Sub-Nanometer Depth Profiling of Native Metal Oxide Layers Within Single Fixed-Angle X-Ray Photoelectron Spectra.

Many metals form nanometer-thin self-passivating oxide layers upon exposure to the atmosphere, which affects a wide range of interfacial properties and shapes the way how metals interact with their environment. Such native oxide layers are commonly analyzed by X-ray photoelectron spectroscopy (XPS), which provides a depth-resolved chemical state and compositional analysis either by ion etching or modeling of the electron escape depths. The latter is commonly used to calculate the average thickness of a native oxide layer. However, the measurement of concentration profiles at the oxide-metal interface remains challenging. Here, a simple and accessible approach for the depth profiling of ultrathin oxide layers within single fixed-angle XPS spectra is proposed. Instead of using only one peak in the spectrum, as is usually the case, all peaks within the energy range of a standard lab device are utilized, thus resembling energy-resolved XPS without the need for a synchrotron. New models that allow the calculation of depth-resolved concentration profiles at the oxide-metal interface are derived and tested, which are also valid for angular- and energy-resolved XPS. The proposed method not only improves the accuracy of earlier approaches but also paves the way for a more holistic understanding of the XPS spectrum.

Nanofibers are a matter of perspective: effects of methodology and subjectivity on diameter measurements.

Nanofibers are currently among the most researched nanomaterials in materials science. Various high-resolution microscopy techniques are used for morphological investigations, with the diameter as primary characteristic. Since methodological factors influencing the diameter distribution are usually ignored, numerical values can hardly be compared across different or even within single studies. Here, we investigate influencing factors such as microscopy technique, degree of magnification, eventual coatings, and the analysts' bias in the image selection and evaluation. We imaged a single nanofiber sample using scanning electron microscopy (SEM), helium ion microscopy (HIM), atomic force microscopy (AFM), and transmission electron microscopy (TEM). These techniques yield significant methodological variations between the diameter distributions. We further observed a strong influence of analysts' subjectivity, with a consistent average deviation between 4 different analysts of up to 31%. The average deviation between micrographs within each category was 14%, revealing a considerable influence of micrograph selection and strong potential for cherry picking. The mean values were mostly comparable with the results using automated image analysis software, which was more reproducible, much faster, and more accurate for images with lower magnification. The results demonstrate that one of the most frequently measured characteristics of nanofibers is subject to strong systematic fluctuations that are rarely if ever addressed.

Exchange Bias in Nanostructures: An Update.

Exchange bias (EB) is a unidirectional anisotropy occurring in exchange-coupled ferromagnetic/antiferromagnetic systems, such as thin films, core-shell particles, or nanostructures. In addition to a horizontal shift of the hysteresis loop, defining the exchange bias, asymmetric loops and even vertical shifts can often be found. While the effect is used in hard disk read heads and several spintronics applications, its origin is still not fully understood. Especially in nanostructures with their additional shape anisotropies, interesting and often unexpected effects can occur. Here, we provide an overview of the most recent experimental findings and theoretical models of exchange bias in nanostructures from different materials.

Hard carbon microspheres with bimodal size distribution and hierarchical porosity via hydrothermal carbonization of trehalose.

Hydrothermal carbonization (HTC) is an efficient thermochemical method for the conversion of organic feedstock to carbonaceous solids. HTC of different saccharides is known to produce microspheres (MS) with mostly Gaussian size distribution, which are utilized as functional materials in various applications, both as pristine MS and as a precursor for hard carbon MS. Although the average size of the MS can be influenced by adjusting the process parameters, there is no reliable mechanism to affect their size distribution. Our results demonstrate that HTC of trehalose, in contrast to other saccharides, results in a distinctly bimodal sphere diameter distribution consisting of small spheres with diameters of (2.1 ± 0.2) µm and of large spheres with diameters of (10.4 ± 2.6) µm. Remarkably, after pyrolytic post-carbonization at 1000 °C the MS develop a multimodal pore size distribution with abundant macropores > 100 nm, mesopores > 10 nm and micropores < 2 nm, which were examined by small-angle X-ray scattering and visualized by charge-compensated helium ion microscopy. The bimodal size distribution and hierarchical porosity provide an extraordinary set of properties and potential variables for the tailored synthesis of hierarchical porous carbons, making trehalose-derived hard carbon MS a highly promising material for applications in catalysis, filtration, and energy storage devices.

