An Experimental Investigation of Controlled Changes in Wettability of Laser-Treated Surfaces after Various Post Treatment Methods

In this paper, a quick nanosecond laser micro structuring process was employed to change the surface wettability of Ti6Al4V alloy. The same laser structuring method was used throughout, but with varying input fluence. The laser processing parameters resulted in high surface melting. After laser treatment, four post-processing methods were used, namely high vacuum, low temperature annealing, storage in a polyethylene bag, and storage in ambient air. Subsequently, the water droplet contact angle was measured over a long time period of 55 days. The results show that the sample stored in ambient air remained hydrophilic. On the other hand, the sample post-processed in a vacuum chamber behaved hydrophobically with a contact angle of approximately 150°. Other post-processing did not lead to specific wettability behavior. After wettability testing, all samples were cleaned ultrasonically in distilled water. This cleaning process led to annulation of all obtained properties through post-processing. In summary, this paper shows that it is more important to study surface chemistry than topography in terms of effects on wettability. Moreover, surface wettability can be controlled by laser structuring, post-processing, and surface cleaning.     

Coexistence and transition between Cassie and Wenzel state on pillared hydrophobic surface

Water droplets on rugged hydrophobic surfaces typically exhibit one of the following two states: (i) the Wenzel state [Wenzel RN (1936) Ind Eng Chem 28:988–994] in which water droplets are in full contact with the rugged surface (referred as the wetted contact) or (ii) the Cassie state [Cassie, ABD, Baxter S (1944) Trans Faraday Soc 40:546–551] in which water droplets are in contact with peaks of the rugged surface as well as the “air pockets” trapped between surface grooves (the composite contact). Here, we show large-scale molecular dynamics simulation of transition between Wenzel state and Cassie state of water droplets on a periodic nanopillared hydrophobic surface. Physical conditions that can strongly affect the transition include the height of nanopillars, the spacing between pillars, the intrinsic contact angle, and the impinging velocity of water nanodroplet (“raining” simulation). There exists a critical pillar height beyond which water droplets on the pillared surface can be either in the Wenzel state or in the Cassie state, depending on their initial location. The free-energy barrier separating the Wenzel and Cassie state was computed on the basis of a statistical-mechanics method and kinetic raining simulation. The barrier ranges from a few tenths of k_BT₀ (where k_B is the Boltzmann constant, and T₀ is the ambient temperature) for a rugged surface at the critical pillar height to ≈8 k_BT₀ for the surface with pillar height greater than the length scale of water droplets. For a highly rugged surface, the barrier from the Wenzel-to-Cassie state is much higher than from Cassie-to-Wenzel state. Hence, once a droplet is trapped deeply inside the grooves, it would be much harder to relocate on top of high pillars.     

Robust omniphobic surfaces

Superhydrophobic surfaces display water contact angles greater than 150° in conjunction with low contact angle hysteresis. Microscopic pockets of air trapped beneath the water droplets placed on these surfaces lead to a composite solid-liquid-air interface in thermodynamic equilibrium. Previous experimental and theoretical studies suggest that it may not be possible to form similar fully-equilibrated, composite interfaces with drops of liquids, such as alkanes or alcohols, that possess significantly lower surface tension than water (γ_lv = 72.1 mN/m). In this work we develop surfaces possessing re-entrant texture that can support strongly metastable composite solid-liquid-air interfaces, even with very low surface tension liquids such as pentane (γ_lv = 15.7 mN/m). Furthermore, we propose four design parameters that predict the measured contact angles for a liquid droplet on a textured surface, as well as the robustness of the composite interface, based on the properties of the solid surface and the contacting liquid. These design parameters allow us to produce two different families of re-entrant surfaces— randomly-deposited electrospun fiber mats and precisely fabricated microhoodoo surfaces—that can each support a robust composite interface with essentially any liquid. These omniphobic surfaces display contact angles greater than 150° and low contact angle hysteresis with both polar and nonpolar liquids possessing a wide range of surface tensions.     

Topographical Anisotropy and Wetting of Ground Stainless Steel Surfaces

Microscopic and physico-chemical methods were used for a comprehensive surface characterization of different mechanically modified stainless steel surfaces. The surfaces were analyzed using high-resolution confocal microscopy, resulting in detailed information about the topographic properties. In addition, static water contact angle measurements were carried out to characterize the surface heterogeneity of the samples. The effect of morphological anisotropy on water contact angle anisotropy was investigated. The correlation between topography and wetting was studied by means of a model of wetting proposed in the present work, that allows quantifying the air volume of the interface water drop-stainless steel surface.     

