Reaction kinetics of lithium-sulfur batteries with a polar Li-ion electrolyte: modeling of liquid phase and solid phase processes.

The present investigation fits the reaction kinetics of a lithium-sulfur (Li-S) battery with polar electrolyte employing a novel two-phase continuum multipore model. The continuum two-phase model considers processes in both the liquid electrolyte phase and the solid precipitates phase, where the diffusion coefficients of the Li+ ions in a solvent-softened solid state are determined from molecular dynamics simulations. Solubility experiments yield the saturation concentration of sulfur and lithium sulfides in the polar electrolyte employed in this study. The model describes the transport of dissolved molecular and ion species in pores of different size in solvated or desolvated form, depending on pore size. The Li-S reaction model in this study is validated for electrolyte 1 M LiPF6 in EC/DMC. It includes seven redox reactions and two cyclic non-electrochemical reactions in the cathode, and the lithium redox reaction at the anode. Electrochemical reactions are assumed to take place in the electrolyte solution or the solid state and cyclic reactions are assumed to take place in the liquid electrolyte phase only. The determination of the reaction kinetics parameters takes place via fitting the model predictions with experimental data of a cyclic voltammetry cycle with in operando UV-vis spectroscopy.

Solubility and dissolution kinetics of sulfur and sulfides in electrolyte solvents for lithium-sulfur and sodium-sulfur batteries.

In this study, we monitor the dissolution of sulfur and sulfides in electrolyte solvents for lithium-sulfur (Li-S) and sodium-sulfur (Na-S) batteries. The first aim of this research is to assemble a comprehensive set of data on solubilities and dissolution kinetics that may be used in the simulation of battery cycling. The investigation also offers important insights to address key bottlenecks in the development and commercialization of metal-sulfur batteries, including the incomplete dissolution of sulfur in discharge and insoluble low-order sulfides in charge, the probability of shuttling of soluble polysulfides, and the pausing of the redox reactions in precipitated low order sulfides depending on their degree of solid state. The tested materials include sulfur, lithium sulfides Li2Sx, x = 1, 2, 4, 6, and 8, and sodium sulfides Na2Sx, x = 1, 2, 3, 4, 6, and 8, dissolved in two alternative electrolyte solvents: DOL:DME 1:1 v/v and TEGDME. The determined properties of the solute dissolution in the solvent include saturation concentration, mass transfer coefficient, and diffusion coefficient of the solvent in the solid solute. In general, the DOL:DME system offers high solubility in Li-S batteries and TEGDME offers the highest solubility in Na-S batteries. Low solubility sulfides are Li2S2 and Li2S for the Li-S batteries, and Na2S3, Na2S2, and Na2S for the Na-S batteries. However, it is noted that Na2S3 dissolves fast in TEGDME and also TEGDME diffuses fast into Na2S3, offering the possibility of a swollen Na2S3 structure in which Na+ ions might diffuse and continue the redox reactions in a semisolid state.

Expanding the Efficacy of Fingermark Enhancement Using ToF-SIMS.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been shown to enhance fingermark recovery compared to standard processes used by police forces, but there is no data to show how generally applicable the improvement is. Additionally, ToF-SIMS can be run in either positive or negative ion mode (or both), and there is no data on which mode of operation is most effective at revealing fingerprints. This study aims to fill these gaps by using ToF-SIMS to image fingerprints deposited on two common exhibit-type surfaces (polyethylene and stainless steel) using 10 donors and ageing fingerprints in either ambient, rainwater, or underground for 1 and 5 months. In all, 120 fingerprints were imaged using ToF-SIMS, and each was run in positive and negative modes. A fingerprint expert compared the fingerprint ridge detail produced by the standard process to the ToF-SIMS images. In over 50% of the samples, ToF-SIMS was shown to improve fingerprint ridge detail visualised by the respective standard process for all surfaces tested. In over 90% of the samples, the ridge detail produced by ToF-SIMS was equivalent to standard development across all different ageing and exposure conditions. The data shows that there is a benefit to running the ToF-SIMS in both positive and negative modes, even if no ridge detail was seen in one mode.

