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A novel process for the formation of pairs of opposing metallic nanotips within linear trenches on a silicon wafer is investigated in detail. The process is based on a spreading knife technique typically used in nanosphere lithography to generate monolayers of colloidal polystyrene beads. Here it is applied to initiate self-assembly of spheres in long linear trenches acting as a template for the sphere arrangement. The optimum blade velocity to deposit the spheres selectively and densely packed in the trench depends on the trench surface fraction and can be described by a modified Dimitrov model. It is demonstrated that the spheres can be used as a shadow mask to deposit metallic nanotips in a channel, which are electrically interconnected on each side of the trench, possibly enabling the control and manipulation of nanoobjects in the channel.
The condensation of hydrazides with aldehydes has been found to be a simple and rapid method for synthesizing catechol-terminated coating reagents for magnetite nanoparticles. This approach allowed the production of biotin- and polyethylene glycol-functionalized nanoparticles, whose interaction with 3T3 fibroblast cells has been assessed. The cellular location of these nanoparticles was imaged by fluorescence microscopy, which was made possible by co-coating with a porphyrin-catechol conjugate. Images show significant interactions between biotinylated nanoparticles and 3T3 fibroblasts, but those with a polyethylene glycol coating did not interact.
A MEMS floating element shear stress sensor has been developed for flow testing applications, targeted primarily in ground and flight testing of aerospace vehicle and components. However, concerns remain about the interaction of the flow with the mechanical elements of the structure at the micro-scale. In particular, there are concerns about the validity of laminar flow cell calibration to measurement in turbulent flows, and the extent to which pressure gradients may introduce errors into the shear stress measurement. In order to address these concerns, a numerical model of the sensor has been constructed.
In this paper, a computational fluid dynamics (CFD) model is described. The CFD model directly models a laminar flow cell experiment that is used to calibrate the shear sensor. The computational model allows us to quantify the contributions (e.g. pressure gradient vs. shear, top surface vs. lateral surfaces) to the sensor output in a manner that is difficult by purely experimental means. The results are compared to experimental data, validating the model and resulting in the following: Surface shear stress contributes approximately 40% of the total flow direction force; pressure gradient effects contribute nearly 45% for the textured shuttle described here; lift forces and pitching moments are non-zero. Thus, it is found that flow interactions are complex and that it is insufficient to simply assume that flow forces on the sensor are the top area multiplied by wall shear, as is sometimes done. Pressure gradient effects, at least, must be included for accurate calibration.
Regenerative engineering was conceptualized by bridging the lessons learned in developmental biology and stem cell science with biomaterial constructs and engineering principles to ultimately generate de novo tissue. We seek to incorporate our understanding of natural tissue development to design tissue-inducing biomaterials, structures and composites than can stimulate the regeneration of complex tissues, organs, and organ systems through location-specific topographies and physico-chemical cues incorporated into a continuous phase. This combination of classical top-down tissue engineering approach with bottom-up strategies used in regenerative biology represents a new multidisciplinary paradigm. Advanced surface topographies and material scales are used to control cell fate and the consequent regenerative capacity.
Musculoskeletal tissues are critical to the normal functioning of an individual and following damage or degeneration they show extremely limited endogenous regenerative capacity. The increasing demand for biologically compatible donor tissue and organ transplants far outstrips the availability leading to an acute shortage. We have developed several biomimetic structures using various biomaterial platforms to combine optimal mechanical properties, porosity, bioactivity, and functionality to effect repair and regeneration of hard tissues such as bone, and soft tissues such as ligament and tendon. Starting with simple structures, we have developed composite and multi-scale systems that very closely mimic the native tissue architecture and material composition. Ultimately, we aim to modulate the regenerative potential, including proliferation, phenotype maturation, matrix production, and apoptosis through cell-scaffold and host –scaffold interactions developing complex tissues and organ systems.
We discuss methods to describe the evolution of dislocation systems in terms of a limited number of continuous field variables while correctly representing the kinematics of systems of flexible and connected lines. We show that a satisfactory continuum representation may be obtained in terms of only four variables. We discuss the consequences of different approximations needed to formulate a closed set of equations for these variables and propose a benchmark problem to assess the performance of the resulting models. We demonstrate that best results are obtained by using the maximum entropy formalism to arrive at an optimal estimate for the dislocation orientation distribution based on its lowest-order angular moments.
A new peptide amphiphile (PA) called C16-W3K has hierarchical structures, presenting unique solution states, micelle structures, and secondary structures. In this work, the effects of salt (sodium dihydrogenorthophosphate) concentration on the hierarchical structural transitions of the C16-W3K solution due to its active hydrogen bonding in the peptide were discussed. In order to analyze the effects of salt on the structural transitions, the mechanical and structural analyses were conducted by viscosity measurements, transmission electron microscopy (TEM), and circular dichroic (CD) spectroscopy. It was found that the C16-W3K solutions with different salt concentrations presented different multi-scale structural transitions from spherical micelles with α-helix molecular conformations in the sol state to wormlike micelles with β-sheet conformations in the gel state. Additionally, we found that the speed of transition increased as the salt concentration increased and the conformational ratio of β-sheet to α-helix in the solutions increased with the increase in the salt concentration.
