Odd-even effects in aryl-substituted alkanethiolate SAMs: nonsymmetrical attachment of aryl unit and its impact on the SAM structure.

Aryl-substituted alkanethiolate (AT) self-assembled monolayers (SAMs) exhibit typically so-called odd-even effects, viz. systematic variations in the film structure, packing density, and molecular inclination depending on the parity of the number of the methylene units in the alkyl linker, n. As an exception to this rule, ATs carrying an anthracen-2-yl group (Ant-n) as tail group were reported to have different behavior due the non-symmetric attachment of the anthracene unit to the AT linker, providing additional degree of freedom for the molecular organization and allowing for partial compensation of the odd-even effects. In this context, the structure of SAMs formed by adsorption of anthracene-substituted ATs (Ant-n; n = 1-6) at room temperature on Au(111) substrate was investigated by high-resolution scanning tunnelling microscopy (STM). Most of these SAMs exhibit a coexistence of two different ordered phases, some of which are common for either n = odd or n = even while other vary over the series, showing a broad variety of different structures. The average packing density of the Ant-n SAMs, derived from the analysis of the STM data, varies by 7.5-10% depending on the parity of n, being, as expected, higher for n = odd. The respective extent of the odd-even effects is noticeably lower than that usually observed for other aryl-substituted monolayers (∼25%), which goes in line with the previous findings and emphasizes the impact of the non-symmetric attachment of the aromatic unit.

How solute atoms control aqueous corrosion of Al-alloys.

Aluminum alloys play an important role in circular metallurgy due to their good recyclability and 95% energy gain when made from scrap. Their low density and high strength translate linearly to lower greenhouse gas emissions in transportation, and their excellent corrosion resistance enhances product longevity. The durability of Al alloys stems from the dense barrier oxide film strongly bonded to the surface, preventing further degradation. However, despite decades of research, the individual elemental reactions and their influence on the nanoscale characteristics of the oxide film during corrosion in multicomponent Al alloys remain unresolved questions. Here, we build up a direct correlation between the near-atomistic picture of the corrosion oxide film and the solute reactivity in the aqueous corrosion of a high-strength Al-Zn-Mg-Cu alloy. We reveal the formation of nanocrystalline Al oxide and highlight the solute partitioning between the oxide and the matrix and segregation to the internal interface. The sharp decrease in partitioning content of Mg in the peak-aged alloy emphasizes the impact of heat treatment on the oxide stability and corrosion kinetics. Through H isotopic labelling with deuterium, we provide direct evidence that the oxide acts as a trap for this element, pointing at the essential role of the Al oxide might act as a kinetic barrier in preventing H embrittlement. Our findings advance the mechanistic understanding of further improving the stability of Al oxide, guiding the design of corrosion-resistant alloys for potential applications.

Enhancing corrosion-resistant alloy design through natural language processing and deep learning.

We propose strategies that couple natural language processing with deep learning to enhance machine capability for corrosion-resistant alloy design. First, accuracy of machine learning models for materials datasets is often limited by their inability to incorporate textual data. Manual extraction of numerical parameters from descriptions of alloy processing or experimental methodology inevitably leads to a reduction in information density. To overcome this, we have developed a fully automated natural language processing approach to transform textual data into a form compatible for feeding into a deep neural network. This approach has resulted in a pitting potential prediction accuracy substantially beyond state of the art. Second, we have implemented a deep learning model with a transformed-input feature space, consisting of a set of elemental physical/chemical property-based numerical descriptors of alloys replacing alloy compositions. This helped identification of those descriptors that are most critical toward enhancing their pitting potential. In particular, configurational entropy, atomic packing efficiency, local electronegativity differences, and atomic radii differences proved to be the most critical.

Complex Interdependency of Microstructure, Mechanical Properties, Fatigue Resistance, and Residual Stress of Austenitic Stainless Steels AISI 304L.

Stainless steels are important in various industries due to their unique properties and durable life cycle. However, with increasing demands for prolonged life cycles, better mechanical properties, and improved residual stresses, new treatment techniques, such as deep cryogenic treatment (DCT), are on the rise to further push the improvement in stainless steels. This study focuses on the effect of DCT on austenitic stainless steel AISI 304L, while also considering the influence of solution annealing temperature on DCT effectiveness. Both aspects are assessed through the research of microstructure, selected mechanical properties (hardness, fracture and impact toughness, compressive and tensile strength, strain-hardening exponent, and fatigue resistance), and residual stresses by comparing the DCT state with conventionally treated counterparts. The results indicate the complex interdependency of investigated microstructural characteristics and residual stress states, which is the main reason for induced changes in mechanical properties. The results show both the significant and insignificant effects of DCT on individual properties of AISI 304L. Overall, solution annealing at a higher temperature (1080 °C) showed more prominent results in combination with DCT, which can be utilized for different manufacturing procedures of austenitic stainless steels for various applications.

