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The dissociation of methane is not only an important reaction step in catalytic processes, but also of fundamental interest. Dynamical effects during the dissociative chemisorption of methane on metal surfaces cause significant differences in computed reaction rates, compared to what is predicted by typical transition state theory (TST) models. It is clear that for a good understanding of the catalytic activation of methane dynamical simulations are required. In this paper, a general blueprint is provided for performing dynamical simulations of the dissociative chemisorption of methane on metal surfaces, by employing either the quasi-classical trajectory or ring polymer molecular dynamics approach. If the computational setup is constructed with great care-since results can be affected considerably by the setup - chemically accurate predictions are achievable. Although this paper concerns methane dissociation, the provided blueprint is, so far, applicable to the dissociative chemisorption of most molecules. [ABSTRACT FROM AUTHOR]

The population growth and consequently lack of fresh water resources, are the main concerns of developed communities. Providing water from air humidity is an efficient, clean, and sustainable solution that can supply sweet and fresh water. In this study, different metal surfaces including copper, steel, and aluminum plates have been prepared as a hydrophobic or hydrophilic surfaces through laser, to investigate the amount of collected water at 294.15 K under fully humid environment (100% humidity), at different encounter angles with plates (45, 70, and 90 °). Moreover, the metal plates along with small or large meshes have been also tested. In addition, polytetrafluoroethylene plates have been prepared via laser in order to water harvesting from humid air. It has been shown that all surfaces treated with laser have better efficiency for water harvesting in comparison with the plates without laser. Likewise, the angle of 45° has had the highest amount of collected water on all surfaces. Eventually, it has been observed that steel plate modified with laser 1 has had higher efficiency for producing drinking water.

The laser surface texturing (LST) technique has recently been used to enhance adhesion bond strength in various coating applications and to create structures with controlled hydrophobic or superhydrophobic surfaces. The texturing processing parameters can be adjusted to tune the surface's polarity, thereby controlling the ratio between the polar and dispersed components of the surface free energy and determining its hydrophobic character. The aim of this work is to systematically select appropriate laser and scan head parameters for high-quality surface topography of metal-based materials. A correlation between texturing parameters and wetting properties was made in view of several technological applications, i.e., for the proper growth of conformal layers onto laser-textured metal surfaces. Surface analyses, carried out by scanning electron microscopy and profilometry, reveal the presence of periodic microchannels decorated with laser-induced periodic surface structures (LIPSS) in the direction parallel to the microchannels. The water contact angle varies widely from about 20° to 100°, depending on the treated material (titanium, nickel, etc.). Nowadays, reducing the wettability transition time from hydrophilicity to hydrophobicity, while also changing environmental conditions, remains a challenge. Therefore, the characteristics of environmental dust and its influence on the properties of the picosecond laser-textured surface (e.g., chemical bonding of samples) have been studied while monitoring ambient conditions. [ABSTRACT FROM AUTHOR]

Vision-based defect recognition in the metal industry is an important and challenging task. Many mainstream methods based on supervised learning need a large amount of annotated defect data. However, the data acquisition in industrial scenarios is quite difficult and time-consuming. To alleviate the problem, in this paper, we propose a few-shot defect recognition (FSDR) method for metal surfaces by attention-embedding and self-supervised learning. The proposed method includes two stages,pre-training and meta learning. In the pre-training stage, an attention embedding network (AEN) is designed for better learning the defect local correlation of multi-receptive field and reducing the background interference, and to train a robust AEN without any annotations, a multi-resolution cropping self-supervised method (MCS) is developed for better generalizing the few-shot recognition task. Then, in the meta learning stage, to generate the embedding features, the defect images are encoded by the pre-trained AEN, and we also design a query-guided weight (QGW) to address the bias of embedding feature vector. The classification information is gained by computing the distance of the embedding feature vector of each category. We evaluate the proposed FSDR on the NEU dataset and the experiments show competitive results in 1-shot and 5-shot defect recognition tasks compared with the mainstream methods. [ABSTRACT FROM AUTHOR]

This study focuses on depositing Ni/W-Al2O3 nanocomposites onto a low-carbon substrate using the pulse electrodeposition technique. The effects of pulse current density on microstructural characteristics, microhardness, phase structure, and wear/corrosion properties of Ni/W-Al2O3 nanocomposites were investigated. Among the investigated nanocomposites, Ni/W-Al2O3 deposited at 0.6 A/dm2 current density showed the finest structure with average Ni-W grain and Al2O3 nanoparticle sizes of 66.7 nm and 39.1 nm, respectively. The Ni/W-Al2O3 nanocomposite deposited under the same conditions exhibited a maximum microhardness of ~ 825.7 HV, while also demonstrating the lowest corrosion current density of ~ 0.72 A/cm2. After 60 min of wear testing, wear loss of Ni/W-Al2O3 nanocomposite deposited at 0.6 A/dm2 was recorded as 42.8 mg, indicating its excellent wear resistance. In contrast, Ni/W-Al2O3 nanocomposite deposited at 0.8 A/dm2 displayed the highest wear loss value of 101.5 mg. [ABSTRACT FROM AUTHOR]

