Condensation or Desublimation: Nanolevel Structural Look on Two Frost Formation Pathways on Surfaces with Different Wettabilities.

Processes of water condensation and desublimation on solid surfaces are ubiquitous in nature and essential for various industrial applications, which are crucial for their performance. Despite their significance, these processes are not well understood due to the lack of methods that can provide insight at the nanolevel into the very first stages of phase transitions. Taking advantage of synchrotron grazing-incidence wide-angle X-ray scattering (GIWAXS) and environmental scanning electron microscopy (ESEM), two pathways of the frosting process from supersaturated vapors were studied in real time for substrates with different wettabilities ranging from highly hydrophilic to superhydrophobic. Within GIWAXS, a fully quantitative structural and orientational characterization of the undergoing phase transition reveals the information on degree of crystallinity of the new phase and determines the ordering at the surfaces and inside the films at the initial stages of water/ice nucleation from vapor onto the substrates. The diversity of frosting scenarios, including direct desublimation from the vapor and two-stage condensation-freezing processes, was observed by both GIWAXS and ESEM for different combinations of substrate wettability and vapor supersaturations. The classical nucleation theory straightforwardly predicts the pathway of the phase transition for hydrophobic and superhydrophobic substrates. The case of hydrophilic substrates is more intricate because the barriers in Gibbs free energy for nucleating both liquid and solid embryos are close to each other and comparable to thermal energy kBT. At that end, classical nucleation theory allows concluding a relation between contact angles for ice and water embryos on the basis of the observed frosting pathway.

An Antimicrobial Copper-Plastic Composite Coating: Characterization and In Situ Study in a Hospital Environment.

A method has been proposed for creating an operationally durable copper coating with antimicrobial properties for the buttons of electrical switches based on the gas dynamic spray deposition of copper on acrylonitrile butadiene styrene (ABS) plastic. It is shown that during the coating process, a polymer film is formed on top of the copper layer. Comparative in situ studies of microbial contamination have shown that the copper-coated buttons have a significant antimicrobial effect compared to standard buttons. Analysis of swabs over a 22-week study in a hospital environment showed that the frequency of contamination for a copper-coated button with various microorganisms was 2.7 times lower than that of a control button. The presented results allow us to consider the developed copper coating for plastic switches an effective alternative method in the fight against healthcare-associated infections.

Study of the Antibacterial Activity of Superhydrophilic and Superhydrophobic Copper Substrates against Multi-Drug-Resistant Hospital-Acquired Pseudomonas aeruginosa Isolates.

The global spread of multidrug-resistant (MDR) hospital-acquired pathogens is a serious problem for healthcare units. The challenge of the spreading of nosocomial infections, also known as hospital-acquired pathogens, including Pseudomonas aeruginosa, must be addressed not only by developing effective drugs, but also by improving preventive measures in hospitals, such as passive bactericidal coatings deposited onto the touch surfaces. In this paper, we studied the antibacterial activity of superhydrophilic and superhydrophobic copper surfaces against the P. aeruginosa strain PA103 and its four different polyresistant clinical isolates with MDR. To fabricate superhydrophilic and superhydrophobic coatings, we subjected the copper surfaces to laser processing with further chemosorption of fluorooxysilane to get a superhydrophobic substrate. The antibacterial activity of superhydrophilic and superhydrophobic copper surfaces was shown, with respect to both the collection strain PA103 and polyresistant clinical isolates of P. aeruginosa, and the evolution of the decontamination of a bacterial suspension is presented and discussed. The presented results indicate the promising potential of the exploitation of superhydrophilic coatings in the manufacture of contact surfaces for healthcare units, where the risk of infection spread and contamination by hospital-acquired pathogens is extremely high.

Effect of Water Adsorption on Lubricating Film Stability in Slippery Coatings.

