Influence of crystal structure and oxygen vacancies on optical properties of nanostructured multi-stoichiometric tungsten suboxides.

Four distinct tungsten suboxide (WO3-x) nanomaterials were synthesized via chemical vapour transport reaction and the role of their crystal structures on the optical properties was studied. These materials grow either as thin, quasi-2D crystals with the WnO3n-1formula (in shape of platelets or nanotiles), or as nanowires (W5O14, W18O49). For the quasi-2D materials, the appearance of defect states gives rise to two indirect absorption edges. One is assigned to the regular bandgap occurring between the valence and the conduction band, while the second is a defect-induced band. While the bandgap values of platelets and nanotiles are in the upper range of the reported values for the suboxides, the nanowires' bandgaps are lower due to the higher number of free charge carriers. Both types of nanowires sustain localized surface plasmon resonances, as evidenced from the extinction measurements, whereas the quasi-2D materials exhibit excitonic transitions. All four materials have photoluminescence emission peaks in the UV region. The interplay of the crystal structure, oxygen vacancies and shape can result in changes in optical behaviour, and the understanding of these effects could enable intentional tuning of selected properties.

Sterilization of polypropylene membranes of facepiece respirators by ionizing radiation.

Ionizing radiation has been identified as an option for sterilization of disposable filtering facepiece respirators in situations where the production of the respirators cannot keep up with demand. Gamma radiation and high energy electrons penetrate deeply into the material and can be used to sterilize large batches of masks within a short time period. In relation to reports that sterilization by ionizing radiation reduces filtration efficiency of polypropylene membrane filters on account of static charge loss, we have demonstrated that both gamma and electron beam irradiation can be used for sterilization, provided that the respirators are recharged afterwards.

Size- and Time-Dependent Particle Removal Efficiency of Face Masks and Improvised Respiratory Protection Equipment Used during the COVID-19 Pandemic.

Size- and time-dependent particle removal efficiency (PRE) of different protective respiratory masks were determined using a standard aerosol powder with the size of particles in the range of an uncoated SARS-CoV-2 virus and small respiratory droplets. Number concentration of particles was measured by a scanning mobility particle sizer. Respiratory protective half-masks, surgical masks, and cotton washable masks were tested. The results show high filtration efficiency of FFP2, FFP3, and certified surgical masks for all sizes of tested particles, while protection efficiency of washable masks depends on their constituent fabrics. Measurements showed decreasing PRE of all masks over time due to transmission of nanoparticles through the mask-face interface. On the other hand, the PRE of the fabric is governed by deposition of the aerosols, consequently increasing the PRE.

Silicon crystallinity control during laser direct microstructuring with bursts of picosecond pulses.

Laser ablation and modification using bursts of picosecond pulses and a tightly focused laser beam are used to manufacture structures in the bulk silicon. We demonstrate precise control of the surface crystallinity as well as the structure depth and topography of the processed areas, achieving homogeneous surface properties. The control is achieved with a combination of a well-defined pulse energy, systematic pulse positioning on the material, and the number of pulses in a burst. A custom designed fiber laser source is used to generate bursts of 1, 5, 10, and 20 pulses at a pulse repetition rate of 40 MHz and burst repetition rate of 83.3 kHz allowing for a fast and stable processing of silicon. We show a controlled transition through different laser-matter interaction regimes, from no observable changes of the silicon at low pulse energies, through amorphization below the ablation threshold energy, to the ablation with either complete, partial or nonexistent amorphization. Single micrometer-sized areas of desired shape and crystallinity were defined on the silicon surface with submicron precision, offering a promising tool for applications in the field of optics.

Modulations of the work function and morphology of a single MoS2 nanotube by charge injection.

Both the miniaturization of transistor components and the ongoing investigation of material systems with potential for quantum information processing have significantly increased current interest of researchers in semiconducting inorganic nanotubes. Here we report on an additional outstanding aspect of these nanostructures, namely the intrinsic coupling of electronic and mechanical properties. We observe electronic and morphology changes in a single MoS2 nanotube, exposed to charge injections by means of an atomic-force-microscopy tip. An elliptic deformation of the nanotube and helical twisting of the nanotube are visible, consistent with the reverse piezoelectric effect. Work-function changes are found to be dependent on the polarity of the injected carriers. An unexpected long-term persistence of the shape deformations is observed and explained with accumulation of structural defects and the resultant strain, which could cause a memory-like charge confinement and a long lasting modulation of the work function.