The paper deals with the task of automated segmentation of images of defects metal surfaces. The aim of the study is to improve segmentation algorithms using deep learning methods. The expediency of using the U-Net neural network, which is effective in the tasks of semantic image segmentation, is substantiated. With the help of a special architecture, the network can create segmentation masks with high efficiency. The training dataset for the neural network contained images of four classes of defects, including chips, cracks, and stains. As a result of analyzing the distribution of defect classes in the training dataset, it was concluded that the classes were unbalanced, which negatively affects the training results. To evaluate the quality of network training, a set of metrics such as Accuracy, F1 Score, and IOUScore is considered. The feasibility of using these metrics is analyzed, taking into account the features of the training data set. It is proved that under conditions of significant imbalance of classes, the Accuracy metric does not reflect the real quality of the model. The influence of different variants of the ResNet architecture backbone on the training results is analyzed. It is determined that the best results are shown by the ResNet18 model, which managed to obtain a Dice coefficient of 69 % and an IOUScore of 53 % on the test data set. It is proved that an increase in the number of model parameters does not always lead to an improvement in the reliability of the results. The article provides examples of test images and defect masks and countures predicted by the neural network. [ABSTRACT FROM AUTHOR]

The development of approaches for the non-thermal sterilization of instruments is an urgent task to ensure the safety of meat industry products, where the use of hot water leads to the formation of condensates and a deterioration in the hygienic condition of the premises. In this study, an installation for sterilizing knives was created, which works by activating aqueous salt solutions with a glow discharge. The power consumption of the installation reactor is only 125–150 Wh. The temperature rise of the sterilizing agent used is about 1.1 ± 0.2 °C/min/L. The effectiveness of the installation for plasma-activation of aqueous solutions of chloride and sodium sulfate by glow discharge (PAW) in relation to the inactivation of microorganisms, including Staphylococcus aureus, Salmonella typhimurium, Pseudomonas gessardii and L. monocytogenes, on steel surfaces was evaluated. Samples of stainless steel (parts of knives) were used in two versions (new and artificially aged). Mono- and polyspecies bacterial biofilms were grown on the surface of the samples. The treatment was carried out by immersing samples of steel plates in plasma-activated aqueous solutions. It was found that the treatment of plates in a knife sterilizer for 1 min had an effective effect on the inhibition of all types of studied bacteria. [ABSTRACT FROM AUTHOR]

We studied the surface-enhanced Raman spectra of amino acids D-alanine and DL-serine and their mixture on silver nanoisland films (SNF) immersed in phosphate-buffered saline (PBS) solution at millimolar amino acid concentrations. It is shown that the spectra from the amino acid solutions differ from the reference spectra for microcrystallites due to the electrostatic orientation of amino acid zwitterions by the metal nanoisland film. Moreover, non-additive peaks are observed in the spectrum of the mixture of amino acids adsorbed on SNF, which means that intermolecular interactions between adsorbed amino acids are very significant. The results indicate the need for a thorough analysis of the Raman spectra from amino acid solutions, particularly, in PBS, in the presence of a nanostructured silver surface, and may also be of interest for studying molecular properties and intermolecular interactions. [ABSTRACT FROM AUTHOR]

In this study, we demonstrate the structural evolution of a two-dimensional (2D) supramolecular assembly system, which is steered by the thermally activated deprotonation of the primary organic building blocks on a Ag(111) surface. Scanning tunneling microscopy revealed that a variety of structures, featuring distinct structural, chiral, and intermolecular bonding characters, emerged with the gradual thermal treatments. According to our structural analysis, in combination with density function theory calculations, the structural evolution can be attributed to the successive deprotonation of the organic building blocks due to the inductive effect. Our finding offers a facile strategy towards controlling the supramolecular assembly pathways and provides a comprehensive understanding of the 2D crystal engineering on surfaces. [ABSTRACT FROM AUTHOR]

Over the past decade, interest has increased in controlling the wettability of metal surfaces with various liquids. In particular, the use of hydrophobic functional surfaces improves the efficiency and reliability of thermal power plants and systems operating in various areas of life. One of the most promising ways to achieve a hydrophobic state of structural materials is surface modification using laser equipment: laser ablation. As a result of exposure to laser radiation, melting, evaporation and recrystallization of the surface layer of the metal occur. By varying the parameters of exposure to laser radiation, it is possible to form a relief with specified geometric characteristics on a metal surface. The creation of hydrophobic metal surfaces using laser equipment includes the following steps: choosing the type of laser source, determining the radiation parameters and the trajectory of the laser beam over the surface, preparing the initial surface, forming the relief, and reducing the surface energy after laser ablation. This paper presents an overview of the results of research on the creation of hydrophobic metal surfaces based on the formation of a structured relief. In most studies, a relief was formed on the surface of metal samples in the form of equidistant lines, a grid, or had no pronounced structure (irregular structure). It has been established that the hydrophobic state of a metal surface with the highest contact angles (more than 150°) is achieved by laser texturing of the relief in the form of equidistant lines or a grid with a step not exceeding 100 μm. The maximum contact angle (approximately 179°) was obtained by forming a relief in the form of a grid with mutually perpendicular lines equidistant at 15 and 20 µm. [ABSTRACT FROM AUTHOR]

Rubrene (C42H28) was adsorbed with submonolayer coverage on Pt(111), Au(111), and graphene-covered Pt(111). Adsorption phases and vibronic properties of C42H28 consistently reflect the progressive reduction of the molecule–substrate hybridization. Separate C42H28 clusters are observed on Pt(111) as well as broad molecular resonances. On Au(111) and graphene-covered Pt(111) compact molecular islands with similar unit cells of the superstructure characterize the adsorption phase. The highest occupied molecular orbital of C42H28 on Au(111) exhibits weak vibronic progression while unoccupied molecular resonances appear with a broad line shape. In contrast, vibronic subbands are present for both frontier orbitals of C42H28 on graphene. They are due to different molecular vibrational quanta with distinct Huang–Rhys factors.