Comparative Study of Metal Substrates for Improved Carbonization of Electrospun PAN Nanofibers.

Carbon nanofibers are used for a broad range of applications, from nano-composites to energy storage devices. They are typically produced from electrospun poly(acrylonitrile) nanofibers by thermal stabilization and carbonization. The nanofiber mats are usually placed freely movable in an oven, which leads to relaxation of internal stress within the nanofibers, making them thicker and shorter. To preserve their pristine morphology they can be mechanically fixated, which may cause the nanofibers to break. In a previous study, we demonstrated that sandwiching the nanofiber mats between metal sheets retained their morphology during stabilization and incipient carbonization at 500 °C. Here, we present a comparative study of stainless steel, titanium, copper and silicon substrate sandwiches at carbonization temperatures of 500 °C, 800 °C and 1200 °C. Helium ion microscopy revealed that all metals mostly eliminated nanofiber deformation, whereas silicone achieved the best results in this regard. The highest temperatures for which the metals were shown to be applicable were 500 °C for silicon, 800 °C for stainless steel and copper, and 1200 °C for titanium. Fourier transform infrared and Raman spectroscopy revealed a higher degree of carbonization and increased crystallinity for higher temperatures, which was shown to depend on the substrate material.

Metallic Supports Accelerate Carbonization and Improve Morphological Stability of Polyacrylonitrile Nanofibers during Heat Treatment.

Electrospun poly(acrylonitrile) (PAN) nanofibers are typical precursors of carbon nanofibers. During stabilization and carbonization, however, the morphology of pristine PAN nanofibers is not retained if the as-spun nanofiber mats are treated without an external mechanical force, since internal stress tends to relax, causing the whole mats to shrink significantly, while the individual fibers thicken and curl. Stretching the nanofiber mats during thermal treatment, in contrast, can result in fractures due to inhomogeneous stress. Previous studies have shown that stabilization and carbonization of PAN nanofibers electrospun on an aluminum substrate are efficient methods to retain the fiber mat dimensions without macroscopic cracks during heat treatment. In this work, we studied different procedures of mechanical fixation via metallic substrates during thermal treatment. The influence of the metallic substrate material as well as different methods of double-sided covering of the fibers, i.e., sandwiching, were investigated. The results revealed that sandwich configurations with double-sided metallic supports not only facilitate optimal preservation of the original fiber morphology but also significantly accelerate the carbonization process. It was found that unlike regularly carbonized nanofibers, the metal supports allow complete deoxygenation at low treatment temperature and that the obtained carbon nanofibers exhibit increased crystallinity.

Identification of Microorganisms from Several Surfaces by MALDI-TOF MS: P. aeruginosa Is Leading in Biofilm Formation.

New ecological trends and changes in consumer behavior are known to favor biofilm formation in household appliances, increasing the need for new antimicrobial materials and surfaces. Their development requires laboratory-cultivated biofilms, or biofilm model systems (BMS), which allow for accelerated growth and offer better understanding of the underlying formation mechanisms. Here, we identified bacterial strains in wildtype biofilms from a variety of materials from domestic appliances using matrix-assisted laser desorption/ionization-time of flight mass spectroscopy (MALDI-TOF-MS). Staphylococci and pseudomonads were identified by MALDI-TOF-MS as the main genera in the habitats and were analyzed for biofilm formation using various in vitro methods. Standard quantitative biofilm assays were combined with scanning electron microscopy (SEM) to characterize biofilm formation. While Pseudomonas putida, a published lead germ, was not identified in any of the collected samples, Pseudomonas aeruginosa was found to be the most dominant biofilm producer. Water-born Pseudomonads were dominantly found in compartments with water contact only, such as in detergent compartment and detergent enemata. Furthermore, materials in contact with the washing load are predominantly colonized with bacteria from the human.

Effect of Isocyanate Absorption on the Mechanical Properties of Silicone Elastomers in Polyurethane Vacuum Casting.