Enhanced Filtration Efficiency of Natural Materials with the Addition of Electrospun Poly(vinylidene fluoride-co-hexafluoropropylene) Fibres.

Pollutants and infectious diseases can spread through air with airborne droplets and aerosols. A respiratory mask can decrease the amount of pollutants we inhale and it can protect us from airborne diseases. With the onset of the COVID-19 pandemic, masks became an everyday item used by a lot of people around the world. As most of them are for a single use, the amount of non-recyclable waste increased dramatically. The plastic from which the masks are made pollutes the environment with various chemicals and microplastic. Here, we investigated the time- and size-dependent filtration efficiency (FE) of aerosols in the range of 25.9 to 685.4 nm of five different natural materials whose FE was enhanced using electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF) fibres. A scanning electron microscope (SEM) was used to determine the morphology and structure of the natural materials as well as the thickness of the PVDF fibres, while the phase of the electrospun fibres was determined by Raman spectroscopy. A thin layer of the electrospun PVDF fibres with the same grammage was sandwiched between two sheets of natural materials, and their FE increased up to 80%. By varying the grammature of the electrospun polymer, we tuned the FE of cotton from 82.6 to 99.9%. Thus, through the optimization of the grammage of the electrospun polymer, the amount of plastic used in the process can be minimized, while achieving sufficiently high FE.

Single-Layer and Double-Layer Filtration Materials Based on Polyvinylidene Fluoride-Co-hexafluoropropylene Nanofibers Coated on Melamine Microfibers.

In this work, we demonstrate selected optimization changes in the simple design of filtration masks to increase particle removal efficiency (PRE) and filter quality factor by combining experiments and numerical modeling. In particular, we focus on single-layer filters fabricated from uniform thickness fibers and double-layer filters consisting of a layer of highly permeable thick fibers as a support and a thin layer of filtering electrospun nanofibers. For single-layer filters, we demonstrate performance improvement in terms of the quality factor by optimizing the geometry of the composition. We show significantly better PRE performance for filters composed of micrometer-sized fibers covered by a thin layer of electrospun nanofibers. This work is motivated and carried out in collaboration with a targeted industrial development of selected melamine-based filter nano- and micromaterials.

Non-Destructive Low-Temperature Contacts to MoS2 Nanoribbon and Nanotube Quantum Dots.

Molybdenum disulfide nanoribbons and nanotubes are quasi-1D semiconductors with strong spin-orbit interaction, a nanomaterial highly promising for quantum electronic applications. Here, it is demonstrated that a bismuth semimetal layer between the contact metal and this nanomaterial strongly improves the properties of the contacts. Two-point resistances on the order of 100 kΩ are observed at room temperature. At cryogenic temperature, Coulomb blockade is visible. The resulting stability diagrams indicate a marked absence of trap states at the contacts and the corresponding disorder, compared to previous devices that use low-work-function metals as contacts. Single-level quantum transport is observed at temperatures below 100 mK.

The Potential of Macroporous Silica-Nanocrystalline Cellulose Combination for Formulating Dry Emulsion Systems with Improved Flow Properties: A DoE Study.

The objective of this study was to explore the possible use of a new combination of two excipients, i.e., nanocrystalline cellulose (NCC) and macroporous silica (MS), as matrix materials for the compounding of dry emulsion systems and the effects these two excipients have on the characteristics of dry emulsion powders produced by the spray drying process. A previously developed liquid O/W nanoemulsion, comprised of simvastatin, 1-oleoyl-rac-glycerol, Miglyol 812 and Tween 20, was employed. In order to comprehend the effects that these two matrix formers have on the spray drying process and on dry emulsion powder characteristics, alone and in combination, a DoE (Design of Experiment) approach was used. The physicochemical properties of dry emulsion samples were characterised by atomic force microscopy, scanning electron microscopy, mercury intrusion porosimetry, energy-dispersive X-ray spectroscopy and laser diffraction analysis. Additionally, total release and dissolution experiments were performed to assess drug release from multiple formulations. It was found that the macroporous silica matrix drastically improved flow properties of dry emulsion powders; however, it partially trapped the oil-drug mixture inside the pores and hindered complete release. NCC showed its potential to reduce oil entrapment in MS, but because of its rod-shaped particles deposited on the MS surface, powder flowability was deteriorated.