Electrocatalytic denitrification is a promising technology for removing NOx species (NO3−, NO2− and NO). For NOx electroreduction (NOxRR), there is a desire for understanding the catalytic parameters that control the product distribution. Here, we elucidate selectivity and activity of catalyst for NOxRR. At low potential we classify metals by the binding of *NO versus *H. Analogous to classifying CO2 reduction by *CO vs. *H, Cu is able to bind *NO while not binding *H giving rise to a selective NH3 formation. Besides being selective, Cu is active for the reaction found by an activity‐volcano. For metals that does not bind NO the reaction stops at NO, similar to CO2‐to‐CO. At potential above 0.3 V vs. RHE, we speculate a low barrier for N coupling with NO causing N2O formation. The work provides a clear strategy for selectivity and aims to inspire future research on NOxRR. [ABSTRACT FROM AUTHOR]

[Display omitted] • For both surfaces, the neutral fractions decrease as the incident energy increases. • Neutral fraction on H 2 O/Cu(1 1 0) is lower than that of Cu(1 1 0). • The work function of H 2 O/Cu(1 1 0) is lightly greater than that of clean Cu(1 1 0). keV-energy Na+ ions are scattered from clean and water covered Cu(1 1 0) surfaces in grazing incidence. For both surfaces the pronounced Na° fractions decrease with incident energy. In particular, the lower Na° fraction has been observed for the water covered Cu(1 1 0) surface. The simple calculations using rate equation are presented to compare with the experimental data. The calculation is in agreement with the experimental data. It indicates that the water covered Cu(1 1 0) surface has the slightly higher work function due to water molecules dissociation and forming hydroxyl groups, so that the neutral fraction on water covered Cu(1 1 0) is lower than that on the clean surface. [ABSTRACT FROM AUTHOR]

Purpose: We investigated the recovery and extraction efficiency of DNA from three metal surfaces (brass, copper, steel) relevant to forensic casework, and plastic (control) using two different swabbing systems; Rayon and Isohelix™ swabs, with sterile water and isopropyl alcohol respectively, as the wetting solutions. Methods: Twenty nanograms of human genomic DNA were applied directly to Isohelix™ and Rayon swabs; and to the metal and plastic substrates. All substrates were left to dry for 24 h, followed by single wet swabbing and extraction with the DNA IQ™ System. DNA extracts were quantified using real time quantitative PCR assays with SYBR green chemistry. Results: DNA was extracted from directly seeded Isohelix™ swabs with a high efficiency of 98%, indicating effective DNA-release from the swab into the extraction buffer. In contrast, only 58% of input DNA was recovered from seeded Rayon swabs, indicating higher DNA retention by these swabs. Isohelix™ swabs recovered 32 – 53% of DNA from metal surfaces, whilst the Rayon swabs recovered 11—29%. DNA recovery was lowest from copper and highest from brass. Interestingly, Rayon swabs appeared to collect more DNA from the plastic surface than Isohelix™ swabs, however, due to the lower release of DNA from Rayon swabs they returned less DNA overall following extraction than Isohelix™ swabs. Conclusion: These results demonstrate that DNA samples deposited on metal surfaces can be more efficiently recovered using Isohelix™ swabs wetted with isopropyl alcohol than Rayon swabs wetted with sterile water, although recovery is affected by the substrate type. [ABSTRACT FROM AUTHOR]

This study illustrates pervasive challenges in studying wetting dynamics, including dynamic contact angles, on irregularly roughened surfaces. We demonstrate that asymmetric water droplet shapes occur more than 50% of the time during static and dynamic contact angle measurements on sandblasted Zn-plated stainless steel with a polymeric overcoat. The pinning that causes the asymmetric drop shape distortion on horizontal surfaces also influences the sliding behavior on inclined surfaces. These effects lead to a poor correlation between the measured dynamic contact angles and the observed sliding angles (critical tilt angles). Our work emphasizes that large variations in the values of these dynamic wetting parameters are inherent to the heterogeneity of the surface roughness, and thus they limit the usefulness of standard dynamic wetting criteria. These findings have implications for academic and industrial research focused on making coated materials that have consistent wettability properties throughout their usage life cycle. [ABSTRACT FROM AUTHOR]

Blood is commonly discovered at crime scenes in various forms, including stains, dried residue, pools, and fingerprints on assorted surfaces. Estimating the age of bloodstains is a crucial aspect of reconstructing crime scenes. This research aimed to investigate how the nature of different surfaces affects the estimation of bloodstain age, utilizing a reliable and non-destructive approach. The study employed ATR-FTIR spectroscopy in conjunction with Chemometric techniques such as PCA (Principal Component Analysis) and OPLSR (Orthogonal Signal Correction Partial Least Square Regression Analysis) to analyze spectral data and develop regression models for estimating bloodstain age on cement, metal, and wooden surfaces for up to eleven days. The chemometric models for bloodstains on all three substrates demonstrated strong performance, with predictive Root Mean Square Error (RMSE) values ranging from 1.1 to 1.43 and R 2 values from 0.84 to 0.89. Notably, the model developed for metal surfaces was found to be the most accurate with minimal prediction error. The findings of the study showed that the porosity of the substrates upon which bloodstains were found had a discernible influence on the age-related transformations observed in bloodstains; the majority of which occured within the spectral range of 2800 cm - 1 to 3500 cm - 1 ., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Jellium model is well known and used to understand the neutralization of alkali-metal ions on metal surfacesbut we find it cannot explain our experiments for the neutralization of 0.4 keV and 0.8 keV Na+ ions on Al(1 1 1) and Cu(1 1 0) surfaces in grazing incidence. As the exit angle increases neutral fractions on Cu(1 1 0) surface decreases first and then increases which is similar to our previous results at large scattering angles. While for the Al(1 1 1) surface we observe opposite characteristics. This anomalous bell-shaped feature cannot be explained by the Jellium model. One possible explanation is the inner 2p electron promotion at smaller exit angles this may cause the Na* excited states to be generated and produce excess Na+ ions while the similar electronic excitation process is inefficient for the Cu(1 1 0) surface in the present energy range. [ABSTRACT FROM AUTHOR]