We report a study on the wetting and spreading of hydrazine-CZTS solution on a series of solid surfaces. The work of adhesion between a hydrazine solution and soda-lime glass, Si, graphite, ITO, SnO2, ZnO, CdS, In2S3, Cu, Au, Ag, Al, Ni, Mo, and carbon single-walled nanotubes was calculated using observed contact angles and the areas of the interface. The surface roughness of drop-casted CZTS precursor films was lower on surfaces with better hydrazine wettability. This suggests that the surface roughness of solution-processed films can be controlled by altering the wetting behavior of the solution on the substrate.
The synthesis of hexadecylamine capped (HDA) CdTe and PbTe via a simple hybrid solution based high temperature route is described. In this method the tellurium is first reduced to form the telluride salt followed by reaction with the metal salt and finally thermolysis in a coordinating solvent. The metal salt and reaction temperature played an important role in the morphology and growth mechanism of the particles. The CdTe particles where in the form of rods and spheres whereas the PbTe nanoparticles were in the form of nanowires. The oriented attachment mechanism is proposed for the growth of elongated particles under certain reaction conditions.
Core-shell quantum dots (QDs) with enhanced photostability compared with bare QDs are promising light absorbers for solar cell applications. In this work, electron injection from excited CdSe/ZnS QDs to Zinc Oxide (ZnO) nanowires (NWs) prepared by two techniques were demonstrated. Arrays of ZnO NWs were fabricated by hydrothermal growth and etching. ZnO NWs were sensitized with hydrophobically ligated colloidal CdSe/ZnS QDs. The electron transfer dynamic in QD/ZnO NW architecture was examined using photoluminescence (PL) and decay lifetime analyses. The quenching of the QD emission peak and lowered average lifetime in QD/ZnO NW architecture confirms the deactivation of the excited QDs via electron transfer to ZnO NWs. Electron transfer was enhanced by using smaller QDs. This study provides insight on charge transfer dynamics at the QD/ZnO NW interface in order to engineer high performance quantum dot sensitized solar cells (QDSSCs).
In this work high-temperature X-ray diffraction has been used to investigate thermal and chemical expansion as well as overall phase stability for various cathode materials: Ba0.5Sr0.5Co0.8Fe0.2O3 (BSCF), La0.3Sr0.7CoO3 (LSC37), La0.6Sr0.4CoO3 (LSC64) and La0.6Sr0.4Fe0.8Co0.2O3 (LSCF), as a function of temperature in reducing conditions. When perovskites materials are under a low oxygen partial-pressure condition, the lattice parameter and overall dimension increase. Their chemical expansion has comparable values. From the viewpoint of the stability of these phases, the high-temperature X-ray diffraction results indicate no phase decomposition can be one of the reasons for material failure at the current experimental oxygen partial pressure. LSF is most stable, while LSC and LSCF form oxygen vacancy-ordered phases and then decompose when heated to 1000°C under atmospheres with pO2 as low as 10-5 atm.
Zirconolite (CaZrTi2O7), a durable and compositionally flexible titanate ceramic for the immobilization of separated actinides, is currently the UK’s preferred candidate phase for the immobilization of plutonium dioxide arising from aqueous reprocessing. Here, its suitability as a waste-form for actinide chlorides arising from pyrochemical reprocessing is investigated through synthesis via a molten salt mediated reaction using a number of different salt eutectics (MgCl2:NaCl, CaCl2:NaCl and KCl:NaCl). It is found that the effectiveness of the molten salt synthesis of zirconolite is governed by the solubility of ZrO2 in the salt medium used; the synthesis proceeding via the formation of a perovskite (CaTiO3) intermediate which then reacts with ZrO2 to form zirconolite via a solution-diffusion mechanism. Most notably, in the KCl:NaCl eutectic different zirconolite polytypes are formed at different synthesis temperatures, with zirconolite-3T forming at 900 °C, giving way to zirconolite-2M at 1200 °C.
A RF magnetron sputtering method was used to prepare Mg2Si films at 300-400oC on (001) Al2O3 substrates from a Mg disc target with Si chips. Mg deposition was not detected at 400°C from a pure Mg disc target without Si chips due to the high vapor pressure of Mg. However, the amount of Mg deposition increased with the increase in Si/(Mg+Si) area ratio of the target surface together with the increase of the Si deposition. The obtained films had a stoichiometric composition of Si/(Mg+Si)=0.33 that consisted of the well crystalline Mg2Si single phase regardless of Si/(Mg+Si) area ratio of the target surface. This showed the existence of a “process window” against supply ratio of Si/(Mg+Si) for Mg2Si single phase films with a stoichiometric composition. This is considered to be due to the vaporization of the excess Mg prepared under the Mg excess condition as reported by Mahan et al. for Mg2Si films prepared at 200°C by ultra-high vacuum evaporation.
