Silicon Oxycarbide Coatings Consisting of Defined Bottom-Up-Grown Nanostructures.

Silicon oxycarbide (SiOC) materials have arisen in the past few decades as a promising new class of glasses and glass-ceramics thanks to their advantageous chemical and thermal properties. Many applications, such as ion storage, sensing, filtering, or catalysis, require materials or coatings with high surface area and might benefit from the high thermal stability of SiOC. This work reports the first facile bottom-up approach to textured high surface area SiOC coatings obtained via direct pyrolysis of polysiloxane structures of well-defined shapes, such as nanofilaments or microrods. This work further investigates the thermal behavior of these structures by means of FT-IR, SEM, and EDX up to 1400 °C. The rods shrink in volume by ≈30% while their aspect ratio remains unaffected by pyrolysis until at least 1100 °C. The nano-sized filaments show signs of viscous flow already at a comparably low temperature of 900 °C which is very probably due to the nano-size effect. This might open a way to experimentally study the size-effect on the glass transition temperature of oxide glasses, an experimentally unexplored but very relevant topic. These structures have great potential, for example, as ion storage materials and supports in high temperature catalysis and CO2 conversion.

Droplet Memory on Liquid-Infused Surfaces.

The knowledge of droplet friction on liquid-infused surfaces (LIS) is of paramount importance for applications involving liquid manipulation. While the possible dissipation mechanisms are well-understood, the effect of surface texture has thus far been mainly investigated on LIS with highly regular solid topographies. In this work, we aim to address this experimental gap by studying the friction experienced by water droplets on LIS based on both random and regular polysilsesquioxane nanostructures. We show that the available models apply to the tested surfaces, but we observe a previously unreported droplet memory effect: as consecutive droplets travel along the same path, their velocity increases up to a plateau value before returning to the original state after a sufficiently long time. We study the features of this phenomenon by evaluating the motion of droplets when they cross the path of a previous sequence of droplets, discovering that moving droplets create a low-friction trace in their wake, whose size matches their base diameter. Finally, we attribute this to the temporary smoothing out of an initially conformal lubricant layer by means of a Landau-Levich-Derjaguin liquid film deposition behind the moving droplet. The proposed mechanism might apply to any LIS with a conformal lubricant layer.

Droplet Size-Assisted Polysiloxane Architecting.

(Super)antiwetting shielding around engineering materials and protecting them against harsh environmental conditions have been achieved via growing various geometry polysiloxane (or silicone) patterns around them by using a droplet-assisted growth method, where the polymerization takes place inside of the water droplets acting as reaction vessels. The size and distribution of these reaction vessels are the main factors in making different geometry silicone patterns; however, very little is known about the fate of these droplets throughout the polymerization. Here, we propose keeping the relative humidity (% RH) inside the reactor stable throughout the polymerization as a new coating parameter to force the size of the reaction vessel water droplets to be the same for building simply shaped silicone rods with controlled geometry and distribution. In this manner, we grew simple geometry cylindric microrods on surfaces and could tune their length, diameter, inter-rod spacing, and thus the (super)hydrophobicity. Here, we also demonstrate that with changes in the amplitude and stability of the % RH, it is possible to fabricate different (super)hydrophobic nanograsses, conical silicone microrods, and isotropic silicone nanofilaments. The proposed new way of tuning initial and in situ reaction vessel droplet size can be used as a single factor to formulate different geometry silicone patterns with tunable dimensions, leading to different roughness and hydrophobicity. To a certain extent, the droplet size-assisted silicone shaping in this work provides a new way to control the length, diameter, morphology, inter-rod spacing, and thus the (super)hydrophobicity of the silicone patterns, especially those in the shape of simple cylindrical microrods. This control over silicone architecting will help to prepare new (super)hydrophobic coatings with more controlled morphology and thus wettability; on the contrary, it will support surface scientists modeling the connection between surface geometry and (super)antiwetting of such irregular pillared surfaces that remain elusive.

One-Step Synthesis of Dynamically Shaped Stiff Nanorods Using Soft Silicone Materials to Control Water Repulsion and Collection.