The characteristics of different shapes of nonmetallic inclusions (NMIs) are determined using different methods. In this respect, various shapes of NMIs, including spherical, octahedral, elongated, bar‐like, plate‐like, polyhedral, and irregular inclusions, are observed in different steels and ferroalloys. The inclusions are investigated using three methods: 1) 2D investigations on a polished cross section (2D method); 2) 3D investigations on a film filter after electrolytic extraction and filtration (EE method); and 3) 3D investigations on a metal surface after electrolytic extraction (MS method). In addition, scanning electron microscopy (SEM) with an energy‐dispersive spectrometer (EDS) is used for the determination of the chemical composition of inclusions. The advantages and limitations of different methods for investigations of different shaped inclusions are discussed. The results show that the 2D method is less precise to detect the morphology, size, and number of inclusions; however, the EE and MS methods are used to determine a more accurate morphology. Furthermore, the MS method is found to be more advantageous in detecting large‐sized inclusions. This study also shows that the results on both the film filter and metal surface should be grouped together to obtain more comprehensive information of the inclusion characteristics. [ABSTRACT FROM AUTHOR]

The modification of metal electrode surfaces with functional organic molecules is an important part of organic electronics. The interaction of the buckminsterfullerene fragment molecule pentaindenocorannulene with a Cu(100) surface is studied by scanning tunneling microscopy, dispersion‐enabled density functional theory, and force field calculations. Experimental and theoretical methods suggest that two adjacent indeno groups become oriented parallel to the surface upon adsorption under mild distortion of the molecular frame. The binding mechanism between molecule and surface is dominated by strong electrostatic interaction owing to Pauli repulsion. Two‐dimensional aggregation at room temperature leads to a single lattice structure in which all molecules are oriented unidirectionally. Their relative arrangement in the lattice suggests noncovalent intermolecular interaction through C−H⋅⋅⋅π bonding. [ABSTRACT FROM AUTHOR]

A method is developed for applying metallic, intermetallic, or ceramic coatings to a metal surface by means of ultrasound (high-frequency acoustic vibrations). The method may also be used to reinforce metallic surfaces by means of particles of another metal or ceramic. Under the action of ultrasound, chemical reactions and solid-phase diffusion are accelerated. That is accompanied by strong adhesion of the metal matrix to the particles; solid-phase transformations; and the formation of intermetallides, oxides, carbides, nitrides, and other compounds, depending on the surrounding gas and the powder composition. As a result, a composite coating or layer with nanostructure or microstructure is formed on the surface. [ABSTRACT FROM AUTHOR]

The salinization and contamination of metal surfaces by chloride‐containing aerosols is of great importance with regard to corrosion phenomena of damaged coated metal surfaces and stainless steels in the maritime sector and in offshore applications. Detailed questions have to be answered to clarify whether and to what extent salinization of the surface has an influence on the adhesion and durability of coatings in repairing applications and on pitting occurrence on stainless steels under atmospheric conditions. The questions arise which degree of salinization is reached after which period of time and how a defined and reproducible salinization can be simulated in the laboratory for further systematic investigations. The article is dedicated to these questions. Results of a field trial on the Island of Heligoland are presented and a simple procedure for a defined loading of metal surfaces with chlorides at a laboratory scale using a design of experiments (DoE) approach is introduced. [ABSTRACT FROM AUTHOR]

Objectives: To evaluate the effects of the surface modification of 316L stainless steel (SS) by low-temperature plasma nitriding on endothelial cells for stent applications. Results: X-ray diffraction (XRD) confirmed the incorporation of nitrogen into the treated steel. The surface treatment significantly increased SS roughness and hydrophilic characteristics. After 4 h the cells adhered to the nitride surfaces and formed clusters. During the 24 h incubation period, cell viability on the nitrided surface was higher compared to the polished surface. Nitriding reduced late apoptosis of rabbit aorta endothelial cell (RAEC) on the SS surface. Conclusion: Low temperature plasma nitriding improved the biocompatible of stainless steel for use in stents. [ABSTRACT FROM AUTHOR]

[Display omitted] • Deposition rate affects roughness, activation barrier influences. • Unrestricted diffusion model leads to higher roughness. • Temperature smooth surfaces, alters growth mechanisms. • Higher temperatures increase layer occupancy, favor diffusion. • Steady state is not reached for any materials in unrestricted model. • Dynamic exponent Beta depends of the diffusion mechanism. The growth behavior of Cr and W surfaces using kinetic Monte Carlo (KMC) simulations based on Density-Functional Theory (DFT) is presented in this study. Three models, a growth model with random deposition and no diffusion, a growth model with restricted diffusion and a growth model with unrestricted diffusion model, were compared to understand their influence on the predicted surface roughness and layer density. The impact of deposition rate and temperature on surface growth for both metals were analyzed. For deposition rate studies, five different rates (0.01 ML/s, 0.1 ML/s, 1.0 ML/s, 10.0 ML/s, and 100 ML/s) were considered at 550 K for Cr and W respectively. The effect of temperature on roughness was also studied employing various temperatures from 300 K to 1100 K for both metals and under the two different evolution models. The results show that the unrestricted diffusion model exhibits higher roughness compared to the restricted model for both metals. The restricted model shows a stable region of roughness, whereas the unrestricted model shows a continuous increase in roughness throughout the simulation. Furthermore, layer density analysis revealed that temperature affects the filling of lower monolayers. Finally, dynamic exponents β and α for each studied model were calculated and discussed. The results highlight the influence of diffusion models, deposition rate and temperature on surface, roughness, and layer density. [ABSTRACT FROM AUTHOR]