Corrosion-Responsive Self-Healing Coatings.

Organic coatings are one of the most popular and powerful strategies for protecting metals against corrosion. They can be applied in different ways, such as by dipping, spraying, electrophoresis, casting, painting, or flow coating. They offer great flexibility of material designs and cost effectiveness. Moreover, self-healing has evolved as a new research topic for protective organic coatings in the last two decades. Responsive materials play a crucial role in this new research field. However, for targeting the development of high-performance self-healing coatings for corrosion protection, it is not sufficient just to focus on smart responsive materials and suitable active agents for self-healing. A better understanding of how coatings can react on different stimuli induced by corrosion, how these stimuli can spread in the coating, and how the released agents can reach the corroding defect is also of high importance. Such knowledge would allow the design of coatings that are optimized for specific applications. Herein, the requirements and possibilities from the corrosion and synthesis perspectives for designing materials for preparing self-healing coatings for corrosion protection are discussed.

Reducing Iron Oxide with Ammonia: A Sustainable Path to Green Steel.

Iron making is the biggest single cause of global warming. The reduction of iron ores with carbon generates about 7% of the global carbon dioxide emissions to produce ≈1.85 billion tons of steel per year. This dramatic scenario fuels efforts to re-invent this sector by using renewable and carbon-free reductants and electricity. Here, the authors show how to make sustainable steel by reducing solid iron oxides with hydrogen released from ammonia. Ammonia is an annually 180 million ton traded chemical energy carrier, with established transcontinental logistics and low liquefaction costs. It can be synthesized with green hydrogen and release hydrogen again through the reduction reaction. This advantage connects it with green iron making, for replacing fossil reductants. the authors show that ammonia-based reduction of iron oxide proceeds through an autocatalytic reaction, is kinetically as effective as hydrogen-based direct reduction, yields the same metallization, and can be industrially realized with existing technologies. The produced iron/iron nitride mixture can be subsequently melted in an electric arc furnace (or co-charged into a converter) to adjust the chemical composition to the target steel grades. A novel approach is thus presented to deploying intermittent renewable energy, mediated by green ammonia, for a disruptive technology transition toward sustainable iron making.

Polymorphism and Building-Block-Resolved STM Imaging of Self-Assembled Monolayers of 4-Fluorobenzenemethanethiol on Au(111).

Self-assembled monolayers (SAMs) of 4-fluorobenzenemethanethiol (p-FBMT) on Au(111), prepared by immersion procedure (1 mM ethanolic solution; 60 °C; 18 h), were characterized by scanning tunneling microscopy (STM). The data suggest the formation of highly ordered monolayer with a commensurate structure, described by the 2 3 × 13 R 13 ∘ unit cell. The STM appearance of this cell occurs, however, in two different forms, with either well-localized individual spots or splitting of these spots in two components. These components are assigned to the tunneling through the entire molecule or sulfur docking group only. The respective spots correspond then to the terminal fluorine atom and sulfur docking group, manifesting, thus, building-block-resolving STM imaging. The accessibility of the docking group for direct tunneling is most likely related to a specific molecular organization for one of the two possible internal structures of the unit cell. The above results represent a showcase for potential of STM for imaging of upright-arranged and densely packed molecular assemblies, such as SAMs.

Design of Nanostructured Protective Coatings with a Sensing Function.

Nanostructured multilayered coatings for metals are prepared to simultaneously provide a function of corrosion mitigation and of corrosion sensing for copper substrates. Silica nanocapsules, embedded in one layer of the coating, are used as a host for a corrosion inhibitor and as a sensor, which detect changes of pH value and release inhibitors via an optical signal. Furthermore, another layer in the coating exists in a nanonetwork loaded with another corrosion inhibitor, which is impregnated with a hydrophobic polymer. We demonstrate that a specific arrangement of layers leads to an optimum anticorrosion and sensing performance while the sensing signal can be prolonged for a long time. It is the first time that the fluorophore detecting corrosion is conjugated to the nanosensor and that nanofibers and nanocapsules are used simultaneously to load and release corrosion inhibitors for anticorrosion applications.

