A novel arc heat treatment technique was applied to design a uniquely graded super duplex stainless steel (SDSS), by subjecting a single sample to a steady state temperature gradient for 10 h. A new experimental approach was used to map precipitation in microstructure, covering aging temperatures of up to 1430 °C. The microstructure was characterized and functionality was evaluated via hardness mapping. Nitrogen depletion adjacent to the fusion boundary depressed the upper temperature limit for austenite formation and influenced the phase balance above 980 °C. Austenite/ferrite boundaries deviating from Kurdjumov–Sachs orientation relationship (OR) were preferred locations for precipitation of σ at 630–1000 °C, χ at 560–1000 °C, Cr2N at 600–900 °C and R between 550 °C and 700 °C. Precipitate morphology changed with decreasing temperature; from blocky to coral-shaped for σ, from discrete blocky to elongated particles for χ, and from polygonal to disc-shaped for R. Thermodynamic calculations of phase equilibria largely agreed with observations above 750 °C when considering nitrogen loss. Formation of intermetallic phases and 475 °C-embrittlement resulted in increased hardness. A schematic diagram, correlating information about phase contents, morphologies and hardness, as a function of exposure temperature, is introduced for evaluation of functionality of microstructures.

Nanocellulose (NC)-based hybrid coatings and films containing CeO2 and SiO2 nanoparticles (NPs) to impart UV screening and hardness properties, respectively, were prepared by solvent casting. The NC film-forming component (75 wt % of the overall solids) was composed entirely of cellulose nanocrystals (CNCs) or of CNCs combined with cellulose nanofibrils (CNFs). Zeta potential measurements indicated that the four NP types (CNC, CNF, CeO2, and SiO2) were stably dispersed in water and negatively charged at pH values between 6 and 9. The combination of NPs within this pH range ensured uniform formulations and homogeneous coatings and films, which blocked UV light, the extent of which depended on film thickness and CeO2 NP content, while maintaining good transparency in the visible spectrum (∼80%). The addition of a low amount of CNFs (1%) reduced the film hardness, but this effect was compensated by the addition of SiO2 NPs. Chiral nematic self-assembly was observed in the mixed NC film; however, this ordering was disrupted by the addition of the oxide NPs. The roughness of the hybrid coatings was reduced by the inclusion of oxide NPs into the NC matrix perhaps because the spherical oxide NPs were able to pack into the spaces between cellulose fibrils. We envision these hybrid coatings and films in barrier applications, photovoltaics, cosmetic formulations, such as sunscreens, and for the care and maintenance of wood and glass surfaces, or other surfaces that require a smooth, hard, and transparent finish and protection from UV damage.

From a circular economyperspective, one-pot strategies for theisolation of cellulose nanomaterials at a high yield and with multifunctionalproperties are attractive. Here, the effects of lignin content (bleachedvs unbleached softwood kraft pulp) and sulfuric acid concentrationon the properties of crystalline lignocellulose isolates and theirfilms are explored. Hydrolysis at 58 wt % sulfuric acid resulted inboth cellulose nanocrystals (CNCs) and microcrystalline celluloseat a relatively high yield (>55%), whereas hydrolysis at 64 wt% gaveCNCs at a lower yield (<20%). CNCs from 58 wt % hydrolysis weremore polydisperse and had a higher average aspect ratio (1.5-2x),a lower surface charge (2x), and a higher shear viscosity (100-1000x).Hydrolysis of unbleached pulp additionally yielded spherical nanoparticles(NPs) that were <50 nm in diameter and identified as lignin bynanoscale Fourier transform infrared spectroscopy and IR imaging.Chiral nematic self-organization was observed in films from CNCs isolatedat 64 wt % but not from the more heterogeneous CNC qualities producedat 58 wt %. All films degraded to some extent under simulated sunlighttrials, but these effects were less pronounced in lignin-NP-containingfilms, suggesting a protective feature, but the hemicellulose contentand CNC crystallinity may be implicated as well. Finally, heterogeneousCNC compositions obtained at a high yield and with improved resourceefficiency are suggested for specific nanocellulose uses, for instance,as thickeners or reinforcing fillers, representing a step toward thedevelopment of application-tailored CNC grades.

This study reports the results obtained from the welding tests carried out within the European project H2020 "NEXTOWER", which aims to create a demonstration plant with concentrated energy (CSP) and high efficiency solar tower, based on the use of liquid lead as an energy storage element. In particular, the study focuses on the development phases of the robotic GMAW and strip cladding SAW welding procedures, to create defect-free coatings on Incoloy® 800H components adopting an innovative Fe-Cr-Al-based consumable, specially developed by Sandvik Kanthal. The paper illustrates the operational and metallurgical aspects associated with the use of the Fe-Cr-Al consumable, evaluating the effect of the different process parameters, as well as any heat treatments, on the mechanical and microstructural properties of the joints. The laboratory test results were compared with the qualification paths required by ASME and EN reference standards.

Dependencies of the relative elongation epsilon under the constantly applied stress at T = 1.8 K on the endurance time t of polycrystalline parahydrogen (p-H-2, similar to 0.2% of o-H-2) of high purity (99.9999 mol.%), with varying deuterium content, were measured. The region of linear dependence between the measured creep rates (epsilon) over dot of samples and the applied stress s was revealed. The conclusion that the low-temperature creep of the studied p-H-2 possesses a vacancy-type diffusion character was made on the basis of linear dependence (epsilon) over dot similar to s. Determination of the low-temperature self-diffusion coefficient of vacancies D in solid p-H-2, which characterizes the rate of low-temperature mass transfer, was performed. The cases of migration of vacancies in the crystal bulk, along boundaries separating individual crystallites, as well as between dislocations existing in crystals, are considered. A significant decrease in the (epsilon) over dot and D values with an increase in the isotope concentration in the samples was observed, while maintaining the linear relationship between (epsilon) over dot and s for the studied p-H-2. Published by AIP Publishing.