The absorption of water by slippery coatings is a ubiquitous phenomenon that arises due to small but finite water dissolution during the contact of aqueous media with lubricants. In this study, using the concept of surface forces, we have analyzed the influence of trace amounts of water in lubricants on the stability of slippery coatings for both coatings with hydrophilic porous bases, prone to form hydrogen bonds with water, and those with hydrophobic porous bases. To perform such analysis, we have considered for the first time the electrostatic problem of the distribution of the electric potential and electric field strength in stratified films that contain two thin dielectric layers imitating the lubricant and a hydrophobic layer sandwiched between the porous substrate and air or water. Based on the developed approach, the equations for the calculation of the excess free energy and the disjoining pressure, associated with water dissolution in the lubricant film, were derived. An analysis of the excess film energy and the contribution of the image interaction to the disjoining pressure isotherm indicates that the dissolved water can both stabilize and destabilize the oil film, depending on the ratio of the static and dynamic dielectric permittivities of the lubricant and the phases confining the film. The results of calculations and simple experiments carried out here indicate much better water contact stability of silicone films impregnating a hydrophobized porous substrate than films impregnating a hydrophilic porous substrate. The obtained results indicate the preference for using the hydrophobic bases for the fabrication of long-lived slippery coatings characterized by better preservation of slippery functional properties under conditions of lubricant depletion and prolonged contact with water.

Recent progress in understanding the anti-icing behavior of materials.

Despite the significant progress in fundamental research in the physics of atmospheric icing or the revolutionary changes in modern materials and coatings achieved due to the recent development of nanotechnology and synthetic chemistry, the problem of reliable protection against atmospheric icing remains a hot topic of surface science. In this paper, we present a brief analysis of the mechanisms of anti-icing behavior that attracted the greatest interest of the scientific community and approaches which realize these mechanisms. We also note the strengths and weaknesses of such approaches and discuss future studies and prospects for the practical application of developed coatings.

The role of nanoparticle charge in crystallization kinetics and ice adhesion strength for dispersions of detonation nanodiamonds.

According to the classical nucleation theory, the presence of solid particles in a liquid should facilitate its heterogeneous nucleation upon supercooling. Here, we have analysed the behaviour of aqueous dispersions of detonation diamond nanoparticles (DND) with different signs of the surface charge in supercooled conditions and the frozen state. The behaviours of the diamond nanoparticles with a typical size of 4.5 nm were compared with each other and with deionized water in ice nucleation and ice shear experiments. The presented experimental data and analysis allowed the description of the significant increase in the freezing delay times for positively charged nanoparticles and the sharp decrease for negatively charged ones in comparison to deionized water, based on the peculiarities of the water structure around the nanoparticles and in the vicinity of a superhydrophobic surface. In addition, this approach has allowed the successful explanation of the difference in the practical work of adhesion for deionized water and dispersions of DND with different particle charges.

The Influence of Prolonged High-Concentration Ozone Exposure on Superhydrophobic Coatings in Static and High-Speed Flow Atmospheres.

The durability of superhydrophobic coatings under exposure to adverse factors that accompany their exploitation in natural and industrial environments remains a key problem in materials science. One such factor is a notable ozone concentration which can be generated as a result of corona discharge, dielectric barrier discharge, piezoelectric direct discharge, UV light photochemical processes, and others characteristic of the power industry. In this work, the mechanisms of degradation of the superhydrophobic coatings under prolonged exposure to high ozone concentrations at dynamic and nearly static conditions were studied. Our results indicate that in dynamic conditions, when the coatings are subjected to joint action of erosion loads initiated by the high-speed flow of the atmospheric air enriched with ozone, with ozone oxidation activity, the superhydrophobic state degrades quite rapidly. At the same time, in nearly static atmospheric conditions with the same ozone content, the degradation is substantially lower. Our study reveals the role of various factors such as the degradation of the layer of the hydrophobic agent, mechanical deterioration of texture, adsorption of ozone, and contact with water in the discovered behavior of the superhydrophobic coatings.

Evolution of Superhydrophilic Aluminum Alloy Properties in Contact with Water during Cyclic Variation in Temperature.

Hydrophilic or superhydrophilic materials in some cases are considered to be potentially icephobic due to a low ice-adhesion strength to such materials. Here, the evolution of the properties of a superhydrophilic aluminum alloy with hierarchical roughness, fabricated by laser processing, was studied in contact with water during prolonged cyclic variation in temperature. It was shown that the chemical interaction of rough alumina with water molecules caused the substitution of the surface oxide by polymorphic crystalline gibbsite or bayerite phases while preserving hierarchical roughness. Due to such substitution, mechanical durability was notably compromised. Thus, in contrast to the superhydrophobic laser-processed samples, the superhydrophilic samples targeted on the exploitation in an open atmosphere as a material with anti-icing properties cannot be considered as the industrially attractive way to combat icing.