One-dimensional silicone nanostructures, such as filaments, wires, and tubes, have attracted significant attention, owing to their remarkable application capabilities in a large range of material and surface science. However, the soft mechanical properties of silicone cause vulnerability and irregularity in the synthesized structures, which limits their applications. Herein, a simple, solvent-free, and efficient dynamic Droplet Assisted Growth and Shaping (d-DAGS) strategy is proposed for the one-step synthesis and in situ control of the shape of silicone nanostructures. The special designed bamboo-shaped silicone nanorods (SNRs) that are produced by the repetitive dynamic regulation of growth conditions, concomitant with the periodic purging and injection of precursors, exhibit highly-regular and tunable structure with a specific number of segments, indicating that they can be tailor-made according to the requirements of various properties. The enhanced mechanical stiffness and chemical durability strongly support their excellent performances in water-resistance under both static and dynamic wetting conditions. The SNRs significantly promote buoyancy and self-cleaning properties; and exhibit very high water-harvesting efficiency compared with existing designs. Notably, the well-structured ultra-long rods with an ultrahigh aspect ratio (≈176) can also be fabricated by the d-DAGS method, and they can remain standing straight upwards and regular, even though they consist of flexible silicone.

Drought reduces water uptake in beech from the drying topsoil, but no compensatory uptake occurs from deeper soil layers.

The intensity and frequency of droughts events are projected to increase in future with expected adverse effects for forests. Thus, information on the dynamics of tree water uptake from different soil layers during and after drought is crucial. We applied an in situ water isotopologue monitoring system to determine the oxygen isotope composition in soil and xylem water of European beech with a 2-h resolution together with measurements of soil water content, transpiration and tree water deficit. Using a Bayesian isotope mixing model, we inferred the relative and absolute contribution of water from four different soil layers to tree water use. Beech took up more than 50% of its water from the uppermost 5 cm soil layer at the beginning of the 2018 drought, but then reduced absolute water uptake from the drying topsoil by 84%. The trees were not able to quantitatively compensate for restricted topsoil water availability by additional uptake from deeper soil layers, which is related to the fine root depth distribution. Absolute water uptake from the topsoil was restored to pre-drought levels within 3 wk after rewetting. These uptake patterns help to explain both the drought sensitivity of beech and its high recovery potential after drought release.

Fluorescent Staining of Silicone Micro- and Nanopatterns for Their Optical Imaging.

Performance of engineered surfaces can be enhanced by making them hydrophobic or superhydrophobic via coating them with low-surface-energy micro- and nanopatterns. However, the wetting phenomena of particularly irregular shape and spacing (super)hydrophobic patterns such as polysiloxane coatings are not yet fully understood from a microscopic perspective. Here, we show a new method to collect 3D confocal images from irregular polysiloxane micro- and nanorods from a single rod resolution to discuss their wetting response over long liquid/solid interaction times and quantify the length and diameter of these rods. To collect such 3D confocal images, fluorescent dye containing water droplets were left on our superhydrophobic and hydrophobic polysiloxane coated surfaces. Then their liquid/solid interfaces were imaged at different staining scenarios: (i) using different fluorescent dyes, (ii) when the droplets were in contact with surfaces, or (iii) after the droplets were taken away from the surface at the end of staining. Using such staining strategies, we could resolve the micro- and nanorods from root to top and determine their length and diameter, which were then found to be in good agreement with those obtained from their electron microscopy images. 3D confocal images in this paper, for the first time, present the long-time existence of more than one wetting state under the same droplet in contact with surfaces, as well as external and internal three-phase contact lines shifting and pinning. In the end, these findings were used to explain the time-dependent wetting kinetics of our surfaces. We believe that the proposed imaging strategy here will, in the future, be used to study many other irregular patterned (super)antiwetting surfaces to describe their wetting theory, which is today impossible due to the complicated surface geometry of these irregular patterns.

Systematic ranking of filaments regarding their particulate emissions during fused filament fabrication 3D printing by means of a proposed standard test method.

The diversity of fused filament fabrication (FFF) filaments continues to grow rapidly as the popularity of FFF-3D desktop printers for the use as home fabrication devices has been greatly increased in the past decade. Potential harmful emissions and associated health risks when operating indoors have induced many emission studies. However, the lack of standardization of measurements impeded an objectifiable comparison of research findings. Therefore, we designed a chamber-based standard method, i.e., the strand printing method (SPM), which provides a standardized printing procedure and quantifies systematically the particle emission released from individual FFF-3D filaments under controlled conditions. Forty-four marketable filament products were tested. The total number of emitted particles (TP) varied by approximately four orders of magnitude (109  ≤ TP ≤ 1013 ), indicating that origin of polymers, manufacturer-specific additives, and undeclared impurities have a strong influence. Our results suggest that TP characterizes an individual filament product and particle emissions cannot be categorized by the polymer type (e.g., PLA or ABS) alone. The user's choice of a filament product is therefore decisive for the exposure to released particles during operation. Thus, choosing a filament product awarded for low emissions seems to be an easily achievable preemptive measure to prevent health hazards.