Additive manufacturing (AM) or industrial 3D printing uses cutting-edge technologies and materials to produce a variety of complex products. However, the effects of the unintentionally emitted AM (nano)particles (AMPs) on human cells following inhalation, require further investigations. The physicochemical characterization of the AMPs, extracted from the filter of a Laser Powder Bed Fusion (L-PBF) 3D printer of iron-based materials, disclosed their complexity, in terms of size, shape, and chemistry. Cell Painting, a high-content screening (HCS) assay, was used to detect the subtle morphological changes elicited by the AMPs at the single cell resolution. The profiling of the cell morphological phenotypes, disclosed prominent concentration-dependent effects on the cytoskeleton, mitochondria, and the membranous structures of the cell. Furthermore, lipidomics confirmed that the AMPs induced the extensive membrane remodeling in the lung epithelial and macrophage co-culture cell model. To further elucidate the biological mechanisms of action, the targeted metabolomics unveiled several inflammation-related metabolites regulating the cell response to the AMP exposure. Overall, the AMP exposure led to the internalization, oxidative stress, cytoskeleton disruption, mitochondrial activation, membrane remodeling, and metabolic reprogramming of the lung epithelial cells and macrophages. We propose the approach of integrating Cell Painting with metabolomics and lipidomics, as an advanced nanosafety methodology, increasing the ability to capture the cellular and molecular phenotypes and the relevant biological mechanisms to the (nano)particle exposure.

Background: Exposure to metalworking fluids (MWFs) is a well-known cause of occupational contact dermatitis. Objectives: We aimed to (1) determine the amount of nickel, chromium, and cobalt in large samples of used and unused MWFs collected from metalworking plants in Denmark, and (2) evaluate a handheld x-ray fluorescence (XRF) device as a screening instrument for metals in MWFs. Methods: A handheld XRF device was used to screen for metals in MWFs. All samples were also analyzed for concentrations of nickel, chromium, and cobalt using graphite furnace atomic absorption spectroscopy (GFAAS). Results: GFAAS analysis showed that 13 of 80 samples (16.3%) contained >1 mg/kg (ppm) nickel (range: 6.4-17.7 mg/kg), 3 of 80 (3.8%) contained >1 (range: 1.4-3.1) mg/kg chromium, and 1 of 80 (1.3%) contained 1.3 mg/kg cobalt. XRF-screening detected nickel in eight samples (range: 2.5-15.5 mg/kg), but only one sample with 3.0 (±0.5) mg/kg was found subsequently to contain 9.9 (0.02) mg/kg nickel by GFAAS. Although no chromium was found by XRF analysis, cobalt was found in two samples with 6 (±1.5) mg/kg and 5 (±1.5) mg/kg, subsequently found to contain 0.1 (±0.01) mg/kg and 0.08 (±0.01) mg/kg by GFAAS. Similar concentrations of nickel were found in used (N = 6, range: 6.4-17.7 mg/kg) and unused MWFs (N = 7, range: 9.1-17.3 mg/kg). Conclusion: Considerable levels of nickel, chromium, and cobalt were found in some used and unused MWFs indicating that these might represent a source of metal allergy. The XRF device is a poor screening test for these metals in MWFs. 

Selective laser melting (SLM) based processing of Mo-based samples is challenging due to solidification cracking. We here demonstrate that the addition of 2 wt% MoS2 to the Mo feedstock markedly improves crack mitigation of SLM-processed Mo/MoS2/Mo2S3 composite micro-lattice structures (SLM-Mo/ Mo(x)S(x+1)). Crack inhibition is suggested to be a result of Mo2S3 formation, decreased lattice strain (0.04 4%), and a decrease in accumulated residual stresses. The increased values of polarization resistance from 42.3 and 19.2 kU cm2 to 437 and 78.2 kU cm2, respectively verified the hindering effect of the composition on stress corrosion cracking (SCC) and surface oxidation cracking. However, an increased corrosion current density, from 1.22 to 10.2 mA/cm2, and cathodic Tafel constant, from 175 to 260.5 mV, confirmed the decreased polarization resistance and occurrence of different types of corrosion such as SCC and pitting. The strategy to add 2 wt% MoS2 to the Mo feedstock enables the fabrication of hightemperature micro-lattice structure components with improved corrosion resistance properties applicable in e.g., electronic, power semiconductor heat sinks, offshore-, aerospace-, defense-, or particularly novel sodium-ion energy storage applications.

Reduced graphene oxide (rGO) is an ideal candidate in nanostructured metallic materials to enhance their electrochemical performance. However, few studies exist on the effects of rGO on the crystallographic, physical, and topological properties of co-electrodeposited Ni/rGO nanocomposites. In this study, the morphology and normalized electro-active specific surface (NESS) of a Ni/rGO nanocomposite were correlated with its crystal-lographic properties by varying the applied co-electrodeposition current density (0.01-0.1 A cm(-2)) and rGO concentration (0.5-2 mg mL(-1)). Tuning was done to achieve the best physical and electrochemical properties of the nanocomposite at alkaline (NaOH) conditions in terms of the highest NESS (12.3 x 10(-4)) and electro-active sensitivity (17.3 mu A mM(-1) cm(-2)) possible. The findings of the study show a possible approach to enhance the performance of electro-active components such as electrochemical devices, sensors, and actuators.

MoS2-based nanocomposites have been widely processed by a variety of conventional and 3D printing techniques. In this study, selective laser melting (SLM) has for the first time successfully been employed to tune the crystallographic structure of bulk MoS2 to a 2H/1T phase and to distribute Mo2S3 nanoparticles in-situ in MoS2/Mo2S3 nanocomposites used in electrochemical energy conversion/storage systems (EECSS). The remarkable results promote further research on and elucidate the applicability of laser-based powder bed processing of 2D nanomaterials for a wide range of functional structures within, e.g., EECSS, aerospace, and possibly high-temperature solid-state EECSS even in space.