One-Step Plasma Synthesis of Nitrogen-Doped Carbon Nanomesh.

A one-step method for plasma synthesis of nitrogen-doped carbon nanomesh is presented. The method involves a molten polymer, which is a source of carbon, and inductively coupled nitrogen plasma, which is a source of highly reactive nitrogen species. The method enables the deposition of the nanocarbon layer at a rate of almost 0.1 µm/s. The deposited nanocarbon is in the form of randomly oriented multilayer graphene nanosheets or nanoflakes with a thickness of several nm and an area of the order of 1000 nm2. The concentration of chemically bonded nitrogen on the surface of the film increases with deposition time and saturates at approximately 15 at.%. Initially, the oxygen concentration is up to approximately 10 at.% but decreases with treatment time and finally saturates at approximately 2 at.%. Nitrogen is bonded in various configurations, including graphitic, pyridinic, and pyrrolic nitrogen.

Synthesis and Characterization of Tungsten Suboxide WnO3n-1 Nanotiles.

WnO3n-1 nanotiles, with multiple stoichiometries within one nanotile, were synthesized via the chemical vapour transport method. They grow along the [010] crystallographic axis, with the thickness ranging from a few tens to a few hundreds of nm, with the lateral size up to several µm. Distinct surface corrugations, up to a few 10 nm deep appear during growth. The {102}r crystallographic shear planes indicate the WnO3n-1 stoichiometries. Within a single nanotile, six stoichiometries were detected, namely W16O47 (WO2.938), W15O44 (WO2.933), W14O41 (WO2.928), W13O38 (WO2.923), W12O35 (WO2.917), and W11O32 (WO2.909), with the last three never being reported before. The existence of oxygen vacancies within the crystallographic shear planes resulted in the observed non-zero density of states at the Fermi energy.

Revealing Inflammatory Indications Induced by Titanium Alloy Wear Debris in Periprosthetic Tissue by Label-Free Correlative High-Resolution Ion, Electron and Optical Microspectroscopy.

The metallic-associated adverse local tissue reactions (ALTR) and events accompanying worn-broken implant materials are still poorly understood on the subcellular and molecular level. Current immunohistochemical techniques lack spatial resolution and chemical sensitivity to investigate causal relations between material and biological response on submicron and even nanoscale. In our study, new insights of titanium alloy debris-tissue interaction were revealed by the implementation of label-free high-resolution correlative microscopy approaches. We have successfully characterized its chemical and biological impact on the periprosthetic tissue obtained at revision surgery of a fractured titanium-alloy modular neck of a patient with hip osteoarthritis. We applied a combination of photon, electron and ion beam micro-spectroscopy techniques, including hybrid optical fluorescence and reflectance micro-spectroscopy, scanning electron microscopy (SEM), Energy-dispersive X-ray Spectroscopy (EDS), helium ion microscopy (HIM) and micro-particle-induced X-ray emission (micro-PIXE). Micron-sized wear debris were found as the main cause of the tissue oxidative stress exhibited through lipopigments accumulation in the nearby lysosome. This may explain the indications of chronic inflammation from prior histologic examination. Furthermore, insights on extensive fretting and corrosion of the debris on nm scale and a quantitative measure of significant Al and V release into the tissue together with hydroxyapatite-like layer formation particularly bound to the regions with the highest Al content were revealed. The functional and structural information obtained at molecular and subcellular level contributes to a better understanding of the macroscopic inflammatory processes observed in the tissue level. The established label-free correlative microscopy approach can efficiently be adopted to study any other clinical cases related to ALTR.