Solvent Treatment of Wet-Spun PEDOT: PSS Fibers for Fiber-Based Wearable pH Sensing.

There is a growing desire for wearable sensors in health applications. Fibers are inherently flexible and as such can be used as the electrodes of flexible sensors. Fiber-based electrodes are an ideal format to allow incorporation into fabrics and clothing and for use in wearable devices. Electrically conducting fibers were produced from a dispersion of poly (3,4-ethylenedioxythiophene)-poly (styrenesulfonate) (PEDOT: PSS). Fibers were wet spun from two PEDOT: PSS sources, in three fiber diameters. The effect of three different chemical treatments on the fibers were investigated and compared. Short 5 min treatment times with dimethyl sulfoxide (DMSO) on 20 µm fibers produced from Clevios PH1000 were found to produce the best overall treatment. Up to a six-fold increase in electrical conductivity was achieved, reaching 800 S cm-1, with no loss of mechanical strength (150 MPa). With a pH-sensitive polyaniline coating, these fibers displayed a Nernstian response across a pH range of 3.0 to 7.0, which covers the physiologically critical pH range for skin. These results provide opportunities for future wearable, fiber-based sensors including real-time, on-body pH sensing to monitor skin disease.

A Time-of-Flight Secondary Ion Mass Spectrometry/Multivariate Analysis (ToF-SIMS/MVA) Approach To Identify Phase Segregation in Blends of Incompatible but Extremely Similar Resins.

This work presents a data analysis extension to a well-established methodology for the assessment of organic coatings using imaging time-of-flight secondary ion mass spectrometry (ToF-SIMS). Such an approach produced results that can be analyzed using a multivariate analysis (MVA) procedure that performs the simultaneous processing of spatially and chemically related datasets. The coatings consist of two commercial resins that yield extremely similar spectra, and there are no peaks of sufficient intensity that are uniquely diagnostic of either material to provide an unambiguous identification of each. In order to resolve the problem, in addition to microtome-based sample preparation steps of tapers for the analysis through sample thickness, standard samples in cured and uncured conditions are introduced and measured in the same fashion as the specimens under investigation. The resulting ToF-SIMS imaging datasets have been processed using non-negative matrix factorization (NMF), which enabled identification of phase separation in the cured coatings.

Exploring the interplay between particulate matter capture, wash-off, and leaf traits in green wall species.

The study investigated inter-species variation in particulate matter (PM) accumulation, wash-off, and retention on green wall plants, with a focus on leaf characteristics. Ten broadleaf plant species were studied in an experimental green wall. Ambient PM concentrations remained relatively stable throughout the measurement period: PM1: 16.60 ± 9.97 µgm-3, PM2.5: 23.27 ± 11.88 µgm-3, and PM10: 39.59 ± 25.72 µgm-3. Leaf samples were taken before and after three rainfall events, and PM deposition was measured using Scanning Electron Microscopy (SEM). Leaf micromorphological traits, including surface roughness, hair density, and stomatal density, exhibited variability among species and leaf surfaces. Notably, I.sempervirens and H.helix had relatively high PM densities across all size fractions. The study underscored the substantial potential of green wall plants for atmospheric PM removal, with higher Wall Leaf Area Index (WLAI) species like A.maritima and T.serpyllum exhibiting increased PM accumulation at plant level. Rainfall led to significant wash-off for smaller particles, whereas larger particles exhibited lower wash-off rates. Leaf micromorphology impacted PM accumulation, although effects varied among species, and parameters such as surface roughness, stomatal density, and leaf size did not consistently affect PM deposition. The composition of deposited particles encompassed natural, vehicular, salt, and unclassified agglomerates, with minimal changes after rainfall. Air Pollution Tolerance Index (APTI) assessments revealed that I.sempervirens displayed the highest air pollution tolerance, while O.vulgare had the lowest. APTI showed a moderate positive correlation with PM deposition across all fractions. The study concluded that the interplay of macro and micromorphology in green wall plant species determines their PM removal potential. Further research is needed to identify the key leaf characteristics for optimal green wall species selection for effective PM removal.

A trait-based investigation into evergreen woody plants for traffic-related air pollution mitigation over time.