Investigation of next-generation manufacturing methods for the processing of functional materials and offering products with improved performance/functionalities has always been a challenge in terms of energy efficiency, cost-effectiveness, and eco-friendliness. Additive manufacturing (AM) attributes to rapid prototyping techniques that provide new opportunities to test new concepts and design complex 3D structures from metals, ceramics, and composites. Moreover, as a well-known transition metal dichalcogenide, Molybdenum disulfide (MoS2) is a two-dimensional (2D) material with outstanding electrochemical, physical, and mechanical properties that make it a potential candidate for energy storage electrodes via intercalation of different H+, Li+, Na+, and K+ cations. In this review, we discuss the existing conventional MoS2-processing methodologies and compare them with the novel additive manufacturing processes (especially laser-based powder bed fusion). The authors are convinced that the processing of prominent MoS2-based functional structures by the novel additive manufacturing processes can provide complex structures for different electrochemical applications, particularly for energy conversion/ storage systems.

Relying on the reduction of oxygenated functional groups of graphene oxide, the engineering of the morphology of Ni-based reduced graphene oxide (Ni-rGO) nanocomposite was carried out via galvanostatic electrochemical co-deposition by changing the current density in a range of 0.001-0.01 A.cm(-2) and loading of 2 g.L-1 of graphene oxide. The morphology has been converted to a porous, rough, and three-dimensional (3D) form by significant incorporation and simultaneous reduction of GO into the structure of Ni-rGO nanocomposite film. Study on 3D morphology by SEM, FT-IR, XRD, and Raman confocal spectroscopy approved simultaneously reduction of oxygenated functional groups. Moreover, we have discussed the impact of rGO incorporated in the structure of Ni-rGO nanocomposite onto the creation of porous 3D-morphology and the enhancement of the electroactive specific surface. This new fascinating mechanism and structure can lead to the enhancement of electroactive components in electrochemical sensors and energy conversion-storage systems.

The resistance to environment-assisted cracking (EAC) of AISI 420 martensitic stainless steel (MSS) was investigated in 0.3 M NaCl solution (room temperature) at constant loads for 30 days. The steel tempered at 250 degrees C was superior to the 500 degrees C-temper, which showed corrosion pits favouring cracking. The fracture surface showed faceted grains, cleavage, striations, and inter- and transgranular cracks, suggesting a mixed stress corrosion cracking (SCC) and hydrogen embrittlement (HE) mechanism as the cause for EAC. Finite element modelling (FEM) indicated strain/stress localization at the mouth of deep pits and at the wall of shallow pits, displaying the favoured locations for pit-to-crack transition.

We report on the encapsulation of the antibiotic clofazimine (CLZ) within the pores of mesoporous silica particles having hydrophilic (CBET value of 137) and more hydrophobic (CBET value of 94 after calcination at 600 °C) surfaces. We studied the effect of pH on the released amount of CLZ in aqueous solutions and observed a maximum at pH 4.1 in correlation with the solubility of the drug. Less release of the drug was observed from the more hydrophobic particles which was attributed to a difference in the affinity of the drug to the carrier particles. Fluorescence lifetime imaging microscopy, emission spectra, and fluorescence lifetimes of single drug loaded particles provided detailed understanding and new knowledge of the physical form of the encapsulated drug and the distribution within the particles. The distribution of CLZ within the particles was independent of the surface chemistry of the particles. The confirmation of CLZ molecules as monomers or aggregates was revealed by controlled removal of the drug with solvent. Additionally, the observed optical "halo effect" in the fluorescent images was interpreted in terms of specific quenching of high concentration of molecules. The emission lifetime experiments suggest stronger interaction of CLZ with the more hydrophobic particles, which is relevant to its release. The results reported in this work demonstrate that tuning the hydrophilicity/hydrophobicity of mesoporous silica particles can be used as a tool to control the release without impacting their loading ability.

Reactions at the biointerfaces between stainless steel and protein-rich dairy products, which contain whey proteins, are important to consider in terms of food safety and material grade selection. Changes in corrosion behavior, metal release, and surface composition of austenitic (AISI 316 L), ferritic (AISI 430), and lean duplex (LDX 2101) stainless steels in simulated milk (SMS) and whey protein solution were investigated. The amount of released metals and the corrosion susceptibility increased according to 2101 < 316 L < 430. All grades revealed low corrosion rates in the whey protein solution without any sign of active/metastable corrosion. Pitting corrosion was evident for 430 in SMS. The total amount of released metals (iron, chromium, and nickel) was significantly higher in whey protein solution compared with SMS. This suggests the metal release process to be mainly governed by complexation reactions. Nickel was preferentially released compared to its bulk composition fraction for both 316 L and 2101 in the highly complexing SMS. Reduced metal release rates with time correlated with the enrichment of chromium in the surface oxide. The extent of metal release was for all metals substantially lower than release limits of metals stipulated in health regulations related to the use of alloys and metals in food-related environments.