This paper describes light trapping in superstrate-type amorphous Si solar cells incorporated with Ag nanostructures (nanodisks) fabricated by a transfer-printing approach. The changes in external quantum efficiency (EQE) and current-voltage characteristics were investigated by changing the position and size (thickness) of the Ag nanodisks in the cells fabricated on flat superstrates. It was confirmed that the optimized Ag nanodisk-configuration led to the enhanced EQE (20%) in the 600-800 nm wavelength range, and the enhanced EQE led to the improved overall conversion efficiency (7.5%) compared to the cell without Ag nanodisks (7.2%). However, the integration of the optimized Ag nanodisk-configuration with the cells fabricated on textured superstrates did not result in the enhanced EQE and conversion efficiency, suggesting further optical designs are necessary to exploit both texture- and plasmon-mediated light trapping effects.
Elongated micro- and nanostructures of Sn doped or Sn and Cr co-doped monoclinic gallium oxide have been grown by a thermal method. The presence of Sn during growth has been shown to strongly influence the morphology of the resulting structures, including Sn doped branched wires, whips, and needles. Subsequent co-doping with Cr is achieved through thermal diffusion for photonic purposes. The formation mechanism of the branched structures has been studied by transmission electron microscopy (TEM). Epitaxial growth has been demonstrated in some cases, revealed by a very high quality interface between the central rod and the branches of the structures, while in other cases, formation of extended defects such as twins has been observed in the interface region. Cathodoluminescence (CL) measurements show a Sn-related complex band in the Sn-doped structures. In the Sn−Cr co-doped samples, the characteristic, very intense Cr3+ red luminescence emission quenches the bands observed in the Sn doped samples. Branched, Sn−Cr co-doped structures were studied with microphotoluminescence imaging and spectroscopy, and waveguiding behavior was observed along the trunks and branches of these structures.
Cu2ZnSnSe4 thin films were prepared by using the synthesized Cu2ZnSnSe4 ingot and Na2Se powder at various Na2Se/Cu2ZnSnSe4 mole ratio as evaporation materials for selenization process. From EPMA analysis, the composition was approximately constant even if the Na2Se/Cu2ZnSnSe4 mole ratio increased. X-ray diffraction studies revealed that the thin films had a kesterite Cu2ZnSnSe4 structure and the foreign phases disappeared with increasing the Na2Se/Cu2ZnSnSe4 mole ratio. The Na2Se addition enhanced to grow thin films having a close-packed structure and columnar grains. The values of Voc and Isc in Cu2ZnSnSe4 thin film solar cells increased with increasing the Na2Se/Cu2ZnSnSe4 mole ratio.
Two methods for the fabrication of flexible and stretchable photonic crystal slabs are demonstrated and compared. In both cases a periodically nanostructured polydimethylsiloxane (PDMS) membrane is used as substrate. The first method is based on oblique-angle vapor deposition of SiO as a high refractive index material onto the nanostructured membrane. The deposition is made at an angle of 45° to the surface. The grooves of the nanostructure are aligned such that shading effects cause an inhomogeneous layer thickness distribution on the surface. This supports controlled, periodic cracking of the high index layer upon stretching. In the second approach ZnO nanoparticles are spin-coated on the nanostructured PDMS membrane. Here, the membrane can be stretched and serves as a photonic crystal slab without the need of any further treatment. For both types of flexible photonic crystal slabs a shift of the guided mode resonances to longer wavelengths is observed upon stretching. For a 20% strain perpendicular to the grating grooves a resonance shift of more than 50 nm is obtained.
Here, we propose novel mesoporous Au-loaded TiO2 nanoparticle assemblies (Au-MTA) as highly effective catalysts for the reduction of nitroaromatic compounds into the corresponding aryl amine products. The obtained materials possess a continuous network of interconnected gold and anatase TiO2 (ca. 9 nm in size) nanoparticles with controllable gold particle size (i.e. ranging from ∼3.2 to ∼9.4 nm) and exhibit large and accessible pore surface area (ca. 100–160 m2/g), as evidenced by SAXS, XRD, TEM and N2 physisorption measurements. Interestingly, the Au-MTA mesophases have exhibited remarkable activity and selectivity for the reduction of nitro into amine groups using NaBH4 as reducing agent. Indeed, the Au loading and particle size have a key effect on hydrogenation reactions, affecting significantly the yield and product composition.
Most recently, magnetic ceramic nanoparticles have attracted considerable scientific interest from the basic research point of view and for their prospective use in chemical sensing, catalysis and electrochemical applications. In this paper we report the successful synthesis of xSnO2-(1-x)α-Fe2O3 system by hydrothermal synthesis and that of xZrO2-(1-x)α-Fe2O3 system by mechanochemical activation. The two nanoparticle systems were analyzed side-by-side using X-ray diffraction (XRD) and Mössbauer spectroscopy. The latter technique was used in its complexity, including the determination of the recoilless fraction using our dual absorber method. This was correlated with the onset of new phases in the systems of interest.