Liquid water can slip on a hydrophilic surface

Understanding and predicting the behavior of water, especially in contact with various surfaces, is a scientific challenge. Molecular-level understanding of hydrophobic effects and their macroscopic consequences, in particular, is critical to many applications. Macroscopically, a surface is classified as hydrophilic or hydrophobic depending on the contact angle formed by a water droplet. Because hydrophobic surfaces tend to cause water slip whereas hydrophilic ones do not, the former surfaces can yield self-cleaning garments and ice-repellent materials whereas the latter cannot. The results presented herein suggest that this dichotomy might be purely coincidental. Our simulation results demonstrate that hydrophilic surfaces can show features typically associated with hydrophobicity, namely liquid water slip. Further analysis provides details on the molecular mechanism responsible for this surprising result.     

Enhanced surface hydrophobicity by coupling of surface polarity and topography

We use atomistic computer simulation to explore the relationship between mesoscopic (liquid drop contact angle) and microscopic (surface atomic polarity) characteristics for water in contact with a model solid surface based on the structure of silica. We vary both the magnitude and direction of the solid surface polarity at the atomic scale and characterize the response of an aqueous interface in terms of the solvent molecular organization and contact angle. We show that when the topography and polarity of the surface act in concert with the asymmetric charge distribution of water, the hydrophobicity varies substantially and, further, can be maximal for a surface with significant polarity. The results suggest that patterning of a surface on several length scales, from atomic to μm lengths, can make important independent contributions to macroscopic hydrophobicity.     

Experimental Studies on Fretting Wear Behavior of PVDF Piezoelectric Thin Films

This paper discusses an in-depth experimental study on the fretting wear behavior of PVDF (polyvinylidene fluoride) piezoelectric thin film against a Si₃N₄ ceramic sphere under air conditions. A fretting wear device with a ball-on-plate contact configuration was applied. The changes of displacement amplitude, normal force, and applied voltage were taken into account. The friction logs were used to determine the contact state of the PVDF thin film during the fretting test. The 3D topography instrument and scanning electron microscope (SEM) were used to measure the details of the surface morphology and wear volume. The test results of PVDF thin films under different normal force, displacement amplitude, and applied voltage are summarized through the collection and analysis of experimental data. It is shown that the creep and plastic deformation lead to obvious winkles at the contact surface, which may decrease the specific wear rate of PVDF thin films.     

Quality and Quantity Assessment of the Water Repellent Properties of Functional Clothing Materials after Washing

The aim of the research was to evaluate the changes in the surface properties of five functional clothing materials with water-repellent finishes (including PFC-free finish) after 1, 5, and 10 washes with three detergents. A new approach to the interpretation of the water-repellent properties of textile materials is presented, based on two techniques, i.e., the spray test method and contact angle measurements. The results showed that washing materials with hydrophobic finishes can cause significant changes in their properties, which are mainly dependent on the composition and structure of the material, as well as the type of hydrophobic finish. The PFC-free finish is the least resistant to washing. For all materials with PFC finishes, the water repellency depends on the fluorine content on the surface and fabric topography. It was also found that increasing washing frequency resulted in a gradual decrease in water repellency. The loss of water repellency below an acceptable level (Grade 3) occurred after the fifth washing for all materials. Significant differences in the interpretation of the results of the spray test and contact angle measurements were observed. Using these methods separately provides information on the changes in the surface properties of the tested materials; however, their parallel application allows for obtaining complementary data, which is important for the proper interpretation of results.     