Disjoining pressure analysis of the lubricant nanofilm stability of liquid-infused surface upon lubricant depletion.

HYPOTHESIS: The structure of the slippery layer and the evolution of functional properties of a lubricant infused substrate (LIS) is determined by the isotherm of disjoining pressure in the lubricant film. METHODS: The macroscopic theory of van der Waals forces was applied to the layered system used to model the structure and properties of LIS. For a lubricant layer sandwiched between the flat substrate and air or water, the isotherms of disjoining pressure were calculated and their analysis was used to conclude about stability of LIS. FINDINGS: The results obtained for silicone oil and perfluorodecalin on smooth and porous hydrophilic and hydrophobic solids allow selecting the LIS components corresponding to stability of lubricant films in air and water. It was found that for hydrophilic substrates in conditions of lubricant depletion, silicone oil and perfluorodecalin show lubricant film stability in both air and water. On flat or post microtexture hydrophobic substrate with flat tops, the perfluorodecalin lubricating layer is typically stable in air and unstable in water. In contrast, silicone oil lubricating layer demonstrates the stability in a wide range of lubricant film thicknesses for the hydrophobic substrate with flat-top textures in water, however, it can be unstable in air.

Superhydrophobic versus SLIPS: Temperature dependence and the stability of ice adhesion strength.

HYPOTHESIS: Ice adhesion to solids, being affected by the ice/solid intermolecular interactions and structure of ice surface layer is dependent on temperature, and ice surface layer equilibration time. EXPERIMENTS: A new centrifugal method of shear ice adhesion strength measurement with accurate temperature control on each stage from ice formation on test surfaces to the adhesion measurement is applied to study ice adhesion to superhydrophobic and slippery surfaces. The determinative advantage of the developed method is related to monitoring in one experiment the ice detachment from numerous samples and accurate measuring the rotation frequency for each ice detachment. FINDINGS: The following findings will be discussed.

The mechanisms of anti-icing properties degradation for slippery liquid-infused porous surfaces under shear stresses.

HYPOTHESIS: Loss of anti-icing properties of slippery liquid-infused porous surfaces (SLIPS) in conditions of repetitive shear stresses is the intrinsic process related to peculiarities of SLIPS structure. EXPERIMENTS: The study of the evolution of the ice adhesion strength to superhydrophobic surfaces (SHS) and SLIPS during repetitive icing/de-icing cycles measured by a centrifugal method was supplemented with the estimation of change in capillary pressure inside the pores, and SEM analysis of the effect of multiple ice detachments on surface morphology. FINDINGS: Obtained data indicated that although for freshly prepared SLIPS, the ice shear adhesion strength at -25 °C was several times lower than for SHS, repetitive icing-deicing cycles resulted in dramatic SLIPS degradation. In contrast, SHS showed weak degradation at least during 50 cycles. Additional to the depletion of an impregnating oil layer, other mechanisms of SLIPS degradation were hypothesized and tested. It was shown that lower capillary pressure required to displace air by water from the surface texture for SLIPSs compared to SHSs resulted in deeper water/ice penetration inside the grooves. The accelerated destruction of the mechanical texture caused by the Rehbinder effect constitutes another mechanism of SLIPSs degradation.

Durable Superhydrophobic Coatings on Tungsten Surface by Nanosecond Laser Ablation and Fluorooxysilane Modification.

Tungsten is an attractive material for a variety of applications, from constructions in high-temperature vacuum furnaces to nontoxic shields for nuclear medicine, because of its distinctive properties, such as high thermal conductivity, high melting point, high hardness and high density. At the same time, the areas of the applicability of tungsten, to a large extent, are affected by the formation of surface oxides, which not only strongly reduce the mechanical properties, but are also prone to easily interacting with water. To alleviate this shortcoming, a series of superhydrophobic coatings for the tungsten surface was elaborated using the method of nanosecond laser treatment followed by chemical vapor deposition of hydrophobic fluorooxysilane molecules. It is shown that the durability of the fabricated coatings significantly depends on surface morphology and composition, which in turn can be effectively controlled by adjusting the parameters of the laser treatment. The coating prepared with optimized parameters had a contact angle of 172.1 ± 0.5° and roll-off angle of 1.5 ± 0.4°, and preserved their high superhydrophobic properties after being subjected to oscillated sand abrasion for 10 h, continuous contact with water droplets for more than 50 h, and to several cycles of the falling sand test.