This study investigated influences of leaf traits on particulate matter (PM) wash-off and (re)capture (i.e., net removal) over time. Leaf samples were taken before and after three rainfall events from a range of 10 evergreen woody plants (including five different leaf types), which were positioned with an optical particle counter alongside a busy road. Scanning electron microscopy was used to quantify the density (no./mm2), mass (µg/cm2), and elemental composition of deposited particles. To enable leaf area comparison between scale-like leaves and other leaf types, a novel metric (FSA: foliage surface area per unit branch length) was developed, which may be utilised by future research. Vehicle-related particles constituted 15 % of total deposition, and there was a notable 50 % decrease in the proportion of tyre wear particles after rainfall. T. baccata presented the lowest proportion (11.1 %) of vehicle-related particle deposition but the most consistent performance in terms of net PM removal. Only four of the 10 plant specimens (C. japonica, C. lawsoniana, J. chinensis, and T. baccata) presented effective PM wash-off across all particle size fractions and rainfall intensities, with a generally positive relationship observed between rainfall intensity and wash-off. Mass deposition was more significantly determined by particle size than number density. Interestingly, larger particles were also less easily washed off than smaller particles. Some traits typically considered to be advantageous (e.g., greater hairiness) may in fact hinder net removal over time due to retention under rainfall. Small leaf area is one trait that may promote both accumulation and wash-off. However, FSA was found to be the most influential trait, with an inverse relationship between FSA and wash-off efficacy. This finding poses trade-offs and opportunities for green infrastructure design, which are discussed. Finally, numerous areas for future research are recommended, underlining the importance of systems approaches in developing vegetation management frameworks.

Unraveling the Degradation Pathway of Inverted Perovskite Solar Cells Based on ISOS-D-1 Protocol.

Perovskite solar cells (PSCs) have shown rapid development recently, whereas nonideal stability remains the chief obstacle toward commercialization. Thus, it is of utmost importance to probe the degradation pathway for the entire device. Here, the extrinsic stability of inverted PSCs (IPSCs) is investigated by using standard shelf-life testing based on the International Summit on Organic Photovoltaic Stability protocols (ISOS-D-1). During the long-term assessment of 1700 h, the degraded power conversion efficiency is mainly caused by the fill factor (53% retention) and short-circuit current density (71% retention), while the open-circuit voltage still maintains 97% of the initial values. Further absorbance evolution and density functional theory calculations disclose that the perovskite rear-contact side, in particular for the perovskite/fullerene interface, is the predominant degradation pathway. This study contributes to understanding the aging mechanism and enhancing the durability of IPSCs for future applications.

Improving the technological readiness of time of Flight-Secondary Ion Mass Spectrometry for enhancing fingermark recovery - towards operational deployment.

The processes routinely used by police forces to visualise fingermarks in casework may not provide sufficient ridge pattern quality to aid an investigation. Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) has been proposed as a technique to enhance fingermark recovery. The technique is currently designated a Category C process in the Fingermark Visualisation Manual (FVM) as it shows potential for effective fingermark visualisation but has not yet been fully evaluated. Here the sensitivity of ToF-SIMS on three common exhibit-type surfaces - paper, polyethylene and stainless-steel was compared to standard processes. An adapted Home Office grading scale was used to evaluate the efficacy of fingerprint development by ToF-SIMS and to provide a framework for comparison with standard processes. ToF-SIMS was shown to visualise more fingerprints than the respective standard process, for all surfaces tested. In addition, ToF-SIMS was applied after the standard processes and successfully enhanced the fingerprint detail, even when the standard process failed to visualise ridge detail. This demonstrates the benefit for incorporating it into current operational fingermark development workflows. Multivariate analysis (MVA), using simsMVA, was additionally explored as a method to simplify the data analysis and image generation process.

Determination of the deposition order of overlapping latent fingerprints and inks using secondary ion mass spectrometry.