Annealing effect for self-assembled monolayers formed from terphenylethanethiol on Au(111).

The structure and morphology of self-assembled monolayers (SAMs) prepared on Au(111) from solutions of terphenylethanethiol (TP2) at room temperature and subsequently annealed at temperatures up to 473 K were investigated using scanning tunneling microscopy. This system is of particular interest because of its metastable character, holding potential for its tailored modification. Indeed, the data suggest the formation of several different structural phases, viz. α, ß, γ, and δ, appearing progressively for the as-prepared and annealed samples. The consecutive α → ß â†’ γ → δ phase transitions occurring with increasing annealing temperature involved a continuous reduction of the molecular packing density and significant changes in the substrate morphology. The major morphological changes were the appearance and progressive growth of monoatomic gold islands, on top of which the TP2 phases were formed, representing in all cases a single domain for a particular island and restricted only by the island size. For all the phases, inclined molecular orientation was assumed while a so-called lying-down arrangement, in which the TP2 backbones are orientated parallel to the gold surface, was not observed. A nearly complete desorption of the TP2 molecules was recorded at an annealing temperature of 473 K, accompanied by the drastic change in the surface morphology.

What is the trigger for the hydrogen evolution reaction? - towards electrocatalysis beyond the Sabatier principle.

The mechanism of the hydrogen evolution reaction, although intensively studied for more than a century, remains a fundamental scientific challenge. Many important questions are still open, making it elusive to establish rational principles for electrocatalyst design. In this work, a comprehensive investigation was conducted to identify which dynamic phenomena at the electrified interface are prerequisite for the formation of molecular hydrogen. In fact, what we observe as an onset of the macroscopic faradaic current originates from dynamic structural changes in the double layer, which are entropic in nature. Based on careful analysis of the activation process, an electrocatalytic descriptor is introduced, evaluated and experimentally confirmed. The catalytic activity descriptor is named as the potential of minimum entropy. The experimentally verified catalytic descriptor reveals significant potential to yield innovative insights for the design of catalytically active materials and interfaces.

On the robustness of the Kelvin probe based potentiometric hydrogen electrode method and its application in characterizing effective hydrogen activity in metal: 5 wt. % Ni cold-rolled ferritic steel as an example.

Quantitative detection of hydrogen in metal is important in providing a better basis for fundamental investigations of hydrogen embrittlement and hydrogen-related corrosion phenomena. Thermal desorption spectroscopy (TDS) has long been used in characterizing different hydrogen traps inside materials. However, in TDS measurements, the diffusible hydrogen (hydrogen at interstitial sites and weakly bound hydrogen) is usually not detected. The Davanathan-Starchurski permeation technique can cover this shortage. However, for such experiments, the stability of the palladium at the exit side, i.e. in aqueous solution under high potential polarization is an important issue. Alternatively, a Kelvin probe-based (KP-based) potentiometric method developed a few years ago has shown to allow quantitative determination of hydrogen in metal. This method is based on measuring the hydrogen electrode potential on the Pd-coated surface. The aim of this work is to check the reliability of this method and to demonstrate its potential applications in determining the hydrogen amount distributed in both shallow and deep traps in steel. The results reveal that different crystallographic orientation, grain shapes and grain sizes of the deposited palladium film (in the range of variation in this work) do not cause relevant effects on the KP-based hydrogen detection. It is shown in this work that the time lag and permeation rate derived from the permeation curves obtained by this method show a very good reliability and the calculated hydrogen amount shows a good agreement with TDS results. 5 wt.% Ni ferritic steel is used as a model material in this work.

Mobility of charge carriers in self-assembled monolayers.

We present a new approach to study charge transport within 2D layers of organic semi-conductors (OSCs) using atomic force microscopy (AFM)-based lithography applied to self-assembled monolayers (SAMs), fabricated from appropriate organothiols. The extent of lateral charge transport was investigated by insulating pre-defined patches within OSC-based SAMs with regions of insulating SAM made from large band gap alkanethiolates. The new method is demonstrated using a phenyl-linked anthracenethiolate (PAT), 4-(anthracene-2-ylethynyl)benzyl thiolate. I-V characteristics of differently shaped PAT-islands were measured using the AFM tip as a top electrode. We were able to determine a relationship between island size and electrical conductivity, and from this dependence, we could obtain information on the lateral charge transport and charge carrier mobility within the thin OSC layers. Our study demonstrates that AFM nanografting of appropriately functionalized OSC molecules provides a suitable method to determine intrinsic mobilities of charge carriers in OSC thin films. In particular, this method is rather insensitive with regard to influence of grain boundaries and other defects, which hamper the application of conventional methods for the determination of mobilities in macroscopic samples.