Structure Analysis of Amyloid Aggregates at Lipid Bilayers by Supercritical Angle Raman Microscopy.

The amyloid-ß peptide is correlated with Alzheimer's disease and is assumed to cause toxicity by its interaction with the neuron membrane. A custom-made microscope objective based on the supercritical angle technique was developed by our group, which allows investigation of interfacial events by performing surface-sensitive and low-invasive spectroscopy. Applied to Raman spectroscopy, this technique was used to collect information about the structure of polypeptides that interact with a supported lipid bilayer. Notably, the conformation used by amyloid-ß(1-40) and amyloid-ß(1-42) when interacting directly with or next to the supported lipid bilayer was characterized. We observed two distinct secondary structures, α-helix and ß-sheet, which were exhibited by the peptide. These two structures were detected simultaneously. The propensity of the peptide to fold into these structures seemed dependent on both their number of amino acids and their proximity with the supported lipid bilayer. The α-helix structure was observed for amyloid-ß(1-42) fragments that were closer to the lipid bilayer. Peptides that were located further away from the bilayer favored the ß-sheet structure. Amyloid-ß(1-40) was less prone to adopt the α-helix secondary structure.

Statistics of a Sharp GP2Y Low-Cost Aerosol PM Sensor Output Signals.

In this work, we characterise the performance of a Sharp optical aerosol sensor model GP2Y1010AU0F. The sensor was exposed to different environments: to a clean room, to a controlled atmosphere with known aerosol size distribution and to the ambient atmosphere on a busy city street. During the exposure, the output waveforms of the sensor pulses were digitised, saved and a following offline analysis enabled us to study the behaviour of the sensor pulse-by-pulse. A linear response of the sensor on number concentration of the monosized dispersed PSL particles was shown together with an almost linear dependence on particle diameters in the 0.4 to 4 micrometer range. The gathered data about the sensor were used to predict its response to an ambient atmosphere, which was observed simultaneously with a calibrated optical particle counter.

Hierarchical Structured Multifunctional Self-Cleaning Material with Durable Superhydrophobicity and Photocatalytic Functionalities.

Self-cleaning materials, which are inspired and derived from natural phenomena, have gained significant scientific and commercial interest in the past decades as they are energy- and labor-saving and environmentally friendly. Several technologies are developed to obtain self-cleaning materials. The combination of superhydrophobic and photocatalytic properties enables the efficient removal of solid particles and organic contaminations, which could reduce or damage the superhydrophobicity. However, the fragility of the nanoscale roughness of the superhydrophobic surface limits its practical application. Here, a hierarchical structure approach combining micro- and nanoscale architectures is created to protect the nanoscale surface roughness from mechanical damage. Glass beads of 75 µm are partially embedded into a low-density polyethylene film. This composite surface is coated with silicone nanofilaments (SNFs) via the droplet-assisted growth and shaping approach, providing the nanoscale surface roughness as well as the support for the photocatalyst with enlarged surface area. TiO2 nanoparticles, which serve as the photocatalyst, are synthesized in situ on SNFs through a hydrothermal reaction. The self-cleaning effect is proved using wettability measurements for various liquids, degradation of organic contamination under UV light, and antibacterial tests. The enhanced mechanical durability of the hierarchical structure of the composite material is verified with an abrasion test.

Room-Temperature Synthesis of Germanium Oxide Nanofilaments and Their Potential Use as Luminescent Self-Cleaning Surfaces.

Germanium oxide nanofilaments (GNFs) have been synthesized under ambient conditions from the gas phase using germanium tetrachloride as a precursor. Non-crystalline GNFs synthesized by this procedure are 1-10 µm in length and 80-110 nm in diameter applying Droplet Assisted Growth and Shaping (DAGS) Chemistry. The relative humidity has been adjusted at various values in order to demonstrate the crucial role of humidity in the gas phase for the nanofilament synthesis. The novel GNFs show a strong luminescence emission in the ultra-violet and light blue region. In addition, a self-cleaning and superhydrophobic properties could be introduced in the luminescent GNF nanofilaments by simple treatment with silane molecules.