A new protocol using time-of-flight secondary ion mass spectrometry (ToF-SIMS) has been developed to identify the deposition order of a fingerprint overlapping an ink line on paper. By taking line scans of fragment ions characteristic of the ink molecules (m/z 358.2 and 372.2) where the fingerprint and ink overlap and by calculating the normalized standard deviation of the intensity variation across the line scan, it is possible to determine whether or not a fingerprint is above ink on a paper substrate. The protocol adopted works for a selection of fingerprints from four donors tested here and for a fingerprint that was aged for six months; for one donor, the very faint fingerprints could not be visualized using either standard procedures (ninhydrin development) or SIMS, and therefore the protocol correctly gives an inconclusive result.

Quantitative atomic force microscopy: A statistical treatment of high-speed AFM data for quality control applications.

Prior to the recent developments of high-speed atomic force microscopy (HS-AFM), atomic force microscopy (AFM) was not favoured by industry because of its complexity and slow image acquisition speed which may lead to poor resolution and unreliable quantified results. HS-AFM, however, is capable of imaging several frames per second and thus capable of quick, accurate, and representative measurements - ideal for quality control applications. This study demonstrates HS-AFM as a useful quality control tool by assessing the roughness of silicon carbide (SiC) monofilament fibres as a challenging example of how large HS-AFM datasets in excess of 200 images can be collected and used for reliable quantification. A comparison of two roughness methods utilising either area or line roughness parameters has been conducted, where very little difference was noted apart from the lower statistical significance of line roughness. The roughness of ten SiC fibre samples was measured with Sa (the area equivalent to Ra) roughness results varying from 34 nm to 53 nm. The small measurement uncertainties, as a result of the large number of measurements, meant that the roughness results were distinguishable from one another even though all ten SiC fibres were very similar to each other, having been produced by the same manufacturer and process. The robustness of the methods have been tested by repeating the analysis for each fibre, and in the one instance where the repeated data did not agree, a further dataset proved which one was incorrect, illustrating how industry can use these methods for quality control. A methodology of identifying the minimum number of frames required to account for sample variability, as well as recommendations on how to use HS-AFM for quantitative measurements in quality control, are also included to enable easy reproduction and adaptation of this work for other samples and measurements.

Interfacial Chemistry Investigation of Initial Fouling Conditions in Isocyanate Production: The Antifouling Performance of AISI 316L Stainless Steel.

The fouling of AISI 316L stainless steel during themanufacture of polymeric methylene diphenyl diisocyanate (pMDI) has been investigated. Studies have been carried out using a laboratory-based rig that simulates the process chemistry of the production plant. A variety of solution concentrations and treatment times have been employed to represent different stages in the production process. Following exposure, steel coupons have been removed and studied by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The thickness of the fouling layer, determined by XPS, is found to vary inversely with exposure time and solution concentration. This is a result of the solubility of the different pMDI derivatives that have been formed at different stages, and a reaction scheme is developed to explain these inverse relationships. ToF-SIMS indicates the formation of metal chlorides as a result of the initial treatment of the steel in the reaction vessel with hydrogen chloride. Fragment ions characteristic of reacted and unreacted pMDI (at m/z = 106 and 132 au, respectively) were used as an indicator of the degree of reacted isocyanate groups within the fouling layer and show a decrease with increasing exposure time, as a result of the formation of intermediates such as amines, ureas, carbodiimides, and uretonimines. The ToF-SIMS data was also processed by principal component analysis (PCA). This generally reinforced the conclusions reached by XPS and ToF-SIMS but, in addition, gave confidence in the repeatability of the analyses with the repeat data (of four analyses) clustering very tightly in the PCA score plots.

Green infrastructure for air quality improvement in street canyons.

Street canyons are generally highly polluted urban environments due to high traffic emissions and impeded dispersion. Green infrastructure (GI) is one potential passive control system for air pollution in street canyons, yet optimum GI design is currently unclear. This review consolidates findings from previous research on GI in street canyons and assesses the suitability of different GI forms in terms of local air quality improvement. Studies on the effects of various GI options (trees, hedges, green walls, green screens and green roofs) are critically evaluated, findings are synthesised, and possible recommendations are summarised. In addition, various measurement methods used for quantifying the effectiveness of street greening for air pollution reduction are analysed. Finally, we explore the findings of studies that have compared plant species for pollution mitigation. We conclude that the influences of different GI options on air quality in street canyons depend on street canyon geometry, meteorological conditions and vegetation characteristics. Green walls, green screens and green roofs are potentially viable GI options in existing street canyons, where there is typically a lack of available planting space. Particle deposition to leaves is usually quantified by leaf washing experiments or by microscopy imaging techniques, the latter of which indicates size distribution and is more accurate. The pollutant reduction capacity of a plant species largely depends on its macromorphology in relation to the physical environment. Certain micromorphological leaf traits also positively correlate with deposition, including grooves, ridges, trichomes, stomatal density and epicuticular wax amount. The complexity of street canyon environments and the limited number of previous studies on novel forms of GI in street canyons mean that offering specific recommendations is currently unfeasible. This review highlights a need for further research, particularly on green walls and green screens, to substantiate their efficacy and investigate technical considerations.