Mapping leaf surface landscapes

Leaf surfaces provide the ecologically relevant landscapes to those organisms that encounter or colonize the leaf surface. Leaf surface topography directly affects microhabitat availability for colonizing microbes, microhabitat quality and acceptability for insects, and the efficacy of agricultural spray applications. Prior detailed mechanistic studies that examined particular fungi-plant and pollinator-plant interactions have demonstrated the importance of plant surface topography or roughness in determining the outcome of the interactions. Until now, however, it has not been possible to measure accurately the topography--i.e., the three-dimensional structure--of such leaf surfaces or to record precise changes in patterns of leaf surface elevation over time. Using contact mode atomic force microscopy, we measured three-dimensional coordinates of upper leaf surfaces of Vaccinium macrocarpon (cranberry), a perennial plant, on leaves of two age classes. We then produced topographic maps of these leaf surfaces, which revealed striking differences between age classes of leaves: old leaves have much rougher surfaces than those of young leaves. Atomic force microscope measurements were analyzed by lag (1) autocorrelation estimates of leaf surfaces by age class. We suggest that the changes in topography result from removal of epicuticular lipids and that the changes in leaf surface topography influence phylloplane ecology. Visualizing and mapping leaf surfaces permit detailed investigations into leaf surface-mediated phenomena, improving our understanding of phylloplane interactions.     

Wetting morphologies at microstructured surfaces

The wetting of microstructured surfaces is studied both experimentally and theoretically. Even relatively simple surface topographies such as grooves with rectangular cross section exhibit a large variety of different wetting morphologies as observed by atomic force microscopy. This polymorphism arises from liquid wedge formation along the groove corners and from contact line pinning along the groove edges. A global morphology diagram is derived that depends only on two system parameters: (i) the aspect ratio of the groove geometry and (ii) The contact angle of the underlying substrate material. For microfluidics, the most interesting shape regimes involve extended liquid filaments, which can grow and shrink in length while their cross section stays essentially constant. Thus, any method by which one can vary the contact angle can be used to switch the length of the filament, as is demonstrated in the context of electrowetting.     

Quantifying the Mechanical Properties of Materials and the Process of Elastic-Plastic Deformation under External Stress on Material

The paper solves the problem of the nonexistence of a new method for calculation of dynamics of stress-deformation states of deformation tool-material systems including the construction of stress-strain diagrams. The presented solution focuses on explaining the mechanical behavior of materials after cutting by abrasive waterjet technology (AWJ), especially from the point of view of generated surface topography. AWJ is a flexible tool accurately responding to the mechanical resistance of the material according to the accurately determined shape and roughness of machined surfaces. From the surface topography, it is possible to resolve the transition from ideally elastic to quasi-elastic and plastic stress-strain states. For detecting the surface structure, an optical profilometer was used. Based on the analysis of experimental measurements and the results of analytical studies, a mathematical-physical model was created and an exact method of acquiring the equivalents of mechanical parameters from the topography of surfaces generated by abrasive waterjet cutting and external stress in general was determined. The results of the new approach to the construction of stress-strain diagrams are presented. The calculated values agreed very well with those obtained by a certified laboratory VÚHŽ.     

Effect of Surrounding Solvents on Interfacial Behavior of Gallium-Based Liquid Metal Droplets

Gallium-based liquid metal (GaLM) alloys have been extensively used in applications ranging from electronics to drug delivery systems. To broaden the understanding and applications of GaLMs, this paper discusses the interfacial behavior of eutectic gallium-indium liquid metal (EGaIn) droplets in various solvents. No significant difference in contact angles of EGaIn is observed regardless of the solvent types. However, the presence or absence of a conical tip on EGaIn droplets after dispensing could indirectly support that the interfacial energy of EGaIn is relatively low in non-polar solvents. Furthermore, in the impact experiments, the EGaIn droplet bounces off in the polar solvents of water and dimethyl sulfoxide (DMSO), whereas it spreads and adheres to the substrate in the non-polar solvents of hexane and benzene. Based on the dimensionless We number, it can be stated that the different impact behavior depending on the solvent types is closely related to the interfacial energy of EGaIn in each solvent. Finally, the contact angles and shapes of EGaIn droplets in aqueous buffer solutions with different pH values (4, 7, and 10) are compared. In the pH 10 buffer solution, the EGaIn droplet forms a spherical shape without the conical tip, representing the high surface energy. This is associated with the dissolution of the “interfacial energy-reducing” surface layer on EGaIn, which is supported by the enhanced concentration of gallium ion released from EGaIn in the buffer solution.     