The Mechanisms of Antibacterial Activity of Magnesium Alloys with Extreme Wettability.

In this study, we applied the method of nanosecond laser treatment for the fabrication of superhydrophobic and superhydrophilic magnesium-based surfaces with hierarchical roughness when the surface microrelief is evenly decorated by MgO nanoparticles. The comparative to the bare sample behavior of such surfaces with extreme wettability in contact with dispersions of bacteria cells Pseudomonas aeruginosa and Klebsiella pneumoniae in phosphate buffered saline (PBS) was studied. To characterize the bactericidal activity of magnesium samples with different wettability immersed into a bacterial dispersion, we determined the time variation of the planktonic bacterial titer in the dispersion. To explore the anti-bacterial mechanisms of the magnesium substrates, a set of experimental studies on the evolution of the magnesium ion concentration in liquid, pH of the dispersion medium, surface morphology, composition, and wettability was performed. The obtained data made it possible to reveal two mechanisms that, in combination, play a key role in the bacterial decontamination of the liquid. These are the alkalization of the dispersion medium and the collection of bacterial cells by microrods growing on the surface as a result of the interaction of magnesium with the components of the buffer solution.

Deep Undercooling of Aqueous Droplets on a Superhydrophobic Surface: The Specific Role of Cation Hydration.

An extraordinary prolonged freezing delay was detected for the first time for deeply undercooled sessile droplets of aqueous solutions of alkali metal chlorides deposited onto a superhydrophobic surface. Accounting for the variation in the hydration energy of ions, their distribution in the vicinity of charged interfaces of solution/air and solution/superhydrophobic surface allows qualitative description of the observed ice nucleation kinetics and ionic specificity in freezing phenomena.

Superhydrophobic copper in biological liquids: Antibacterial activity and microbiologically induced or inhibited corrosion.

The bactericidal activity of copper and copper alloys is well appreciated and was already exploited in medical practice in 19th century. However, despite of being an essential nutrient required by organisms to perform life functions, excess copper is extremely toxic and detrimental to health. Recent studies have shown that superhydrophobic surfaces have a significant antibacterial potential for reduction of nosocomial infections. At the same time, the prolonged contact with biological liquids may cause a degradation of the superhydrophobic copper surface and corrosion with increasing egress of toxic copper ions. These aspects are poorly studied so far. In this paper, we analyze the evolution of the properties of both the superhydrophobic copper surface and the suspension of Escherichia coli bacteria during their prolonged contact and study the impact of such contact on the bactericidal activity of the surface. It is shown that by controlling the corrosion resistance and the wettability of the superhydrophobic copper substrate, it becomes possible to sustain the bactericidal action of copper substrates for a long time, simultaneously avoiding the excessive corrosive degradation and release of copper ions in the environment.

Van der Waals forces in free and wetting liquid films.

Van der Waals interactions induced by fluctuations of electromagnetic field bear universal nature and act between individual atoms, condensed particles or bodies of any type. Continuously growing interest to theoretical understanding as well as to precise evaluation of van der Waals forces is caused by their fundamental role in many physical, chemical, and biological processes. In this paper, we scrutinize progress in the studies of van der Waals forces, related to recent active development of Coupled Dipole Method (CDM) for the analysis of the behavior and properties of nanosized systems. The application of CDM for the analysis of thin liquid films allowed achieving substantial progress in understanding the behavior of free and wetting films. It was shown that both the macroscopic properties, such as excess free energy and Hamaker constants and the local microscopic parameters, such as polarizabilities, can be successfully calculated based only on properties of individual molecules. The impact of lateral film confinement on the specific excess free energy and the film stability was elucidated, and effect of spatial constraints on the spectrum of vibrational states for liquid film and the underlying substrate was analyzed. It was shown that van der Waals interactions between molecules represent the universal mechanism for dynamic structuring and formation of boundary layers and that the CDM allows self-consistently calculating the properties of these layers in both solid and liquid phases.

Modus Operandi of Protective and Anti-icing Mechanisms Underlying the Design of Longstanding Outdoor Icephobic Coatings.