The corrosion and metal release characteristics of additively manufactured stainless steels are key factors for their applicability in biomedical applications. The effect of building direction on the microstructure, corrosion behavior and metal release of selective laser melted (SLM) AISI 316L stainless steel were therefore investigated in a protein-rich synthetic body fluid (PBS+BSA, pH 7.3) and in diluted hydrochloric acid (HCl, pH 1.5). A multi-analytical approach was applied to characterize SLM 316L surfaces printed in different building directions (denoted XY and XZ) and a post heat treated SLM surface (XZ-HT) compared with wrought surfaces. All SLM specimens revealed an austenitic microstructure without any amounts of delta-ferrite and without large-angled grain boundaries in contrast to the wrought 316L surface. The building direction strongly affected the grain size distribution due to the temperature gradients in the melt pools. The SLM 316L specimens released initially slightly less Fe, Cr and Ni compared with the wrought 316L specimen. Slightly less metal was released from the heat treated SLM specimen (XZ-HT) specimen compared to the other SLM specimens. Relatively high amounts of released Cr were observed in PBS+BSA, most probably attributed to protein-bound Cr, whereas substantially more Ni was released in HCl compared to PBS+BSA due to pitting corrosion and a reduced surface oxide thickness. The surface oxide composition of as-printed SLM specimens was strongly dependent on the building direction and the post heat treatment, whereas no differences were observed after abrasion either among the SLM specimens or compared with the wrought 316L specimen. Cr became in all cases enriched within the outermost surface oxide in PBS+BSA and strongly enriched in the HCl solution, coupled to a strongly reduced amount of released metals with time. The heat treated SLM specimen (XZ-HT) gained a superior charge transfer resistance, the lowest passive current density, and the highest OCP value among all specimens. In HCl, the SLM specimens showed a lower pitting susceptibility compared to the wrought specimens. No pitting was observed in PBS+BSA. No differences in corrosion or metal release characteristics were observed related to the building direction of abraded SLM specimens.

One technique of additive manufacturing is the binder-jetting technique that has the advantages of low costs, printing at room temperature and in air, and no need of a support structure. The aim of this study was to investigate the corrosion behavior of printed 316L surfaces with and without different post surface treatments of blasting and superfinishing. Comparative studies were performed on abraded wrought 316L. Surface topography, porosity, surface oxide composition, and electrochemical characteristics, including pitting corrosion, were investigated at room temperature as a function of post surface treatments in diluted hydrochloric acid at pH 1.5. The blasting and superfinishing treatment significantly reduced the surface roughness and level of surface porosity. Blasting detrimentally affected on the pitting corrosion resistance. The superfinishing process induced an enrichment of chromium in the surface oxide and improved the pitting corrosion resistance. All surfaces revealed slightly reduced susceptibility to pit initiation and metastable pitting as compared to wrought 316L, possibly explained by the absence of inclusions. Once pitting propagation was induced, repassivation was hindered for all surfaces compared with the wrought surface. The pitting corrosion resistance of the as-superfinished 316L was improved compared with wrought 316L.

Stainless steel is an important transport and processing contact material for bovine milk and dairy products. Release (migration) of metals, ions, complexes or wear debris/particles, and metal-induced protein aggregation in such environments are hence important to consider both from a corrosion and food safety perspective. This study aims on investigating the release of iron (Fe), chromium (Cr), and nickel (Ni) from AISI 316L stainless steel in contact with whey protein solutions relevant for protein drinks, and on how the whey proteins are influenced by stirring with a magnetic stir bar and metal release. Mechanistic insight is gained by parallel investigations of metal release from two reference non-protein containing solutions, a metal-complexing (citrate-containing) simulated milk solution (SMS) and a low complexing phosphate buffered saline solution (PBS). All immersion exposures were conducted at pH 6.8 for 0.5, 4, 24 and 48 hat room temperature at static and stirring conditions. All solutions and samples were investigated using different chemical, spectroscopic, microscopic, and electrochemical methods. Significantly higher amounts of Fe, Cr, and Ni were released into the whey protein solution (80 g/L) as compared to SMS and PBS. Strong enrichment of Cr in the surface oxide and reduction of the surface oxide thickness were associated with a higher amount of Ni release in the metal-complexing solutions (SMS and whey protein) compared with PBS. Stirring conditions resulted in higher amounts of metal release, enrichment of Cr in the surface oxide, and clear signs of wear of the 316L surface in all solutions compared to static conditions. The wear mechanism in the whey protein solution was different as compared to corresponding processes in SMS and PBS, involving an etching-like process and larger-sized wear debris. Electrochemical measurements at static conditions confirmed observed differences between the solutions, with the lowest corrosion resistance observed for coupons exposed in the whey protein solution, followed by SMS and PBS. Released metals in solution from the 316L coupons in contact with the whey protein solution resulted in enhanced rates of protein aggregation and precipitation of protein aggregates from solution. Further studies should be made to investigate other relevant test conditions and assess toxicological risks.

Healthy material alternatives based on renewable resources and sustainable technologies have the potential to disrupt the environmentally damaging production and consumption practices established throughout the modern industrial era. In this study, a mycelium–nanocellulose biocomposite with hybrid properties is produced by the agitated liquid culture of a white-rot fungus (Trametes ochracea) with nanocellulose (NC) comprised as part of the culture media. Mycelial development proceeds via the formation of pellets, where NC is enriched in the pellets and depleted from the surrounding liquid media. Micrometer-scale NC elements become engulfed in mycelium, whereas it is hypothesized that the nanometer-scale fraction becomes integrated within the hyphal cell wall, such that all NC in the system is essentially surface-modified by mycelium. The NC confers mechanical strength to films processed from the biocomposite, whereas the mycelium screens typical cellulose–water interactions, giving fibrous slurries that dewater faster and films that exhibit significantly improved wet resistance in comparison to pure NC films. The mycelium–nanocellulose biocomposites are processable in the ways familiar to papermaking and are suggested for diverse applications, including packaging, filtration, and hygiene products.

The structure of water adjacent to silica is sensitive to the degree of deprotonation of surface silanol groups. As a result, close inspection of signals originating from these water molecules can be used to reveal the surface charge density. We have used nonlinear vibrational spectroscopy of the water O-H stretching band over a temperature range of 10-75 °C to account for the increase in surface potential from deprotonation. We demonstrate that the behavior at the silica surface is a balance between increasing surface charge and a decreasing contribution of water molecules aligned by the surface charge. Together with a model that accounts for two different types of silanol sites, we use our data to report the changes in enthalpy and entropy for deprotonation at each site. This is the first experimental determination of these thermodynamic parameters for hydrated silanol groups at the silica surface, critical to a wide range of geochemical and technological applications.