Inert metal surfaces present more chances of hosting organic intact radicals than other substrates, but large amounts of delocalized electronic states favor charge transfer and thus spin quenching. Lowering the molecule–substrate interaction is a usual strategy to stabilize radicals on surfaces. In some works, thin insulating layers were introduced to provide a controllable degree of electronic decoupling. Recently, retinoid molecules adsorbed on gold have been manipulated with a scanning tunneling microscope (STM) to exhibit a localized spin, but calculations failed to find a radical derivative of the molecule on the surface. Now the formation of a neutral radical spatially localized in a tilted and lifted cyclic end of the molecule is presented. An allene moiety provokes a perpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated allene in its lifted subpart. DFT calculations and STM manipulations give support to the proposed mechanism. Spinning on the surface: An allene formed by a sigmatropic reaction on retinoic acid shows a long‐lived magnetism on a gold surface after dehydrogenation. An allene moiety provokes a perpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated product in its lifted subpart. [ABSTRACT FROM AUTHOR]

Abstract We review our recent studies of photochemistry and plasmon chemistry of dimethyl disulfide, (CH 3 S) 2 , molecules adsorbed on metal surfaces using a scanning tunneling microscope (STM). The STM has been used not only for the observation of surface structures at atomic spatial resolution but also for local spectroscopies. The STM combined with optical excitation by light can be employed to investigate chemical reactions of single molecules induced by photons and localized surface plasmons. This technique allows us to gain insights into reaction mechanisms at a single molecule level. The experimental procedures to examine the chemical reactions using the STM are briefly described. The mechanism for the photodissociation reaction of (CH 3 S) 2 molecules adsorbed on metal surfaces is discussed based on both the experimental results obtained with the STM and the electronic structures calculated by density functional theory. The dissociation reaction of the (CH 3 S) 2 molecule induced by the optically excited plasmon in the STM junction between a Ag tip and metal substrate is also described. The reaction mechanism and pathway of this plasmon-induced chemical reaction are discussed by comparison with those proposed in plasmon chemistry. [ABSTRACT FROM AUTHOR]

Understanding the behavior of proteins at material interfaces has become increasingly important as the intersection between the biological and synthetic worlds continues to grow. By inducing changes in protein structure, interactions with materials may lead to a loss of function and/or biological activity, as well as undesirable cellular interactions in vivo , including the foreign body reaction to implantable materials. Despite extensive research, the understanding of the mechanisms that lead to protein conformational changes on surfaces remains incomplete. Here, we highlight recent advances in understanding and controlling protein conformation on the surface of synthetic materials, including nanomaterials, polymer films and brushes, metal coatings and particles, and graphitic materials. We also review developments in the use of biophysical and computational methods for characterizing the structure of proteins at solution–solid interfaces. These approaches have provided important new insights into the physico-chemical factors that control protein conformation in near-surface environments, which represents a critical step towards the rational design of biotic–abiotic interfaces in biomedical and biotechnological applications. Graphical abstract Image 1 Highlights • The mechanistic understanding of protein unfolding on surfaces remains incomplete. • Lack of understanding has hindered the use of materials in biological environments. • Review highlights advances in elucidating impact of materials on protein structure. • Recent findings show lack of consistent observations between different systems. • Protein unfolding on surfaces may be confounded by various types of heterogeneities. [ABSTRACT FROM AUTHOR]

In this work we present a model for the surface oxide film growth considering the influence of space charge. The space charge field Esp is assumed proportional to the charge of moving metal ions and electrons in the oxide layer. The surface charge field Eox decreases as the Cabrera and Motts’ oxide thickness X grows to its limit X1 (Eox = VM/X). Eox remains constant for further growth of the oxide film (Eox = VM/X1). The obtained equation for the growing rate of the oxide film covers two stages. The first stage is characterized by a negligible space charge and is described by the typical inverse logarithmic law. During transition from thin to thick film, the oxidation growth rate is described by a direct logarithmic law which is confirmed by many experiments. At the end of this stage, the drift of metal ions is replaced by their diffusion that leads to parabolic law. [ABSTRACT FROM AUTHOR]

Abstract: Multimetallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ4‐nitrido cluster [Fe4(μ4‐N)(CO)12]−, this analogy is limited owing to the electron‐withdrawing effect of carbonyl ligands on the iron nitride core. Described here is the synthesis and reactivity of [Fe4(μ4‐N)(CO)8(CNArMes2)4]−, an electron‐rich analogue of [Fe4(μ4‐N)(CO)12]−, where the interstitial nitride displays significant nucleophilicity. This characteristic enables rational expansion with main‐group and transition‐metal centers to yield unsaturated sites. The resulting clusters display surface‐like reactivity through coordination‐sphere‐dependent atom rearrangement and metal–metal cooperativity. [ABSTRACT FROM AUTHOR]