Atmospheric icing has become a global concern due to hazardous consequences of ice accretion on air, land, and sea transport and infrastructure. Icephobic surfaces due to their physicochemical properties facilitate a decrease in ice and snow accumulation under outdoor conditions. However, a serious problem of most superhydrophobic surfaces described in the literature is poor operational durability under harsh corrosive and abrasive loads characteristic of atmospheric operation. Here, we elucidate main surface phenomena determining the anti-icing behavior and show experimentally how different mechanisms contribute to long-term durability. For comprehensive exploitation of those mechanisms, we have applied a recently proposed strategy based on fine-tuning of both laser processing and protocols of deposition of the fluorooxysilanes onto the nanotextured surface. Prolonged outdoor tests evidence that a developed strategy for modification of materials on the nanolevel allows overcoming the main drawbacks of icephobic coatings reported so far and results in resistance to destroying atmospheric impacts.

Bactericidal Activity of Superhydrophobic and Superhydrophilic Copper in Bacterial Dispersions.

A method based on nanosecond laser processing was used to design superhydrophilic and superhydrophobic copper substrates. Three different protocols were used to analyze the evolution of the bactericidal activity of the copper substrates with different wettability. Scanning electron microscopy was used to study the variation of cell morphology after the attachment to superhydrophilic and superhydrophobic surfaces. The dispersions of Escherichia coli K12 C600 and Klebsiella pneumoniae 811 in Luria Bertani broth in contact with the superhydrophilic copper surface showed enhanced bacterial inactivation, associated with toxic action of both hierarchically textured copper surface and high content of Cu2+ ions in the dispersion medium. In contrast, the bacterial dispersions in contact with the superhydrophobic copper substrates demonstrated an increase in cell concentration with time until the development of corrosion processes. The resistance of bacterial cells to contact the copper substrates is discussed on the basis of surface forces, determining the primary adhesion and of the protective action of a superhydrophobic state of the surface against electrochemical and biological corrosion.

Laser Tailoring the Surface Chemistry and Morphology for Wear, Scale and Corrosion Resistant Superhydrophobic Coatings.

A strategy, combining laser chemical modification with laser texturing, followed by chemisorption of the fluorinated hydrophobic agent was used to fabricate the series of superhydrophobic coatings on an aluminum alloy with varied chemical compositions and parameters of texture. It was shown that high content of aluminum oxynitride and aluminum oxide formed in the surface layer upon laser treatment allows solving the problem of enhancement of superhydrophobic coating resistance to abrasive loads. Besides, the multimodal structure of highly porous surface layer leads to self-healing ability of fabricated coatings. Long-term behavior of designed coatings in "hard" hot water with an essential content of calcium carbonate demonstrated high antiscaling resistance with self-cleaning potential against solid deposits onto the superhydrophobic surfaces. Study of corrosion protection properties and the behavior of coatings at long-term contact with 0.5 M NaCl solution indicated extremely high chemical stability and remarkable anticorrosion properties.

Combination of Functional Nanoengineering and Nanosecond Laser Texturing for Design of Superhydrophobic Aluminum Alloy with Exceptional Mechanical and Chemical Properties.

Industrial application of metallic materials is hindered by several shortcomings, such as proneness to corrosion, erosion under abrasive loads, damage due to poor cold resistance, or weak resistance to thermal shock stresses, etc. In this study, using the aluminum-magnesium alloy as an example of widely spread metallic materials, we show that a combination of functional nanoengineering and nanosecond laser texturing with the appropriate treatment regimes can be successfully used to transform a metal into a superhydrophobic material with exceptional mechanical and chemical properties. It is demonstrated that laser chemical processing of the surface may be simultaneously used to impart multimodal roughness and to modify the composition and physicochemical properties of a thick surface layer of the substrate itself. Such integration of topographical and physicochemical modification leads to specific surface nanostructures such as nanocavities filled with hydrophobic agent and hard oxynitride nanoinclusions. The combination of superhydrophobic state, nano- and micro features of the hierarchical surface, and the appropriate composition of the surface textured layer allowed us to provide the surface with the outstanding level of resistance of superhydrophobic coatings to external chemical and mechanical impacts. In particular, experimental data presented in this study indicate high resistance of the fabricated coatings to pitting corrosion, superheated water vapor, sand abrasive wear, and rapid temperature cycling from liquid nitrogen to room temperatures, without notable degradation of superhydrophobic performance.