Preprocessing of pharmaceutical powders is a common procedure to condition the materials for a better manufacturing performance. However, such operations may induce undesired material properties modifications when conditioning particle size through milling, for example. Modification of both surface and bulk material structure will change the material properties, thus affecting the processability of the powder. Hence it is essential to control the material transformations that occur during milling. Topographical and mechanical changes in surface properties can be a preliminary indication of further material transformations. Therefore a surface evaluation of the alpha-lactose monohydrate after short and prolonged milling times has been performed. Unprocessed alpha-lactose monohydrate and spray dried lactose were evaluated in parallel to the milled samples as reference examples of the crystalline and amorphous lactose structure. Morphological differences between un-processed a-lactose, 1 h and 20 h milled lactose and spray dried lactose were detected from SEM and AFM images. Additionally, AFM was used to simultaneously characterize particle surface amorphicity by measuring energy dissipation. Extensive surface amorphicity was detected after 1 h of milling while prolonged milling times showed only a moderate particle surface amorphisation. Bulk material characterization performed with DSC indicated a partial amorphicity for the 1 h milled lactose and a fully amorphous thermal profile for the 20 h milled lactose. The temperature profiles however, were shifted somewhat in the comparison to the amorphous reference, particularly after extended milling, suggesting a different amorphous state compared to the spraydried material. Water loss during milling was measured with TGA, showing lower water content for the lactose amorphized through milling compared to spray dried amorphous lactose. The combined results suggest a surface-bulk propagation of the amorphicity during milling in combination with a different amorphous structural conformation to that of the amorphous spray dried lactose. The hardened surface may be due to either surface crystallization of lactose or to formation of a low-water glass transition.

In this work, thermodynamic calculations for α + β Type Ti–Fe–Cu–Sn alloy were carried out by the Thermo-Calc software. Powders from this alloy were obtained by plasma sputtering and used for subsequent 3D printing of experimental samples. The effect of various selective laser melting (SLM) parameters on porosity and hot cracking susceptibility as well as the electrochemical characteristics of the alloy have been studied. The optimal technological regime for the manufacture of samples by the SLM method was determined. It has been established that to obtain relatively dense samples without cracks, regimes with volumetric energy density Ev = 250–300 J/mm3 are required. It has been established that a change in the electrochemical behavior of the Ti94Fe1Cu1Sn4 alloy is related to the formation of a nonequilibrium Ti2Cu phase. Based on the findings we recomended directions for further research.

Hyaluronic acid and phospholipids are two components that are present in the synovial fluid, and both are implicated as important facilitators of joint lubrication. In this work we aim to clarify how hyaluronic acid interacts with a phospholipid bilayer through their molecular interactions at the bilayer surface. To this end we performed molecular dynamics simulations of one hyaluronic acid molecule at a phospholipid bilayer in aqueous solution. The simulations were carried out for two aqueous solutions of equal concentrations, containing either NaCl or CaCl2. We analyzed hydrogen bonds, hydrophobic contacts and cation mediated bridges to clarify how hyaluoronic acid binds to a phospholipid bilayer. The analysis shows that calcium ions promote longer lasting bonds between the species as they create calcium ion bridges between the carboxylate group of hyaluronic acid and the phosphate group of the phospholipid. This type of additional bonding does not significantly influence the total number of contact created, but rather stabilizes the contact. The presented results can facilitate understanding of the role of hyaluronic acid and phospholipid interactions in terms of lubrication of articular cartilage.

The lubrication mechanism in synovial fluid and joints is not yet fully understood. Nevertheless, intermolecular interactions between various neutral and ionic species including large macromolecular systems and simple inorganic ions are the key to understanding the excellent lubrication performance. An important tool for characterizing the intermolecular forces and their structural consequences is molecular dynamics. Albumin is one of the major components in synovial fluid. Its electrostatic properties, including the ability to form molecular complexes, are closely related to pH, solvation, and the presence of ions. In the context of synovial fluid, it is relevant to describe the possible interactions between albumin and hyaluronate, taking into account solution composition effects. In this study, the influence of Na+, Mg2+, and Ca2+ ions on human serum albumin-hyaluronan interactions were examined using molecular dynamics tools. It was established that the presence of divalent cations, and especially Ca2+, contributes mostly to the increase of the affinity between hyaluronan and albumin, which is associated with charge compensation in negatively charged hyaluronan and albumin. Furthermore, the most probable binding sites were structurally and energetically characterized. The indicated moieties exhibit a locally positive charge which enables hyaluronate binding (direct and water mediated).

Hyaluronic acid and phospholipids are two components in the synovial joint cavity that contribute to joint lubrication synergistically. Molecular dynamics simulations were performed and hydrogen bonds in hyaluronic acid were analyzed to identify specific sites that are responsible for its physical cross-linking. Two molecular masses of hyaluronic acid, 10 kDa and 160 kDa, were considered. We use molecular dynamics simulations and the small world network approach to investigate dynamic couplings using a distance map applied to oxygen atoms in a chain of hyaluronic acid in the presence of phospholipids and water. The distance characterizing the coupling can be defined in various ways to bring out the most evident differences between various scenarios of the polymer chain conformation We show herein a physical distance understood as H-bond length and classes of these distances which are defined in a coarse-grained picture of the molecule. Simulation results indicate that addition of phospholipids has little influence on hyaluronic acid crosslinking. However, longer chains and addition of lipids promote appreciably long lasting (resilient) networks that may be of importance in biological systems. Specific sites for hydrogen bonding of phospholipids to hyaluronic acid have also been identified.