Enhanced photovoltage for inverted planar heterojunction perovskite solar cells.

The highest power conversion efficiencies (PCEs) reported for perovskite solar cells (PSCs) with inverted planar structures are still inferior to those of PSCs with regular structures, mainly because of lower open-circuit voltages (Voc). Here we report a strategy to reduce nonradiative recombination for the inverted devices, based on a simple solution-processed secondary growth technique. This approach produces a wider bandgap top layer and a more n-type perovskite film, which mitigates nonradiative recombination, leading to an increase in Voc by up to 100 millivolts. We achieved a high Voc of 1.21 volts without sacrificing photocurrent, corresponding to a voltage deficit of 0.41 volts at a bandgap of 1.62 electron volts. This improvement led to a stabilized power output approaching 21% at the maximum power point.

Note: A versatile mass spectrometer chamber for molecular beam and temperature programmed desorption experiments.

A dual purpose mass spectrometer chamber capable of performing molecular beam scattering (MBS) and temperature programmed desorption (TPD) is detailed. Two simple features of this design allow it to perform these techniques. First, the diameter of entrance aperture to the mass spectrometer can be varied to maximize signal for TPD or to maximize angular resolution for MBS. Second, the mass spectrometer chamber can be radially translated so that it can be positioned close to the sample to maximize signal or far from the sample to maximize angular resolution. The performance of this system is described and compares well with systems designed for only one of these techniques.

Next generation device grade silicon-germanium on insulator.

High quality single crystal silicon-germanium-on-insulator has the potential to facilitate the next generation of photonic and electronic devices. Using a rapid melt growth technique we engineer tailored single crystal silicon-germanium-on-insulator structures with near constant composition over large areas. The proposed structures avoid the problem of laterally graded SiGe compositions, caused by preferential Si rich solid formation, encountered in straight SiGe wires by providing radiating elements distributed along the structures. This method enables the fabrication of multiple single crystal silicon-germanium-on-insulator layers of different compositions, on the same Si wafer, using only a single deposition process and a single anneal process, simply by modifying the structural design and/or the anneal temperature. This facilitates a host of device designs, within a relatively simple growth environment, as compared to the complexities of other methods, and also offers flexibility in device designs within that growth environment.

Adsorption of poly(methyl methacrylate) and poly(vinyl chloride) blends onto polypyrrole. Study by X-ray photoelectron spectroscopy, time-of-flight static secondary ion mass spectroscopy, and inverse gas chromatography.

Poly(vinyl chloride) (PVC) and poly(methyl methacrylate) (PMMA) were co-adsorbed onto conducting, nitrate-doped, polypyrrole (PPyNO3) from tetrahydrofuran and 1,4-dioxane. The surface composition of PPyNO3 before and following polymer adsorption was monitored by X-ray photoelectron spectroscopy and time-of-flight static secondary ion mass spectroscopy which indicated that PMMA and PVC co-adsorb. However, PVC adsorption is substantially higher from 1,4-dioxane, hence a solvent effect. Inverse gas chromatography permitted to determine the dispersive contribution to the surface energy (gamma(s)d) and acid-base descriptors of the untreated and polymer blend-coated polypyrrole specimens. Whilst gamma(s)d values clearly indicate that the polymer coatings are patchy, acid-base descriptors suggest that the blend patches have a PMMA-rich surface, especially in the case of adsorption from 1,4-dioxane.