Polyurethane vacuum casting with silicone molds is a widely used industrial process for the production of prototypes and small batches. Since the silicone casting molds absorb the isocyanate component of the curing PUR casting resin at the cavity surface, the service life of the molds is typically restricted to very few casting cycles. The successive deterioration of the material properties results from the polymerization of the absorbed isocyanate with moisture to polyurea derivatives within the silicone matrix. In this study, we show for the first time the influence of isocyanate absorption on the mechanical properties of silicone elastomers as well as quantitative differences between commercial materials. The changes in mechanical properties were quantified in terms of Shore A hardness, Young's modulus, tensile strength, elongation at break, and complex shear modulus. It was found that the influence of the isocyanate type on the relative property changes of the silicone was significantly greater than that of the silicone used. The results show that, regardless of its hardness, the silicone absorbs considerably less methylene diphenyl diisocyanate (MDI) than hydrogenated MDI, although the latter causes less deterioration of the mechanical properties and achieves a longer mold service life.

Imaging of SARS-CoV-2 infected Vero E6 cells by helium ion microscopy.

Helium ion microscopy (HIM) offers the opportunity to obtain direct views of biological samples such as cellular structures, virus particles, and microbial interactions. Imaging with the HIM combines sub-nanometer resolution, large depth of field, and high surface sensitivity. Due to its charge compensation capability, the HIM can image insulating biological samples without additional conductive coatings. Here, we present an exploratory HIM study of SARS-CoV-2 infected Vero E6 cells, in which several areas of interaction between cells and virus particles, as well as among virus particles, were imaged. The HIM pictures show the three-dimensional appearance of SARS-CoV-2 and the surface of Vero E6 cells at a multiplicity of infection of approximately 1 with great morphological detail. The absence of a conductive coating allows for a distinction between virus particles bound to the cell membrane and virus particles lying on top of the membrane. After prolonged imaging, it was found that ion-induced deposition of hydrocarbons from the vacuum renders the sample sufficiently conductive to allow for imaging even without charge compensation. The presented images demonstrate the potential of the HIM in bioimaging, especially for the imaging of interactions between viruses and their host organisms.

Fusion of purple membranes triggered by immobilization on carbon nanomembranes.

A freestanding ultrathin hybrid membrane was synthesized comprising two functional layers, that is, first, a carbon nanomembrane (CNM) produced by electron irradiation-induced cross-linking of a self-assembled monolayer (SAM) of 4'-nitro-1,1'-biphenyl-4-thiol (NBPT) and second, purple membrane (PM) containing genetically modified bacteriorhodopsin (BR) carrying a C-terminal His-tag. The NBPT-CNM was further modified to carry nitrilotriacetic acid (NTA) terminal groups for the interaction with the His-tagged PMs forming a quasi-monolayer of His-tagged PM on top of the CNM-NTA. The formation of the Ni-NTA/His-tag complex leads to the unidirectional orientation of PM on the CNM substrate. Electrophoretic sedimentation was employed to optimize the surface coverage and to close gaps between the PM patches. This procedure for the immobilization of oriented dense PM facilitates the spontaneous fusion of individual PM patches, forming larger membrane areas. This is, to our knowledge, the very first procedure described to induce the oriented fusion of PM on a solid support. The resulting hybrid membrane has a potential application as a light-driven two-dimensional proton-pumping membrane, for instance, for light-driven seawater desalination as envisioned soon after the discovery of PM.

On the reliability of highly magnified micrographs for structural analysis in materials science.

Highly magnified micrographs are part of the majority of publications in materials science and related fields. They are often the basis for discussions and far-reaching conclusions on the nature of the specimen. In many cases, reviewers demand and researchers deliver only the bare minimum of micrographs to substantiate the research hypothesis at hand. In this work, we use heterogeneous poly(acrylonitrile) nanofiber nonwovens with embedded nanoparticles to demonstrate how an insufficient or biased micrograph selection may lead to erroneous conclusions. Different micrographs taken by transmission electron microscopy and helium ion microscopy with sometimes contradictory implications were analyzed and used as a basis for micromagnetic simulations. With this, we try to raise awareness for the possible consequences of cherry-picking for the reliability of scientific literature.

Chemical and Morphological Transition of Poly(acrylonitrile)/Poly(vinylidene Fluoride) Blend Nanofibers during Oxidative Stabilization and Incipient Carbonization.