Most traditional techniques to recover latent fingermarks from metallic surfaces do not consider the metal surface properties and instead focus on the fingermark chemistry. The scanning Kelvin probe (SKP) technique is a non-contact, non-destructive method, used under ambient conditions, which can be utilised to recover latent prints from metallic surfaces and does not require any enhancement techniques or prevent subsequent forensic analysis. Where a fingermark ridge contacted the metal, the contact potential difference (CPD) contrast between the background surface and the fingermark contact area was 10-50mV. Measurements were performed on the untreated brass, nickel-coated brass and copper metal surfaces and compared to traditional forensic enhancement techniques such as Vacuum Metal Deposition (VMD) using Au-Zn and Au-Ag. Using VMD, the CPD change ranged from 0 to 150mV between the dissimilar metal surfaces affected by the fingermark. In general, SKP worked best without additional enhancement techniques. Scanning Electron Microscope (SEM) scans were used to identify the fingermark contact areas through a sodium, chlorine and oxygen electron probe micro-analyzer (EPMA). The fingermark was observed in the backscattered electron image as the carbon deposits scattered the electrons less than the surrounding metal surface. The fingermark is shown clearly in a Cathodoluminescence scan on the copper sample as it blocks the photon emission at band gap (2.17eV) from the underlying copper oxide (Cu2O) surface. For the first time, SEM, EPMA and Cathodoluminescence techniques were compared to SKP data. Visible and latent fingermarks were tested with latent, eccrinous fingermarks more easily imaged by SKP. Results obtained were very encouraging and suggest that the scanning Kelvin probe technique, which does not need vacuum, could have a place as a first stage analysis tool in serious crime investigation. [ABSTRACT FROM AUTHOR]

The transmissivity of metal-metal sealing joints is investigated experimentally and compared to predictions obtained by modeling. The focus is laid upon a wavy surface contacting a flat rigid part, representative of a seat-to-plug contact in an internal sealing valve encountered in nuclear power plants for instance. Experimental transmissivities are obtained from water leak-rate and pressure drop measurements carried out on a model ring-shape sample seat holding a controlled wavy defect and pressed against a rigid flat plug with a controlled normal load. The sample seat surface is manufactured by face turning a tubular part under radial stress and waviness is obtained after elastic relaxation. Modeling is performed on a three-dimensional finite element model of the assembly, composed of the plug, the sample seat, and its holder. The upper sample seat surface, in which topography is recorded by confocal microscopy, is reconstructed using a modal decomposition on the basis of vibrational eigenmodes. Its lower surface, in contact with the holder, is considered as perfectly flat or with its own defects. The contact aperture field between the seat and the plug is computed for a given normal load and is used to solve the incompressible Reynolds equation with a boundary element method, yielding the transmissivity. Predicted transmissivities reveal to be in good agreement with experimental data at low clamping loads and are overestimated for larger ones. Defects on the lower surface of the seat are shown to have a significant impact on the seat-to plug contact transmissivity. [ABSTRACT FROM AUTHOR]

There is an increased interest in incorporating multi-wall carbon nanotubes (MWCNTs) into polymer matrices to control the adhesion of bacteria to surfaces and the subsequent formation of biofilm growth on the surface of water pipes, food packages, and medical devices. Microbial interactions with carbon nanotube-polymer composites in the environment are not well understood. The growth of Pseudomonas fluorescens (gram-negative) and Mycobacterium smegmatis (gram-positive) biofilms on copper, polyethylene (PE), polyvinyl chloride, and stainless steel was compared with growth on MWCNT-PE composites in order to gain insight into the effect of the surface properties of nanomaterials on the attachment and proliferation of microorganism which could result in the engineering of better, non-fouling materials. A statistical analysis of the biofilm growth showed a significant impact of materials for both P . fluorescens ( p  < 0.0001) and M . smegmatis ( p  = 0.00426). Biofilm growth after 56 days on PE compared to biofilm growth on copper surfaces decreased by 46.4% and 34.9% for P . fluorescens and M . smegmatis , respectively. Biofilm growth on PE-multiwall-carbon-nanotubes (MWCNTs)-composites surface compared to PE decreased by 89.3% and 29% for P . fluorescens and M . smegmatis , respectively. Bacterial species ( p  < 0.0006) and surface roughness ( p  < 0.0001) were important factors in determining the attachment and initial biofilm growth rate. The interactions between cells and material surface could be attributed to the complicated and collective effect of electrostatic forces, hydrophobic interactions, and hydrogen/covalent bonding. Further study is needed to determine whether or not there is a difference between the cell attachment in the exponential growth phase and the stationary, or decay, phase cells. [ABSTRACT FROM AUTHOR]

Abstract Atomic hydrogen is a highly reactive species of interest because of its role in a wide range of applications and technologies. Knowledge about the interactions of incident H atoms on metal surfaces is important for our understanding of many processes such as those occurring in plasma-enhanced catalysis and nuclear fusion in tokamak reactors. Herein we review some of the numerous experimental surface science studies that have focused on the interactions of H atoms that are incident on low-Miller index metal single-crystal surfaces. We briefly summarize the different incident H atom reaction mechanisms and several of the available methods to create H atoms in UHV environments before addressing the key thermodynamic and kinetic data available on metal and modified metal surfaces. Generally, H atoms are very reactive and exhibit high sticking coefficients even on metals where H 2 molecules do not dissociate under UHV conditions. This reactivity is often reduced by adsorbates on the surface, which also create new reaction pathways. Abstraction of surface-bound D(H) adatoms by incident H(D) atoms often occurs by an Eley-Rideal mechanism, while a hot atom mechanism produces structural effects in the abstraction rates and forms homonuclear products. Additionally, incident H atoms can often induce surface reconstructions and populate subsurface and bulk absorption sites. The absorbed H atoms recombine to desorb H 2 at lower temperature and can also exhibit higher subsequent reactivity with adsorbates than surface-bound H adatoms. Incident H atoms, either directly or via sorbed hydrogen species, hydrogenate adsorbed hydrocarbons, sulfur, alkali metals, oxygen, halogens, and other adatoms and small molecules. Thus, H atoms from the gas phase incident on surfaces and adsorbed layers create new reaction channels and products beyond those found from interactions of H 2 molecules. Detailed aspects of the dynamics and energy transfer associated with these interactions and the important applications of hydrogen in plasma processing of semiconductors are beyond the scope of this review. [ABSTRACT FROM AUTHOR]