A global transition towards more sustainable, affordable and reliable energy systems is being stimulated by the Paris Agreement and the United Nation's 2030 Agenda for Sustainable Development. This poses a challenge for the corrosion industry, as building climate-resilient energy systems and infrastructures brings with it a long-term direction, so as a result the long-term behaviour of structural materials (mainly metals and alloys) becomes a major prospect. With this in mind “Corrosion Challenges Towards a Sustainable Society” presents a series of cases showing the importance of corrosion protection of metals and alloys in the development of energy production to further understand the science of corrosion, and bring the need for research and the consequences of corrosion into public and political focus. This includes emphasis on the limitation of greenhouse gas emissions, on the lifetime of infrastructures, implants, cultural heritage artefacts, and a variety of other topics. 

For more than a hundred years of interfacial science, long chain fatty acids have been the primary system for the study of floating monolayers at the air–water interface due to their amphiphilic nature and system simplicity: an insoluble hydrocarbon chain and a soluble carboxyl group at a flat air–water interface. Despite―or perhaps rather due to―the assumed simplicity of such systems and the maturity of the research field, the seemingly fundamentally rooted notion of a two-dimensional water surface has yet to be challenged.

The naturally occurring methyl-branched long chain fatty acid 18-methyleicosanoic acid and one of its isomers form monolayers consisting of monodisperse domains of tens of nanometres, varying in size with the placement of the methyl branch. The ability of domain-forming monolayers to three-dimensionally texture the air–water interface is investigated as a result of hydrocarbon packing constraints owing to the methyl branch.

In this work, neutron reflectometry has been used to study monolayers of branched long chain fatty acids directly at the air–water interface, which allowed precise probing of how a deformable water surface is affected by monolayer structure. Such films were also transferred by Langmuir–Blodgett deposition to the air–solid interface, and subsequently imaged by atomic force microscopy. Combined, the results unanimously―and all but unambiguously―show that the self-assembly of branched long chain fatty acids texture the air–water interface, inducing domain formation by a local curvature of the water surface, and thus controverting the preconceived notion of a planar air–water interface. The size and shape of the observed domains are shown to be tuneable using three different parameters: in mixed systems of branched and unbranched fatty acids, with varying hydrocarbon length of the straight chain, and altering subphase electrolyte properties. Each of these factors effectively allows changing the local curvature of the monolayer, much like analogous three-dimensional systems in bulk lyotropic crystals. This precise tuneability opens up for sustainable nanopatterning. Finally, the results lead to a plausible hypothesis of self-healing properties as to why the surface of hair and wool have a significant proportion of branched fatty acid.

A simple, insoluble monolayer of fatty acid is shown to induce 3D nanotexturing of the air–water interface. This advance has been achieved through the study of monolayers of a methyl-branched long chain fatty acid, analogous to those found on the surface of hair and wool, directly at the air–water interface. Specular neutron reflectometry combined with AFM probing of deposited monolayers shows pronounced 3D surface domains, which are absent for unbranched analogues and are attributed to hydrocarbon packing constraints. The resulting surface topographies of the water far exceed the height perturbation that can be explained by the presence of capillary waves of a free liquid surface. These have hitherto been considered the only source of perturbation of the flatness of a planar water interface under gravity in the absence of topographical features from the presence of extended, globular or particulate matter. This amounts to a paradigm shift in the study of interfacial films and opens the possibility of 3D texturing of the air–water interface.

It is shown that the air-liquid interface can be made to display the same rich curvature phenomena as common lyotropic liquid crystal systems. Through mixing an insoluble, naturally occurring, branched fatty acid, with an unbranched fatty acid of the same length, systematic variation in the packing constraints at the air-water interface could be obtained. The combination of atomic force microscopy and neutron reflectometry is used to demonstrate that the water surface exhibits significant tuneable topography. By systematic variation of the two fatty acid proportions, ordered arrays of monodisperse spherical caps, cylindrical sections, and a mesh phase are all observed, as well as the expected lamellar structure. The tuneable deformability of the air-water interface permits this hitherto unexplored topological diversity, which is analogous to the phase elaboration displayed by amphiphiles in solution. It offers a wealth of novel possibilities for the tailoring of nanostructure.

3D texturing by self-assembly at the air-water interface has recently been proposed. The hypothesis of this work is that, if this is true, such domain formation should be inferable directly from pressure-area isotherms and be thermodynamically stable. Monolayers of branched fatty acid mixtures with straight chain analogues and their stability are thus studied using a combination of pressure-area isotherms, thermodynamic analysis, in situ Brewster angle microscopy, and atomic force microscopy of both LB-deposited and drop-cast films on silicon wafers. Isotherms reflecting the behavior of monodisperse 3D domains are shown to be independent of compression rate and display long-term stability. Gibbs analysis further confirms the thermodynamic rather than kinetic origin of such novel species by revealing that deviations from ideal mixing can be explained only a priori by differences in the topography of the water surface, thus also indirectly confirming the self-assembly deformation of the water interface. The intrinsic self-assembly curvature and miscibility of the two fatty acids is confirmed by drop-casting, which also provides a rapid, tunable thin-film preparation approach. Finally, the longevity of the nanostructured films is extraordinary, the long-range order of the deposited films increases with equilibration time at the water interface, and the integrity of the nanopatterns remains intact on the scale of years.

Correction for 'Physical crosslinking of hyaluronic acid in the presence of phospholipids in an aqueous nano-environment' by Piotr Bełdowski et al., Soft Matter, 2018, DOI: 10.1039/c8sm01388h. 