Employing stable isotopes to determine the residence times of soil water and the temporal origin of water taken up by Fagus sylvatica and Picea abies in a temperate forest.

We assessed how the seasonal variability of precipitation δ2 H and δ18 O is propagated into soil and xylem waters of temperate trees, applied a hydrological model to estimate the residence time distribution of precipitation in the soil, and identified the temporal origin of water taken up by Picea abies and Fagus sylvatica over 4 yr. Residence times of precipitation in the soil varied between a few days and several months and increased with soil depth. On average, 50% of water consumed by trees throughout a year had precipitated during the growing season, while 40% had precipitated in the preceding winter or even earlier. Importantly, we detected subtle differences with respect to the temporal origin of water used by the two species. We conclude that both current precipitation and winter precipitation are important for the water supply of temperate trees and that winter precipitation could buffer negative impacts of spring or summer droughts. Our study additionally provides the means to obtain realistic estimates of source water δ2 H and δ18 O values for trees from precipitation isotope data, which is essential for improving model-based interpretations of δ18 O and δ2 H values in plants.

Eco-Efficient Process Improvement at the Early Development Stage: Identifying Environmental and Economic Process Hotspots for Synergetic Improvement Potential.

We present here a new eco-efficiency process-improvement method to highlight combined environmental and costs hotspots of the production process of new material at a very early development stage. Production-specific and scaled-up results for life cycle assessment (LCA) and production costs are combined in a new analysis to identify synergetic improvement potentials and trade-offs, setting goals for the eco-design of new processes. The identified hotspots and bottlenecks will help users to focus on the relevant steps for improvements from an eco-efficiency perspective and potentially reduce their associated environmental impacts and production costs. Our method is illustrated with a case study of nanocellulose. The results indicate that the production route should start with carrot pomace, use heat and solvent recovery, and deactivate the enzymes with bleach instead of heat. To further improve the process, the results show that focus should be laid on the carrier polymer, sodium alginate, and the production of the GripX coating. Overall, the method shows that the underlying LCA scale-up framework is valuable for purposes beyond conventional LCA studies and is applicable at a very early stage to provide researchers with a better understanding of their production process.

Functional Silver-Silicone-Nanofilament-Composite Material for Water Disinfection.

The roughness of superhydrophobic silicone nanofilaments (SNFs) is exploited to enlarge the contact area of conventional filter material. As an efficient wetting of the filter material is crucial for water treatment, the wettability of SNFs is readily modified from superhydrophobic to hydrophilic during the functionalization process. SNFs are coated on glass beads and subsequently modified with biocidal silver nanoparticles (AgNPs). The enlarged surface area of SNFs allows a 30 times higher loading of AgNPs in comparison to glass beads without SNF coating. Thus, in column experiments, the AgNP-SNF-nanocomposite-modified glass beads exert superior antibacterial activity towards suspensions of E. coli K12 compared to AgNP functionalized glass beads without SNFs. Additionally, reusing the AgNP-SNF-nanocomposite-coated glass beads with fresh bacteria contaminated medium increases their efficacy and reduces the colony forming units by ≈6 log units. Thereby, the silver loss during percolation is below 0.1 µg mL-1 . These results highlight, first, the potential of AgNP-SNF-nanocomposite-modified glass beads as an effective filter substrate for water disinfection, and second, the efficiency of SNF coating in increasing the contact area of conventional filter material.

Directed In Situ Shaping of Complex Nano- and Microstructures during Chemical Synthesis.

Chemical composition and shape determine the basic properties of any object. Commonly, chemical synthesis and shaping follow each other in a sequence, although their combination into a single process would be an elegant simplification. Here, a pathway of simultaneous synthesis and shaping as applied to polysiloxanes on the micro- and nanoscale is presented. Complex structures such as stars, chalices, helices, volcanoes, rods, or combinations thereof are obtained. Varying the shape-controlling reaction parameters including temperature, water saturation, and the type of substrate allows to direct the reaction toward specific structures. A general mechanism of growth is suggested and analytical evidence and thermodynamic calculations to support it are provided. An aqueous droplet in either gaseous atmosphere or in a liquid organic solvent serves as a spatially confined polymerization volume. By substituting the starting materials, germanium-based nanostructures are also obtained. This transferability marks this approach as a major step toward a generally applicable method of chemical synthesis including in situ shaping.