This paper presents a review of the experimental and theoretical investigations of halogen interaction with metal surfaces. The emphasis was placed on the recent measurements performed with a scanning tunneling microscope in combination with density functional theory calculations. The surface structures formed on metal surface after halogen interaction are classified into three groups: chemisorbed monolayer, surface halide, bulk-like halide. Formation of monolayer structures is described in terms of surface phase transitions. Surface halide phases are considered to be intermediates between chemisorbed halogen and bulk halide. The modern theoretical approaches in studying the dynamics of metal halogenation reactions are also presented. [ABSTRACT FROM AUTHOR]

Butyl rubber as a commercial elastomer has got many applications in various products such as tires, protective clothes, sealants, hose (steam and automotive), inner coating of tanks, etc. Considering these usages, butyl rubber might be subjected to acidic or alkaline environments. Acid and alkaline materials can diffuse through the rubber and cause degradation of its structure which leads to deterioration of rubber properties including adhesion strength. In this study, the effects of environments having different pH values on adhesion strength between rubber compounds--based on butyl rubber and bromobutyl rubber--and aluminum surface are investigated. Samples were immersed in solutions with different pH values of 0.7, 3, 7, 11 and 13.7. By conducting tensile and tack tests, changes in adhesion strength and tackiness property of samples are studied. Considering the broad range of examined pH values, results demonstrate that solutions with more acidic and alkaline pH values severely reduce adhesion strength and leads to about 60% reduction in adhesion. However, pH values closer to neutral pH have a less negative effect and cause up to 49% decrement in adhesion strength. Furthermore, Samples which were immersed in alkaline solutions lost their tackiness property, whereas the samples which were immersed in acidic solution retained their tackiness. However, in these cases, tack property was reduced to 1/7 of its value before being immersed in the acidic solution. [ABSTRACT FROM AUTHOR]

The aim of this study was to analyze the impact of hydrodynamic forces on the multiplication ofE. coli, and biofilm formation and dispersion. The experiments were provided in a flow chamber simulating a cleaning-in-place system. Biofilm biomass was measured using a crystal violet dye method. The results show that hydrodynamic forces affect not only biofilm formation and dispersion but the multiplication ofE. coliin the first place. We found more biofilm biomass on the rough surface than on the smooth one. The results of the biofilm formation test show that laminar flow promotes the biofilm growth over 72 h, meanwhile turbulent flow after 48 h causes decrease in biomass. The results of the biofilm dispersion test, in contrast, show that laminar flow removed less biofilm from both materials that turbulent flow did. Therefore, taking into account these findings in cleaning-in-place technology can substantially reduceE. colimultiplication and biofilm formation. [ABSTRACT FROM PUBLISHER]

• Dopant atoms enhanced the adsorption behavior of benzene. • The highest adsorption energy was found in Pt 2 Pd 2 -Ag configuration AB. • A remarkable change from physisorption to chemisorption binding for benzene molecule. Heterogeneous catalysis, molecular sensors, and photovoltaics all rely on the interfaces between organic molecules and metal surfaces. Here, we study the adsorption of benzene on Ag(100) surface doped by Au n , Pd n , Pt n (n = 1–4), Au 2 Pd 2 , Au 2 Pt 2 and Pd 2 Pt 2 using density-functional theory (DFT), with the inclusion of van der Waals interactions, and compare with available computational and experimental result. The calculated quantities reveal that the interaction strength of Benzene with the surface gradually increases when it is doped by Pd or Pt atoms, showing a change in the nature of the interaction, from physisorption to chemisorption. We found that with surface allowing, one can tune the interaction strength. The charge transfer was found to occur from the molecule to the clean and doped surfaces with Au atoms and from the doped surface with Pd to the molecule. The redistribution of charge density indicates modifications in the features of the interface between the doped Ag(100) surfaces and benzene. In addition, alloying the Ag(100) surface with reactive TM changes substantially its electronic properties, which impacts its interactions with benzene. Finally, mixing two dopants or more can tune the electronic structure in designing more effective interfaces for various applications. [Display omitted] [ABSTRACT FROM AUTHOR]

Conversion of energy at the gas–solid interface lies at the heart of many industrial applications such as heterogeneous catalysis. Dissipation of parts of this energy into the substrate bulk drives the thermalization of surface species, but also constitutes a potentially unwanted loss channel. At present, little is known about the underlying microscopic dissipation mechanisms and their (relative) efficiency. At metal surfaces, prominent such mechanisms are the generation of substrate phonons and the electronically non-adiabatic excitation of electron–hole pairs. In recent years, dedicated surface science experiments at defined single-crystal surfaces and predictive-quality first-principles simulations have increasingly been used to analyze these dissipation mechanisms in prototypical surface dynamical processes such as gas-phase scattering and adsorption, diffusion, vibration, and surface reactions. In this topical review we provide an overview of modeling approaches to incorporate dissipation into corresponding dynamical simulations starting from coarse-grained effective theories to increasingly sophisticated methods. We illustrate these at the level of individual elementary processes through applications found in the literature, while specifically highlighting the persisting difficulty of gauging their performance based on experimentally accessible observables.