Synthesis and aqueous solution properties of polyelectrolyte-grafted silica particles prepared by surface-initiated atom transfer radical polymerization.

A range of polyelectrolyte-grafted silica particles have been prepared by grafting suitable initiators onto near-monodisperse, 304-nm-diameter silica particles using siloxane chemistry, followed by surface-initiated atom transfer radical polymerization (ATRP) of four ionic vinyl monomers, namely sodium 4-styrenesulfonate (SStNa), sodium 4-vinylbenzoate (NaVBA), 2-(dimethylamino)ethyl methacrylate (DAM), and 2-(diethylamino)ethyl methacrylate (DEA) in protic media. The resulting polyelectrolyte-grafted silica particles were characterized using dynamic light scattering (DLS), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), helium pycnometry, and diffuse reflectance infrared Fourier transfer spectroscopy (DRIFTS). The TGA results indicated that the polyelectrolyte contents of the silica particles could be varied from 0.6% to 6.0% in weight. SEM studies revealed several surface morphologies for the grafted polyelectrolytes and XPS analysis of the particle surface also provided good evidence for surface grafting. Combined aqueous electrophoresis and DLS studies confirmed that these polyelectrolyte-grafted silica particles had pH-dependent colloid stabilities, as expected. Cationic polyelectrolyte-grafted silica particles were colloidally stable at low or neutral pH, but became aggregated at high pH. Conversely, anionic polyelectrolyte-coated silica particles became unstable at low pH. It was found that the rate of surface-initiated ATRP was substantially slower than the analogous solution polymerization. Finally, there was some evidence to suggest that, at least in some cases, a significant fraction of polymer chains became detached from the silica particles during polymerization.

Determination of surface heterogeneity of D-mannitol by sessile drop contact angle and finite concentration inverse gas chromatography.

The sensitivity of two techniques in tracking changes in surface energetics was investigated for a crystalline excipient, D-mannitol. Macroscopic crystals of D-mannitol were grown from saturated water solution by slow cooling, and sessile drop contact angle was employed to measure the anisotropic surface energy. The facet-specific surface energy was consistent with localised hydroxyl group concentrations determined by X-ray photoelectron spectroscopy (XPS), and was also in excellent agreement with the surface energy distribution of the powder form of mannitol measured via a new methodology using inverse gas chromatography (IGC) at finite concentrations. The gamma(SV)(d) was found to vary between 39.5 mJ/m(2) and 44.1 mJ/m(2) for contact angle and between 40 mJ/m(2) and 49 mJ/m(2) for IGC measurements. We report here, a high level of surface heterogeneity on the native mannitol crystal surfaces. When the surfaces of both D-mannitol samples (powder and large single crystals) were modified by dichlorodimethylsilane to induce surface hydrophobicity, both IGC and contact angle revealed a homogeneous surface due to functionalisation of mannitol crystal surface with methyl groups resulting in gamma(SV)(d) of approximately 34 mJ/m(2). It was shown that both IGC and contact angle techniques are able to detect surface chemical variations and detailed surface energetic distribution.

Organic-inorganic hybrid nanoparticles: surface characteristics and interactions with a polyester resin.

Organic-inorganic hybrid nanoparticles, derived from silica precursors with different organic functionalities (methyl, ethyl, vinyl, and phenyl) synthesized via a modified Stöber method have been investigated. These particles are intended as modifiers for polymers and polymer matrix composites. Therefore, the characteristics of a polyester matrix have also been determined, and the likely interactions with the particles have been proposed. Particles have been characterized using inverse gas chromatography (IGC), X-ray photoelectron spectroscopy (XPS), and infrared spectroscopy (FT-IR). The particles show two different sets of characteristics, with methyl, ethyl, and vinyl modified silicas showing one type of behavior and the phenyl modified silica behaving rather differently. The methyl, ethyl, and vinyl groups exhibit the appearance of uniform coverage, as they are comparatively small and tightly packed, which will prevent interaction of matrix resin with retained silanol groups. The phenyl group, which is comparatively large, is not able to pack as closely, which results in a reduction of the presence and availability of silanol groups, compared to an unmodified fumed silica, but not complete inaccessibility as far as the matrix resin is concerned.