Pretreatment with a ß-Cyclodextrin-Corrosion Inhibitor Complex Stops an Initiated Corrosion Process on Zinc.

Metal pretreatment is typically the first step in a reliable corrosion protection system. This work explores the incorporation of complexes between the cyclic oligosaccharide ß-cyclodextrin (ß-CD) and the molecular organic corrosion inhibitor 2-mercaptobenzothiazole (MBT) into an oxide-based pretreatment layer on metallic zinc. The layers were produced by a precorrosion step in the presence of ß-CD. The resulting films have a morphology dominated by spherical particles. X-ray photoelectron spectroscopy investigations of the surfaces show the sulfur atoms of MBT to be partially oxidized but mostly intact. Samples pretreated with such a layer were subsequently coated with a model polymer coating, and the delamination of this model coating from an artificial defect was monitored by a scanning Kelvin probe (SKP). The SKP results show a slow down of delamination after several hours of the ongoing corrosion process for surfaces pretreated with the complexes. Finally, an increase in the electrode potential in the defect was observed, with a subsequent complete stop in delamination and repassivation of the defect after ≈10 h. This repassivation is attributed to the release of MBT after the initiation of the corrosion process. Most likely, the increase of pH, combined with the availability of aqueous solution, facilitates the MBT release after the initiation of a corrosion process. Consequently, complexes formed from ß-CD and corrosion inhibitors can be effectively incorporated into inorganic pretreatments, and the inhibitor component can be released upon start of the corrosion process.

Cyclodextrin inhibits zinc corrosion by destabilizing point defect formation in the oxide layer.

Corrosion inhibitors are added in low concentrations to corrosive solutions for reducing the corrosion rate of a metallic material. Their mechanism of action is typically the blocking of free metal surface by adsorption, thus slowing down dissolution. This work uses electrochemical impedance spectroscopy to show the cyclic oligosaccharide ß-cyclodextrin (ß-CD) to inhibit corrosion of zinc in 0.1M chloride with an inhibition efficiency of up to 85%. Only a monomolecular adsorption layer of ß-CD is present on the surface of the oxide covered metal, with Raman spectra of the interface proving the adsorption of the intact ß-CD. Angular dependent X-ray photoelectron spectroscopy (ADXPS) and ultraviolet photoelectron spectroscopy (UPS) were used to extract a band-like diagram of the ß-CD/ZnO interface, showing a large energy level shift at the interface, closely resembling the energy level alignment in an n-p junction. The energy level shift is too large to permit further electron transfer through the layer, inhibiting corrosion. Adsorption hence changes the defect density in the protecting ZnO layer. This mechanism of corrosion inhibition shows that affecting the defect chemistry of passivating films by molecular inhibitors maybe a viable strategy to control corrosion of metals.

Balanced work function as a driver for facile hydrogen evolution reaction - comprehension and experimental assessment of interfacial catalytic descriptor.

A major step in the development of (electro)catalysis would be the possibility to estimate accurately the energetics of adsorption processes related to reaction intermediates. Computational chemistry (e.g. using DFT) developed significantly in that direction and allowed the fast prediction of (electro)catalytic activity trends and improved the general understanding of adsorption at electrochemical interfaces. However, building a reliable and comprehensive picture of electrocatalytic reactions undoubtedly requires experimental assessment of adsorption energies. In this way, the results obtained by computational chemistry can be complemented or challenged, which often is a necessary pathway to further advance the understanding of electrochemical interfaces. In this work an interfacial descriptor of the electrocatalytic activity for hydrogen evolution reaction, analogue to the adsorption energy of the Had intermediate, is identified experimentally using in situ probing of the surface potentials of the metals, under conditions of continuous control of the humidity and the gas exposure. The derived activity trends give clear indication that the electrocatalytic activity for hydrogen evolution reaction is a consequence of an interplay between metal-hydrogen and metal-water interactions. In other words it is shown that the M-H bond formation strongly depends on the nature of the metal-water interaction. In fact, it seems that water dipoles at the metal/electrolyte interface play a critical role for electron and proton transfer in the double layer.