The effect that the ionizing radiation caused by radioactive contamination of soil exerts on the surface of carbon steel 20 samples, on their corrosion resistance, and on operation reliability according to lowcycle fatigue tests (taking into account that fatigue is one of the main causes of failures resulting from corrosion and mechanical damage of thin-wall metal structures, in particular, of pipelines) was studied. It was shown that even low activity levels (below maximum permissible levels) caused corrosion loss of the metal and a decrease in the operation reliability. Synergistic protective compounds suppressing the destructive radiation effects and ensuring reliable operation of metal structures due to chelation of the surface metal atoms were developed using computer simulation. [ABSTRACT FROM AUTHOR]

Depth profiling using surface sensitive analysis methods in combination with sputter ion etching is a common procedure for thorough material investigations, where clean surfaces free of any contamination are essential. Hence, surface analytic studies are mostly performed under ultra-high vacuum (UHV) conditions, but the cleanness of such UHV environments is usually overrated. Consequently, the current study highlights the in principle known impact of the residual gas on metal surfaces (Fe, Mg, Al, Cr and Zn) for various surface analytics methods, like X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and low-energy ion scattering (LEIS). The investigations with modern, state-of-the-art equipment showed different behaviors for the metal surfaces in UHV during acquisition: (i) no impact for Zn, even after long time, (ii) solely adsorption of oxygen for Fe, slight and slow changes for Cr and (iii) adsorption accompanied by oxide formation for Al and Mg. The efficiency of different counter measures was tested and the acquired knowledge was finally used for ZnMgAl coated steel to obtain accurate depth profiles, which exhibited before serious artifacts when data acquisition was performed in an inconsiderate way. [ABSTRACT FROM AUTHOR]

The energetics at organic-metal interfaces are, to large extend, determined by the structure of the molecular adsorbate on the substrate surface. As shown by low-energy electron diffraction (LEED) the zigzag shape of picene leads to a peculiar monolayer structure on Ag(111), Ag(110), and Cu(111) with one molecule in the unit cell lying essentially flat and the other one adopting an edge-on orientation. The adsorbate-substrate coupling is weak as shown by ultraviolet photoelectron spectroscopy (UPS). This is in striking contrast to monolayers of straight pentacene, where all molecules lie flat and are strongly coupled, involving charge transfer complex formation on most of these surfaces. The peculiar packing structure of picene leads to weak interfacial coupling on clean metal surfaces. In contrast, pentacene is chemisorbed on Ag and Cu surfaces involving electron transfer from the substrate. [ABSTRACT FROM AUTHOR]

Chirality is a property of matter which manifests at any length scale and can equally appear as quantum phenomena and in three-dimensional macroscopic structures. However, while chirality can be easily achieved by removing the inversion symmetry operation in hexagonal or tetragonal metal structures, chirality in metals is an unusual and barely developed phenomenon. Nevertheless, chirality can greatly alter mechanical and functional features of materials, making them suitable for catalysis, optics, electromagnetism, thermoelectricity and superconductivity; properties strictly dependent on the anisotropy of the crystal and on the direction of the applied force. This review aims to extend the definition of chirality to describe nanoclusters, metal surfaces and crystals and to provide an interdisciplinary overview on how symmetry can affect their properties. This review was submitted as part of the 2016 Materials Literature Review Prize of the Institute of Materials, Minerals and Mining run by the Editorial Board of MST. Sponsorship of the prize by TWI Ltd is gratefully acknowledged. [ABSTRACT FROM AUTHOR]

Charge transfer interactions between C 60 and the metal surfaces of Ag(111), Cu(111), Au(111) and Pt(111) have been studied using synchrotron-based photoemission, resonant photoemission and X-ray absorption spectroscopies. By placing the X-ray absorption and valence band spectra on a common binding energy scale, the energetic overlap of the unoccupied molecular orbitals with the density of states of the underlying metal surface have been assessed in the context of possible charge transfer pathways. Resonant photoemission and resonant Auger data, measuring the valence region as a function of photon energy for C 60 adsorbed on Au(111) reveals three constant high kinetic energy features associated with Auger-like core-hole decay involving an electron transferred from the surface to the LUMO of the molecule and electrons from the three highest occupied molecular orbitals, respectively and in the presence of ultra-fast charge transfer of the originally photoexcited molecule to the surface. Data for the C 60 /Ag(111) surface reveals an additional Auger-like feature arising from a core-hole decay process involving more than one electron transferred from the surface into the LUMO. An analysis of the relative abundance of these core-hole decay channels estimates that on average 2.4 ± 0.3 electrons are transferred from the Ag(111) surface into the LUMO. A core-hole clock analysis has also been applied to assess the charge transfer coupling in the other direction, from the molecule to the Au(111) and Ag(111) surfaces. Resonant photoemission and resonant Auger data for C 60 molecules adsorbed on the Pt(111) and Cu(111) surfaces are shown to exhibit no super-Auger features, which is attributed to the strong modification of the unoccupied molecular orbitals arising from stronger chemical coupling of the molecule to the surface. [ABSTRACT FROM AUTHOR]

In this article, we propose a Frozen Gaussian Sampling (FGS) algorithm for simulating nonadiabatic quantum dynamics at metal surfaces with a continuous spectrum. This method consists of a Monte-Carlo algorithm for sampling the initial wave packets on the phase space and a surface-hopping type stochastic time propagation scheme for the wave packets. We prove that to reach a certain accuracy threshold, the sample size required is independent of both the semiclassical parameter ε and the number of metal orbitals N , which makes it one of the most promising methods to study the nonadiabatic dynamics. The algorithm and its convergence properties are also validated numerically. Furthermore, we carry out numerical experiments including exploring the nuclei dynamics, electron transfer and finite-temperature effects, and demonstrate that our method captures the physics which can not be captured by classical surface hopping trajectories. • An efficient Frozen Gaussian Sampling (FGS) algorithm for simulating nonadiabatic dynamics at metal surfaces is proposed. • The sample size required is independent of the number of orbitals N and the semiclassical parameter ε. • FGS algorithm can capture the physics that classical surface hopping trajectories fail to capture. [ABSTRACT FROM AUTHOR]