Thermally stabilized and subsequently carbonized nanofibers are a promising material for many technical applications in fields such as tissue engineering or energy storage. They can be obtained from a variety of different polymer precursors via electrospinning. While some methods have been tested for post-carbonization doping of nanofibers with the desired ingredients, very little is known about carbonization of blend nanofibers from two or more polymeric precursors. In this paper, we report on the preparation, thermal treatment and resulting properties of poly(acrylonitrile) (PAN)/poly(vinylidene fluoride) (PVDF) blend nanofibers produced by wire-based electrospinning of binary polymer solutions. Using a wide variety of spectroscopic, microscopic and thermal characterization methods, the chemical and morphological transition during oxidative stabilization (280 °C) and incipient carbonization (500 °C) was thoroughly investigated. Both PAN and PVDF precursor polymers were detected and analyzed qualitatively and quantitatively during all stages of thermal treatment. Compared to pure PAN nanofibers, the blend nanofibers showed increased fiber diameters, strong reduction of undesired morphological changes during oxidative stabilization and increased conductivity after carbonization.

Electrospinning on 3D Printed Polymers for Mechanically Stabilized Filter Composites.

Electrospinning is a frequently used method to prepare air and water filters. Electrospun nanofiber mats can have very small pores, allowing for filtering of even the smallest particles or molecules. In addition, their high surface-to-volume ratio allows for the integration of materials which may additionally treat the filtered material through photo-degradation, possess antimicrobial properties, etc., thus enhancing their applicability. However, the fine nanofiber mats are prone to mechanical damage. Possible solutions include reinforcement by embedding them in composites or gluing them onto layers that are more mechanically stable. In a previous study, we showed that it is generally possible to stabilize electrospun nanofiber mats by 3D printing rigid polymer layers onto them. Since this procedure is not technically easy and needs some experience to avoid delamination as well as damaging the nanofiber mat by the hot nozzle, here we report on the reversed technique (i.e., first 3D printing a rigid scaffold and subsequently electrospinning the nanofiber mat on top of it). We show that, although the adhesion between both materials is insufficient in the case of a common rigid printing polymer, nanofiber mats show strong adhesion to 3D printed scaffolds from thermoplastic polyurethane (TPU). This paves the way to a second approach of combining 3D printing and electrospinning in order to prepare mechanically stable filters with a nanofibrous surface.

New Polymers for Needleless Electrospinning from Low-Toxic Solvents.

Electrospinning is a new technology whose scope is gradually being developed. For this reason, the number of known polymer⁻solvent combinations for electrospinning is still very low despite the enormous variety of substances that are potentially available. In particular, electrospinning from low-toxic solvents, such as the use of dimethyl sulfoxide (DMSO) in medical technology, is rare in the relevant scientific literature. Therefore, we present in this work a series of new polymers that are applicable for electrospinning from DMSO. From a wide range of synthetic polymers tested, poly(vinyl alcohol) (PVOH), poly(2ethyl2oxazolene) (PEOZ), and poly(vinylpyrrolidone) (PVP) as water-soluble polymers and poly(styrene-co-acrylonitrile) (SAN), poly(vinyl alcohol-co-ethylene) (EVOH), and acrylonitrile butadiene styrene (ABS) as water-insoluble polymers were found to be suitable for the production of nanofibers. Furthermore, the influence of acetone as a volatile solvent additive in DMSO on the fiber morphology of these polymers was investigated. Analyses of the fiber morphology by helium ion microscopy (HIM) showed significantly different fiber diameters for different polymers and a reduction in beads and branches with increasing acetone content.

Three-Dimensional (3D) Printing of Polymer-Metal Hybrid Materials by Fused Deposition Modeling.

Fused deposition modeling (FDM) is a three-dimensional (3D) printing technology that is usually performed with polymers that are molten in a printer nozzle and placed line by line on the printing bed or the previous layer, respectively. Nowadays, hybrid materials combining polymers with functional materials are also commercially available. Especially combinations of polymers with metal particles result in printed objects with interesting optical and mechanical properties. The mechanical properties of objects printed with two of these metal-polymer blends were compared to common poly (lactide acid) (PLA) printed objects. Tensile tests and bending tests show that hybrid materials mostly containing bronze have significantly reduced mechanical properties. Tensile strengths of the 3D-printed objects were unexpectedly nearly identical with those of the original filaments, indicating sufficient quality of the printing process. Our investigations show that while FDM printing allows for producing objects with mechanical properties similar to the original materials, metal-polymer blends cannot be used for the rapid manufacturing of objects necessitating mechanical strength.