nanoisland films on Si : is Stranski–Krastanow fragmentation unavoidable?

The formation of Ge quantum dot arrays by deposition from a low-temperature plasma environment is investigated by kinetic Monte Carlo numerical simulation. It is demonstrated that balancing of the Ge influx from the plasma against surface diffusion provides an effective control of the surface processes and can result in the formation of very small densely packed quantum dots. In the supply-controlled mode, a continuous layer is formed which is then followed by the usual Stranski-Krastanow fragmentation with a nanocluster size of 10 nm. In the diffusion-controlled mode, with the oversupply relative to the surface diffusion rate, nanoclusters with a characteristic size of 3 nm are formed. Higher temperatures change the mode to supply controlled and thus encourage formation of the continuous layer that then fragments into an array of large size. The use of a high rate of deposition, easily accessible using plasma techniques, changes the mode to diffusion controlled and thus encourages formation of a dense array of small nanoislands.

Effect of a floating electrode on a plasma jet

Two kinds of floating electrode, floating dielectric barrier covered electrode (FDBCE) and floating pin electrode (FPE), which can enhance the performance of plasma jet are reported. The intense discharge between the floating electrode and power electrode decreased the voltage to trigger the plasma jet substantially. The transition of plasma bullet from ring shape to disk shape in the high helium concentration region happened when the floating electrode was totally inside the powered ring electrode. The enhanced electric field between propagating plasma bullet and ground electrode is the reason for this transition. The double plasma bullets happened when part of the FDBCE was outside the powered ring electrode, which is attributed to the structure and surface charge of FDBCE. As part of the FPE was outside the powered ring electrode, the return stroke resulted in a single intensified plasma channel between FPE and ground electrode.

Study of surface evolution in the wheel-rail interface

This paper aims to trace surface evolution in the wheel-rail interface using data obtained from a twin-disc testing machine and the surface replication technique. Changes in the surface profile of the rail testing disc are explicitly analysed according to the wear mechanism, which helps elaborate a better understanding of the attrition of asperities during the wearing-in process of surface modification. The surface profile amplitude was seen to decrease during the initial running-in phase of the experiment cycle, and after reaching a saturation value, the profile amplitude then increased. Ultimately the results show that grinding will roughen the rail surface and the wheel-rail contact conditions will then remove this surface damage to some saturation value of the profile height. The variation in the rail surface profile beyond this point is then only dependant on the contact conditions which exist between the wheel and rail during normal operation.

Nanofiber orientation and surface functionalization modulate human mesenchymal stem cell behavior in vitro

Electrospun nanofiber meshes have emerged as a new generation of scaffold membranes possessing a number of features suitable for tissue regeneration. One of these features is the flexibility to modify their structure and composition to orchestrate specific cellular responses. In this study, we investigated the effects of nanofiber orientation and surface functionalization on human mesenchymal stem cell (hMSC) migration and osteogenic differentiation. We used an in vitro model to examine hMSC migration into a cell-free zone on nanofiber meshes and mitomycin C treatment to assess the contribution of proliferation to the observed migration. Poly (ɛ-caprolactone) meshes with oriented topography were created by electrospinning aligned nanofibers on a rotating mandrel, while randomly oriented controls were collected on a stationary collector. Both aligned and random meshes were coated with a triple-helical, type I collagen-mimetic peptide, containing the glycine-phenylalanine-hydroxyproline-glycine-glutamate-arginine (GFOGER) motif. Our results indicate that nanofiber GFOGER peptide functionalization and orientation modulate cellular behavior, individually, and in combination. GFOGER significantly enhanced the migration, proliferation, and osteogenic differentiation of hMSCs on nanofiber meshes. Aligned nanofiber meshes displayed increased cell migration along the direction of fiber orientation compared to random meshes; however, fiber alignment did not influence osteogenic differentiation. Compared to each other, GFOGER coating resulted in a higher proliferation-driven cell migration, whereas fiber orientation appeared to generate a larger direct migratory effect. This study demonstrates that peptide surface modification and topographical cues associated with fiber alignment can be used to direct cellular behavior on nanofiber mesh scaffolds, which may be exploited for tissue regeneration.