Hyaluronan-collagen composites have been employed in numerous biomedical applications. Understanding the interactions between hyaluronan and collagen is particularly important in the context of joint cartilage function and the treatment of joint diseases. Many factors affect the affinity of collagen for hyaluronan. One of the important factors is the ratio of 3- or 4-hydroxy proline to proline residues. This article presents the results from molecular dynamics calculations of HA-collagen type II interactions with hyaluronan. The applied protocol employed docking and geometry optimization of complexes built using collagen structures with different numbers of hydroxyl groups attached to proline moieties. It was established that the hydroxyproline/proline ratio affects both structural and energetic features of the collagen-hyaluronan complex. Proline hydroxylation was found to significantly influence the number of all identified types of molecular forces, hydrophobic interactions, water bridges and hydrogen bonds, which can be formed between collagen and hyaluronan. Importantly, an increase in the hydroxyproline/proline ratio in the collagen chain increases the binding affinity for hyaluronan. This is illustrated by the linear correlation between the binding free energy and the hydroxylation degree. A comparison of the results obtained for 3 and 4 hydroxylation of proline indicates that the hydroxyl group attachment position plays a minor role in complex stabilization. However, a slightly stronger affinity was observed for 4 hydroxylation. In order to evaluate the effect of the aqueous environment on the collagen-hyaluronan complex stability, the enthalpic and entropic contributions to the free energy of solvation were analyzed.

Polytetrafluoroethylene (PTFE) has shown an outstanding lubricity as a solid lubricant, but its application is limited due to its low-mechanical strength and high-wear rate. In this study, core-shell nanoparticles were synthesized using PTFE as the core and polymethylmethacrylate (PMMA) as the shell. The formed core-shell nanocomposites by leveraging the core-shell nanoparticles as basic structural units exhibit remarkable enhancement on uniformity, tensile strength, and wear resistance, compared to mechanically mixed composites with the same composition. Our experiments demonstrated the following results: (1) Owing to the excellent uniformity, the maximum tensile strength of core-shell nanocomposites was 62 MPa, three times higher than that of mechanically mixed composites. (2) The composite matrix formed by PMMA shell had better reinforcement and protection effect on inner PTFE phase, resulting in a reduced wear rate of 0.3 × 10−5 mm3/(N m), one order of magnitude lower than that of mechanically mixed composites. (3) The friction coefficient and interfacial mechanical properties of the core-shell nanocomposites at different temperatures have been systematically studied to get insights into lubrication mechanisms. It is proved that the temperature can decrease the modulus and increase the interfacial adhesion as well as the loss tangent of the core-shell nanocomposites, thus affecting the lubrication properties in multiple ways. 

Increasing the use of hygienic high-touch surfaces with antimicrobial properties in health care and public spaces is one way to hinder the spread of bacteria and infections. This study investigates the antimicrobial efficacy and surface reactivity of commercial laminate and powder coated surfaces treated with silver-doped phosphate glass as antimicrobial additive towards two model bacterial strains, Escherichia coli and Bacillus subtilis, in relation to surface weathering and repeated cleaning. High-touch conditions in indoor environments were simulated by different extents of pre-weathering (repeated daily cycles in relative humidity at constant temperature) and simplified fingerprint contact by depositing small droplets of artificial sweat. The results elucidate that the antimicrobial efficacy was highly bacteria dependent (Gram-positive or Gram-negative), not hampered by differences in surface weathering but influenced by the amount of silver-doped additive. No detectable amounts of silver were observed at the top surfaces, though silver was released into artificial sweat in concentrations a thousand times lower than regulatory threshold values stipulated for materials and polymers in food contact. Surface cleaning with an oxidizing chemical agent was more efficient in killing bacteria compared with an agent composed of biologically degradable constituents. Cleaning with the oxidizing agent resulted further in increased wettability and presence of residues on the surfaces, effects that were beneficial from an antimicrobial efficacy perspective.

Context. Gas hydrates can be stabilised outside their window of thermodynamic stability by the formation of an ice layer - a phenomenon termed self-preservation. This can lead to a positive buoyancy for clathrate particles containing CO2 that would otherwise sink in the oceans of Enceladus, Pluto, and similar oceanic worlds.Aims. Here we investigate the implications of Lifshitz forces and low occupancy surface regions on type I clathrate structures for their self-preservation through ice layer formation, presenting a plausible model based on multi-layer interactions through dispersion forces.Methods. We used optical data and theoretical models for the dielectric response for water, ice, and gas hydrates with a different occupancy. Taking this together with the thermodynamic Lifshitz free energy, we modelled the energy minima essential for the formation of ice layers at the interface between gas hydrate and liquid water.Results. We predict the growth of an ice layer between 0.01 and 0.2 mu m thick on CO, CH4, and CO2 hydrate surfaces, depending on the presence of surface regions depleted in gas molecules. Effective hydrate particle density is estimated, delimiting a range of particle size and compositions that would be buoyant in different oceans. Over geological time, the deposition of floating hydrate particles could result in the accumulation of kilometre-thick gas hydrate layers above liquid water reservoirs and below the water ice crusts of their respective ocean worlds. On Enceladus, the destabilisation of near-surface hydrate deposits could lead to increased gas pressures that both drive plumes and entrain stabilised hydrate particles. Furthermore, on ocean worlds, such as Enceladus and particularly Pluto, the accumulation of thick CO2 or mixed gas hydrate deposits could insulate its ocean against freezing. In preventing freezing of liquid water reservoirs in ocean worlds, the presence of CO2-containing hydrate layers could enhance the habitability of ocean worlds in our Solar System and on the exoplanets and exomoons beyond.

Gas hydrates formed in oceans and permafrost occur in vast quantities on Earth representing both a massive potential fuel source and a large threat in climate forecasts. They have been predicted to be important on other bodies in our solar systems such as Enceladus, a moon of Saturn. CO 2 -hydrates likely drive the massive gas-rich water plumes seen and sampled by the spacecraft Cassini, and the source of these hydrates is thought to be due to buoyant gas hydrate particles. Dispersion forces can in some cases cause gas hydrates at thermal equilibrium to be coated in a 3-4 nm thick film of ice, or to contact water directly, depending on which gas they contain. As an example, the results are valid at a quadruple point of the water-CO 2 gas hydrate system, where a film is formed not only for the model with pure ice but also in the presence of impurities in water or in the ice layer. These films are shown to significantly alter the properties of the gas hydrate clusters, for example, whether they float or sink. It is also expected to influence gas hydrate growth and gas leakage.