Multi-stoichiometric quasi-two-dimensional WnO3n-1 tungsten oxides.

Quasi-two-dimensional tungsten oxide structures, which nucleate by epitaxial growth on W19O55 nanowires (NW) and grow as thin platelets, were identified. Both the nanowires and the platelets accommodate oxygen deficiency by the formation of crystallographic shear planes. Stoichiometric phases, W18O53 (WO2.944), W17O50 (WO2.941), W16O47 (WO2.938), W15O44 (WO2.933), W14O41 (WO2.929), W10O29 (WO2.9), and W9O26 (WO2.889), syntactically grow inside a single platelet. These layered crystals show a new kind of polycrystallinity, where crystallographic shear planes accommodate oxygen deficiency and at the same time stabilize this multi-stoichiometric structure.

Quantitative measurement of charge accumulation along a quasi-one-dimensional W5O14 nanowire during electron field emission.

We use an electron holographic method to determine the charge distribution along a quasi-one-dimensional W5O14 nanowire during in situ field emission in a transmission electron microscope. The results show that the continuous charge distribution along the nanowire is not linear, but that there is an additional accumulation of charge at its apex. An analytical expression for this additional contribution to the charge distribution is proposed and its effect on the field enhancement factor and emission current is discussed.

A redispersible dry emulsion system with simvastatin prepared via fluid bed layering as a means of dissolution enhancement of a lipophilic drug.

The purpose of the study was to develop a redispersible dry emulsion, containing a lipophilic, poorly water soluble model drug simvastatin, by employing fluid bed coating technology. The presented dry emulsion manufacturing approach produces pellets in a way, where a layer of the dry emulsion is applied to a neutral core. In the preliminary formulation development phase 1-oleoyl-rac-glycerol was chosen as the oily lipid phase, based on the high drug solubility and potential bioavailability enhancement capability. Mannitol, HPMC and Tween 20 were selected as the solid carriers and surfactant, respectively. The design of experiments, specifically the mixture design approach, was used to obtain the optimal formulation composition. The emulsion reconstitution ability and stability were the main responses, used as the decisive parameters for formulation optimisation. Optimised formulations showed narrow droplet size distribution upon reconstitution, high stability, suitable drug loading and enhanced dissolution profile, compared to a non-lipid based tablet and the pure drug. The scanning electron microscopy, Raman spectroscopy and image analysis disclosed a uniform morphology of the applied layer with separated droplets with simvastatin and uniform size distribution and a circular shape of coated pellets. The study represents the proof of concept of designing redispersible dry emulsions using a fluid bed layering approach.

In situ tribochemical sulfurization of molybdenum oxide nanotubes.

MoS2 nanoparticles are typically obtained by high temperature sulfurization of organic and inorganic precursors under a S rich atmosphere and have excellent friction reduction properties. We present a novel approach for making the sulfurization unnecessary for MoO3 nanotubes during the synthesis process for friction and wear reduction applications while simultaneously achieving a superb tribological performance. To this end, we report the first in situ sulfurization of MoO3 nanotubes during sliding contact in the presence of sulfur-containing lubricant additives. The sulfurization leads to the tribo-chemical formation of a MoS2-rich low-friction tribofilm as verified using Raman spectroscopy and can be achieved both during sliding contact and under extreme pressure conditions. Under sliding contact conditions, MoO3 nanotubes in synergy with sulfurized olefin polysulfide and pre-formed zinc dialkyl dithiophosphate tribofilms achieve an excellent friction performance. Under these conditions, the tribochemical sulfurization of MoO3 nanotubes leads to a similar coefficient of friction to the one obtained using a model nanolubricant containing MoS2 nanotubes. Under extreme pressure conditions, the in situ sulfurization of MoO3 nanotubes using sulfurized olefin polysulfide results in a superb load carrying capacity capable of outperforming MoS2 nanotubes. The reason is that while MoO3 nanotubes are able to continuously sulfurize during sliding contact conditions, MoS2 nanotubes progressively degrade by oxidation thus losing lubricity.