Visible light enhanced oxidant free dehydrogenation of aromatic alcohols using Au-Pd alloy nanoparticle catalysts

We find that visible light irradiation of gold–palladium alloy nanoparticles supported on photocatalytically inert ZrO2 significantly enhances their catalytic activity for oxidant-free dehydrogenation of aromatic alcohols to the corresponding aldehydes at ambient temperatures. Dehydrogenation is also the dominant process in the selective oxidation of the alcohols to the corresponding aldehydes with molecular oxygen. The alloy nanoparticles strongly absorb light and exhibit superior catalytic and photocatalytic activity when compared to either pure palladium or gold nanoparticles. Analysis with a free electron gas model for the bulk alloy structure reveals that the alloying increases the surface charge heterogeneity on the alloy particle surface, which enhances the interaction between the alcohol molecules and the metal NPs. The increased surface charge heterogeneity of the alloy particles is confirmed with density function theory applied to small alloy clusters. Optimal catalytic activity was observed with a Au : Pd molar ratio of 1 : 186, which is in good agreement with the theoretical analysis. The rate-determining step of the dehydrogenation is hydrogen abstraction. The conduction electrons of the nanoparticles are photo-excited by the incident light giving them the necessary energy to be injected into the adsorbed alcohol molecules, promoting the hydrogen abstraction. The strong chemical adsorption of alcohol molecules facilitates this electron transfer. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive the dehydrogenation. These findings provide useful insight into the design of catalysts that utilize light for various organic syntheses at ambient temperatures.

New encapsulating materials for implantable devices

Synthetic, natural, or composite, biomaterials occupy a key position in the management of disease and support continuous advancement of health care. Clinical utility of many permanent and biodegradable implants can be significantly improved via surface modification. Here, we discuss a novel polymer material developed from essential oil-based monoterpene alcohol using plasma polymerisation. The developed coatings are cytocompatible and limit adhesion and proliferation of a variety of pathogens. The coating can also be used to control degradation behaviour of resorbable materials, such as magnesium.

Fabrication and characterization of polyterpenol as an insulating layer and incorporated organic field effect transistor

A non-synthetic polymer material, polyterpenol, was fabricated using a dry polymerization process namely RF plasma polymerization from an environmentally friendly monomer and its surface, optical and electrical properties investigated. Polyterpenol films were found to be transparent over the visible wavelength range, with a smooth surface with an average roughness of less than 0.4 nm and hardness of 0.4 GPa. The dielectric constant of 3.4 for polyterpenol was higher than that of the conventional polymer materials used in the organic electronic devices. The non-synthetic polymer material was then implemented as a surface modification of the gate insulator in field effect transistor (OFET) and the properties of the device were examined. In comparison to the similar device without the polymer insulating layer, the polyterpenol based OFET device showed significant improvements. The addition of the polyterpenol interlayer in the OFET shifted the threshold voltage significantly; + 20 V to -3 V. The presence of trapped charge was not observed in the polyterpenol interlayer. This assisted in the improvement of effective mobility from 0.012 to 0.021 cm 2/Vs. The switching property of the polyterpenol based OFET was also improved; 107 compared to 104. The results showed that the non-synthetic polyterpenol polymer film is a promising candidate of insulators in electronic devices.

Infrared spectroscopic investigation of the effects of titania photocatalyst on the degradation of linear low density polyethylene film for commercial applications

There is a need in industry for a commodity polyethylene film with controllable degradation properties that will degrade in an environmentally neutral way, for applications such as shopping bags and packaging film. Additives such as starch have been shown to accelerate the degradation of plastic films, however control of degradation is required so that the film will retain its mechanical properties during storage and use, and then degrade when no longer required. By the addition of a photocatalyst it is hoped that polymer film will breakdown with exposure to sunlight. Furthermore, it is desired that the polymer film will degrade in the dark, after a short initial exposure to sunlight. Research has been undertaken into the photo- and thermo-oxidative degradation processes of 25 ìm thick LLDPE (linear low density polyethylene) film containing titania from different manufacturers. Films were aged in a suntest or in an oven at 50 °C, and the oxidation product formation was followed using IR spectroscopy. Degussa P25, Kronos 1002, and various organic-modified and doped titanias of the types Satchleben Hombitan and Hunstsman Tioxide incorporated into LLDPE films were assessed for photoactivity. Degussa P25 was found to be the most photoactive with UVA and UVC exposure. Surface modification of titania was found to reduce photoactivity. Crystal phase is thought to be among the most important factors when assessing the photoactivity of titania as a photocatalyst for degradation. Pre-irradiation with UVA or UVC for 24 hours of the film containing 3% Degussa P25 titania prior to aging in an oven resulted in embrittlement in ca. 200 days. The multivariate data analysis technique PCA (principal component analysis) was used as an exploratory tool to investigate the IR spectral data. Oxidation products formed in similar relative concentrations across all samples, confirming that titania was catalysing the oxidation of the LLDPE film without changing the oxidation pathway. PCA was also employed to compare rates of degradation in different films. PCA enabled the discovery of water vapour trapped inside cavities formed by oxidation by titania particles. Imaging ATR/FTIR spectroscopy with high lateral resolution was used in a novel experiment to examine the heterogeneous nature of oxidation of a model polymer compound caused by the presence of titania particles. A model polymer containing Degussa P25 titania was solvent cast onto the internal reflection element of the imaging ATR/FTIR and the oxidation under UVC was examined over time. Sensitisation of 5 ìm domains by titania resulted in areas of relatively high oxidation product concentration. The suitability of transmission IR with a synchrotron light source to the study of polymer film oxidation was assessed as the Australian Synchrotron in Melbourne, Australia. Challenges such as interference fringes and poor signal-to-noise ratio need to be addressed before this can become a routine technique.