We present a critical overview comparing theoretical predictions and measurements of van der Waals dispersion forces in media on the basis of the respective Hamaker constants. To quantify the agreement, we complement the reported experimental errors with those for the theoretical predictions, which are because of the uncertainties in the underlying spectroscopic data. Our main finding is that the theoretical errors are often larger than their experimental counterparts. Within these uncertainties, the comparison confirms the standard Lifshitz theory based on the Abraham electromagnetic stress tensor against the recently suggested alternative account on the basis of the Maxwell stress tensor.

Due to their advanced tribological and electric properties, ionic liquids (ILs) are seen as potential lubricant additives in emerging green technologies. To verify their potential in complex machinery, an evaluation of tribological performance at the component and machine level is necessary. This work presents the effect of using a non-halogenated ionic liquid as a grease additive in bearings operating under driving cycle conditions. These harsh conditions are designed to be analogous to what a grease-bearing system must endure in an electric vehicle motor. One-month experiments, equivalent to 23,000 km of vehicle operation, were used to evaluate grease additive performance. Our results reveal that the addition of the ionic liquid resulted in a high-impact improvement, reducing bearing friction losses by up to 45%. Grease rheology and surface wetting measurements indicate that the sharp drop in friction torque is related to a complex balance of factors that results in a limited amount of highly effective lubricant products at the contact inlets (optimum degree of starvation).

Inhalation therapy treating severe infectious disease is among the more complex and emerging topics in controlled drug release. Micron-sized carriers are needed to deposit drugs into the lower airways, while nano-sized carriers are of preference for cell targeting. Here, we present a novel and versatile strategy using micron-sized spherical particles with an excellent aerodynamic profile that dissolve in the lung fluid to ultimately generate nanoparticles enabling to enhance both extra- and intra-cellular drug delivery (i.e., dual micro-nano inhalation strategy). The spherical particles are synthesised through the condensation of nano-sized amorphous silicon dioxide resulting in high surface area, disordered mesoporous silica particles (MSPs) with monodispersed size of 2.43 μm. Clofazimine (CLZ), a drug shown to be effective against multidrug-resistant tuberculosis, was encapsulated in the MSPs obtaining a dry powder formulation with high respirable fraction (F.P.F. <5 μm of 50%) without the need of additional excipients. DSC, XRPD, and Nitrogen adsorption-desorption indicate that the drug was fully amorphous when confined in the nano-sized pores (9–10 nm) of the MSPs (shelf-life of 20 months at 4 °C). Once deposited in the lung, the CLZ-MSPs exhibited a dual action. Firstly, the nanoconfinement within the MSPs enabled a drastic dissolution enhancement of CLZ in simulated lung fluid (i.e., 16-fold higher than the free drug), increasing mycobacterial killing than CLZ alone (p = 0.0262) and reaching concentrations above the minimum bactericidal concentration (MBC) against biofilms of M. tuberculosis (i.e., targeting extracellular bacteria). The released CLZ permeated but was highly retained in a Calu-3 respiratory epithelium model, suggesting a high local drug concentration within the lung tissue minimizing risk for systemic side effects. Secondly, the micron-sized drug carriers spontaneously dissolve in simulated lung fluid into nano-sized drug carriers (shown by Nano-FTIR), delivering high CLZ cargo inside macrophages and drastically decreasing the mycobacterial burden inside macrophages (i.e., targeting intracellular bacteria). Safety studies showed neither measurable toxicity on macrophages nor Calu-3 cells, nor impaired epithelial integrity. The dissolved MSPs also did not show haemolytic effect on human erythrocytes. In a nutshell, this study presents a low-cost, stable and non-invasive dried powder formulation based on a dual micro-nano carrier to efficiently deliver drug to the lungs overcoming technological and practical challenges for global healthcare.

In this work, a novel in-situ grown layered double hydroxide (LDH) film co-intercalated with inhibitors (vanadates) and low surface energy substance (laurates) was immobilized on Al substrates. A long-term monitoring of electrochemical impedance spectra (EIS) of the various samples in 3.5 wt.% NaCl solution demonstrated the synergetic protection of the intercalated two functional species. Meanwhile, the X-ray diffraction (XRD) result of the samples after immersion in NaCl solution for a long time presented the anion-exchange process between vanadates/laurates and chlorides. The synergetic effect of the two species loaded film significantly contributed to the enhanced long-term corrosion protection of aluminum.

Corrosion of steel in concrete has resulted in shorter service life of concrete constructions and it may also cause serious safety accident. Chloride attack and carbonation of the concrete are two of the most crucial trigger factors for the initiation of corrosion. In order to protect the reinforced steel in concrete from corrosion, in this work, a composite inhibitor of layered double hydroxides (LDHs) intercalated with organic phthalates (PTL) and hydroxide ions (MgAl-LDHs-OH-PTL) were synthesized by calcination-reconstruction methods in ambient atmosphere. The structure, composition and morphology of the prepared MgAl-LDHs-OH-PTL were obtained by X-ray diffraction, Fourier transform infrared spectroscopy and Scanning Electron Microscopy, respectively. The electrochemical measurements indicated that the inhibition efficiency of MgAl-LDHs-OH-PTL for carbon steel in the simulated carbonated concrete pore (SCCP) solutions reached more than 90% when its concentration was 20 g/L. It was found that the MgAl-LDHs-OH-PTL possessed multifunctional protection roles for the carbon steel in concrete, which mainly included decrease of aggressive Cl-ions, increase of the pH of SCCP solutions and release of PTL anions to the solution gradually. The work indicated the promising potential of LDHs compounds as effective multifunctional inhibitors in the field of corrosion protection of reinforced concrete.