Side-Group-Induced Polymorphism in Self-Assembled Monolayers: 3,5-Bis(trifluoromethyl)benzenethiolate Films on Au(111).

The structure and molecular organization of self-assembled monolayers (SAMs) depend on a complex interplay of intermolecular and molecule-substrate interactions, so that even a small change in molecular composition can result in noticeable changes in the SAM structure. Herein we show that decoration of the most basic aromatic SAM constituent, benzenethiol, with two trifluoromethyl groups leads to distinct polymorphism in the respective SAMs, in which the appearance of a specific structural phase or a combination of several different phases is dependent on the parameters of the preparation procedure. High-quality films with a single crystallographic phase and significantly large domains could only be prepared after a short immersion time (5 min) and an additional re-immersion of the sample in pure ethanol at an elevated temperature. A standard 24 h immersion at room temperature led to poorly defined films with a large defect density and only a small portion of the surface covered by well-ordered molecular domains.

The Origin of the Catalytic Activity of a Metal Hydride in CO2 Reduction.

Atomic hydrogen on the surface of a metal with high hydrogen solubility is of particular interest for the hydrogenation of carbon dioxide. In a mixture of hydrogen and carbon dioxide, methane was markedly formed on the metal hydride ZrCoHx in the course of the hydrogen desorption and not on the pristine intermetallic. The surface analysis was performed by means of time-of-flight secondary ion mass spectroscopy and near-ambient pressure X-ray photoelectron spectroscopy, for the in situ analysis. The aim was to elucidate the origin of the catalytic activity of the metal hydride. Since at the initial stage the dissociation of impinging hydrogen molecules is hindered by a high activation barrier of the oxidised surface, the atomic hydrogen flux from the metal hydride is crucial for the reduction of carbon dioxide and surface oxides at interfacial sites.

Charge carrier mobilities in organic semiconductors: crystal engineering and the importance of molecular contacts.

We have conducted a combined experimental and theoretical study on the optimization of hexa-peri-hexabenzocoronene (HBC) as organic semiconductor. While orientations with high electronic coupling are unfavorable in the native liquid crystalline phase of HBC, we enforced such orientations by applying external constraints. To this end, self-assembled monolayers (SAMs) were formed by a non-conventional preparation method on an Au-substrate using electrochemical control. Within these SAMs the HBC units are forced into favorable orientations that cannot be achieved by unconstrained crystallization. For simulating the charge transport we applied a recently developed approach, where the molecular structure and the charge carrier are propagated simultaneously during a molecular dynamics simulation. Experiments as well as simulations are mutually supportive of an improved mobility in these novel materials. The implication of these findings for a rational design of future organic semiconductors will be discussed.

Regenerative nano-hybrid coating tailored for autonomous corrosion protection.

A novel bilayer coating system for autonomous corrosion-triggered self-healing is demonstrated. The storage of the encapsulated monomer and the catalyst is separated in two different layers. The encapsulated catalyst is stored inside a metallic coating, which ensures its activity even for an extended exposure time. The release from the capsules is triggered by corrosion and the correlated pH increase.

Chemistry-dependent X-ray-induced surface charging.

Materials science in general, and surface/interface science in particular, have greatly benefited from the development of high energy synchrotron radiation facilities. Irradiation with intense ionizing beams can however influence relevant sample properties. Permanent radiation damage and irradiation-induced sample modifications have been investigated in detail during the last decades. Conversely, reversible sample alterations taking place only during irradiation are still lacking comprehensive in situ characterization. Irradiation-induced surface charging phenomena are particularly relevant for a wide range of interface science investigations, in particular those involving surfaces of solid substrates in contact with gaseous or liquid phases. Here, we demonstrate partially reversible radiation-induced surface charging phenomena, which extend far beyond the spatial dimensions of the X-ray beam mainly as a consequence of the interaction between the surface and ionized ambient molecules. The charging magnitude and sign are found to be surface chemistry specific and dependent on the substrates' bulk conductivity and grounding conditions. These results are obtained by combining a scanning Kelvin probe with a synchrotron surface diffractometer to allow simultaneous in situ work function measurements during precisely controlled hard X-ray micro-beam irradiation.