Reinforced hydrogels for silicone copolymer delivery for scar remediation

Hypertrophic scars are formed by collagen overproduction in wounded areas and often occur in victims of severe burns. There are several methods for hypertrophic scar remediation and silicone gel therapy is one of the more successful methods. Research by others has shown that the activity of these gels may be due to migration of amphiphilic silicone oligomers from the gel and into the dermis, down-regulating production of collagen by fibroblasts. Normal silicone oil (PDMS) does not produce the same effect on fibroblasts. The main purpose of this project is the introduction of a particular amphiphilic silicone rake copolymer into an appropriate network which can absorb and release the silicone copolymer on the scarred area. Hydrogels are polymeric crosslinked networks which can swell in water or a drug solution, and gradually release the drug when applied to the skin. The application of gel enhances the effectiveness of the therapy, reduces the period of treatment and can be comfortable for patients to use. Polyethylene glycol (PEG) based networks have been applied in this research, because the amphiphilic silicone rake copolymer to be used as a therapy has polyethylene oxide (PEO) as a side chain. These PEO side chains have very similar chemical structure to a PEG gel chain so enhancing both the compatibility and the diffusion of the amphiphilic silicone rake copolymer into and out of the gel. Synthesis of PEG-based networks has been performed by two methods: in situ silsesquioxane formation as crosslink with a sol-gel reaction under different conditions and UV curing. PEG networks have low mechanical properties which is a fundamental limitation of the polymer backbone. For mechanical properties enhancement, composite networks were synthesized using nano-silica with different surface modification. The chemical structure of in situ silsesquioxane in the dry network has been examined by Solid State NMR, Differential Scanning Calorimetry (DSC) and swelling measurements in water. Mechanical properties of dry networks were tested by Dynamic Mechanical Thermal Analysis (DMTA) to determine modulus and interfacial interaction between silica and the network. In this way a family of self-reinforced networks has been produced that have been shown to absorb and deliver the active amphiphilic silicone- PEO rake copolymer.

Glycosaminoglycan and growth factor mediated murine calvarial cell proliferation

Understanding the complex mechanisms underlying bone remodeling is crucial to the development of novel therapeutics. Glycosaminoglycans (GAGs) localised to the extracellular matrix (ECM) of bone are thought to play a key role in mediating aspects of bone development. The influence of isolated GAGs was studied by utilising in vitro murine calvarial monolayer and organ culture model systems. Addition of GAG preparations extracted from the cell surface of human osteoblasts at high concentrations (5 microg/ml) resulted in decreased proliferation of cells and decreased suture width and number of bone lining cells in calvarial sections. When we investigated potential interactions between the growth factors fibroblast growth factor-2 (FGF2), bone morphogenic protein-2 (BMP2) and transforming growth factor-beta1 (TGFbeta1) and the isolated cell surface GAGs, differences between the two model systems emerged. The cell culture system demonstrated a potentiating role for the isolated GAGs in the inhibition of FGF2 and TGFbeta1 actions. In contrast, the organ culture system demonstrated an enhanced stimulation of TFGbeta1 effects. These results emphasise the role of the ECM in mediating the interactions between GAGs and growth factors during bone development and suggest the GAG preparations contain potent inhibitory or stimulatory components able to mediate growth factor activity.

Microscale study of electrical characteristics of epoxy-multiwall carbon nanotube nanocomposites

Epoxy-multiwall carbon nanotube nanocomposite thin films were prepared by spin casting. High power air plasma was used to preferentially etch a coating of epoxy and expose the underlying carbon nanotube network. Scanning electron microscopy (SEM) examination revealed well distributed and spatially connected carbon nanotube network in both the longitudinal direction (plasma etched surface) and traverse direction (through-thickness fractured surface). Topographical examination and conductive mode imaging of the plasma etched surface using atomic force microscope (AFM) in the contact mode enabled direct imaging of topography and current maps of the embedded carbon nanotube network. Bundles consisting of at least three single carbon nanotubes form part of the percolating network observed under high resolution current maps. Predominantly non-ohmic response is obtained in this study; behaviour attributed to less than effective polymer material removal when using air plasma etching.

Dynamic covalent chemistry on surfaces employing highly reactive cyclopentadienyl moieties

Silicon substrates coated with a bromide-terminated silane are transformed into highly reactive, cyclopentadiene covered analogues. These surfaces undergo rapid cycloaddition reactions with various dienophile-capped polymers. Mild heating of the substrates causes the retro-Diels-Alder reaction to occur, thus reforming the reactive cyclopentadiene surface, generating an efficiently switchable surface.