Simultaneous Surface-Near and Solution Fluorescence Correlation Spectroscopy.

We report the first simultaneous measurement of surface-confined and solution fluorescence correlation spectroscopy (FCS). We use an optical configuration for tightly focused excitation and separate detection of light emitted below (undercritical angle fluorescence, UAF) and above (supercritical angle fluorescence, SAF) the critical angle of total internal reflection of the coverslip/sample interface. This creates two laterally coincident detection volumes which differ in their axial extent. While detection of far-field UAF emission producesa standard confocal volume, near-field-mediated SAF produces a highly surface-confined detection volume at the coverslip/sample interface which extends only ~200 nm into the sample. A characterization of the two detection volumes by FCS of free diffusion is presented and compared with analytical models and simulations. The presented FCS technique allows to determine bulk solution concentrations and surface-near concentrations at the same time.

Superamphiphobic surfaces.

Superamphiphobicity is an effect where surface roughness and surface chemistry combine to generate surfaces which are both superhydrophobic and superoleophobic, i.e., contact angles (θCA) greater than 150° along with low contact angle hysteresis (CAH) not only towards probing water but also for low-surface-tension 'oils'. In this review, we summarize the research on superamphiphobic surfaces, including the characterization of superamphiphobicity, different techniques towards the fabrication of surface roughness and surface modification with low-surface-energy materials as well as their functional applications.

Oil/water separation with selective superantiwetting/superwetting surface materials.

The separation of oil from oily water is an important pursuit because of increasing worldwide oil pollution. Separation by the use of materials with selective oil/water absorption is a relatively recent area of development, yet highly promising. Owing to their selective superantiwetting/superwetting properties towards water and oil, superhydrophobic/superoleophilic surfaces and underwater superoleophobic surfaces have been developed for the separation of oil/water-free mixtures and emulsions. In this Review, after a short introduction to oil/water separation, we describe the principles of materials with selective oil/water absorption and outline recent advances in oil/water separation with superwetting/superantiwetting materials, including their design, their fabrication, and models of experimental setups. Finally, we discuss the current state of this new field and point out the remaining problems and future challenges.

Protein biomineralized nanoporous inorganic mesocrystals with tunable hierarchical nanostructures.

Mesocrystals with the symmetry defying morphologies and highly ordered superstructures composed of primary units are of particular interest, but the fabrication has proved extremely challenging. A novel strategy based on biomineralization approach for the synthesis of hematite mesocrystals is developed by using silk fibroin as a biotemplate. The resultant hematite mesocrystals are uniform, highly crystalline, and porous nanostructures with tunable size and morphologies by simply varying the concentration of the silk fibroin and iron(III) chloride in this biomineralization system. In particular, we demonstrate a complex mesoscale biomineralization process induced by the silk fibroin for the formation of hematite mesocrystals. This biomimetic strategy features precisely tunable, high efficiency, and low-cost and opens up an avenue to access new novel functional mesocrystals with hierarchical structures in various practical applications.

Superficial dopants allow growth of silicone nanofilaments on hydroxyl-free substrates.

We report new types of silicone nanostructures by a gas-phase reaction of trichloromethylsilane: 1-D silicone nanofilaments with a raveled end and silicone nanoteeth. Filaments with a raveled end are obtained on poly(vinyl chloride), which is superficially doped with the detergent Span 20. Silicone nanoteeth grow on sodium chloride using dibutyl phthalate as superficial dopant. Without dopants, no structures are observed. The dopants are identified by mass spectroscopy and the silicone nanostructures are analyzed by infrared spectroscopy and energy-dispersive analysis of X-rays. The growth of silicone nanostructures on a hydrophobic substrate (poly(vinyl chloride)/Span 20) and a substrate free of hydroxyl groups (sodium chloride/dibutyl phthalate) questions the currently discussed mechanisms for the growth of 1-D silicone nanofilaments, which is discussed. We suggest superficial doping as an alternative pretreatment method to oxidizing activation and prove this principle by the successful coating of copper, which is superficially doped with Span 20.