Nanowall Textured Hydrophobic Surfaces and Liquid Droplet Impact

Water droplet impact on nanowires/nanowalls’ textured hydrophobic silicon surfaces was examined by assessing the influence of texture on the droplet impact dynamics. Silicon wafer surfaces were treated, resulting in closely packed nanowire/nanowall textures with an average spacing and height of 130 nm and 10.45 μm, respectively. The top surfaces of the nanowires/nanowalls were hydrophobized through the deposition of functionalized silica nanoparticles, resulting in a droplet contact angle of 158° ± 2° with a hysteresis of 4° ± 1°. A high-speed camera was utilized to monitor the impacting droplets on hydrophobized nanowires/nanowalls’ textured surfaces. The nanowires/nanowalls texturing of the surface enhances the pinning of the droplet on the impacted surface and lowers the droplet spreading. The maximum spreading diameter of the impacting droplet on the hydrophobized nanowires/nanowalls surfaces becomes smaller than that of the hydrophobized as-received silicon, hydrophobized graphite, micro-grooved, and nano-springs surfaces. Penetration of the impacted droplet fluid into the nanowall-cell structures increases trapped air pressure in the cells, acting as an air cushion at the interface of the droplet fluid and nanowalls’ top surface. This lowers the droplet pinning and reduces the work of droplet volume deformation while enhancing the droplet rebound height.     

Synthesis of a Superhydrophobic Fluorinated Nano-Emulsion and Its Modification on the Wettability of Tight Sandstone

The water-blocking effect is a serious problem when developing tight sandstone gas reservoirs, which can cause a sharp reduction in gas production. Wettability alteration of near-wellbore sand rock surface from superhydrophilicity to superhydrophobicity is an effective method to decrease capillary pressure. In this study, a superhydrophobic fluorinated nano-emulsion was synthesized via a soap-free emulsion polymerization process using methacryloxyethyl trimethyl ammonium chloride, trifluoctyl methacrylate, and styrene as monomers. The effect of the fluorinated monomer concentration on wettability alteration was evaluated by measuring the contact angle of the formation water droplet on the modified glass slides using nano-emulsions with different fluorinated monomer concentrations. The results showed that the nano-emulsion had a good dispersibility and homogeneous particle size of around 90 nm, and with the increase in fluorinated monomer concentration, the contact angle increased. The contact angle was the largest when the fluorinated monomer mass rate concentration reached 50%. The adsorption of nanoparticles could alter the rock wettability from a super hydrophilic state (θ = 7°) to a superhydrophobic state (θ = 150°). The spontaneous imbibition experiments showed that the formation water adsorption quality of the core decreased by 49.7% after being modified by the nano-emulsion. The nano-emulsion showed a good superhydrophobicity and had the potential to be used to reduce the water-blocking damage in the tight gas reservoirs.     

Effect of Chemical Surface Texturing on the Superhydrophobic Behavior of Micro–Nano-Roughened AA6082 Surfaces

Superhydrophobic surfaces on 6082 aluminum alloy substrates are tailored by low-cost chemical surface treatments coupled to a fluorine-free alkyl-silane coating deposition. In particular, three different surface treatments are investigated: boiling water, HF/HCl, and HNO₃/HCl etching. The results show that the micro-nano structure and the wetting behavior are greatly influenced by the applied surface texturing treatment. After silanization, all the textured surfaces exhibit a superhydrophobic behavior. The highest water contact angle (WCA, ≈180°) is obtained by HF/HCl etching. Interestingly, the water sliding angle (WSA) is affected by the anisotropic surface characteristics. Indeed, for the HF/HCl and the HNO₃/HCl samples, the WSA in the longitudinal direction is lower than the transversal one, which slightly affects the self-cleaning capacity. The results point out that the superhydrophobic behavior of the aluminum alloys surface can be easily tailored by performing a two-step procedure: (i) roughening treatment and (ii) surface chemical silanization. Considering these promising results, the aim of further studies will be to improve the knowledge and optimize the process parameters in order to tailor a superhydrophobic surface with an effective performance in terms of stability and durability.     

Wettability and Surface Roughness Analysis of Laser Surface Texturing of AISI 430 Stainless Steel

Due to its wide applicability in industry, devising microstructures on the surface of materials can be easily implemented and automated in technological processes. Laser Surface Texturing (LST) is applied to modify the chemical composition, morphology, and roughness of surfaces (wettability), cleaning (remove contaminants), reducing internal stresses of metals (hardening, tempering), surface energy (polymers, metals), increasing the adhesion (hybrid joining, bioengineering) and decreasing the growth of pathogenic bacteria (bioengineering). This paper is a continuation and extension of our previous studies in laser-assisted texturing of surfaces. Three different patterns (crater array-type C, two ellipses at 90° overlapping with its mirror-type B and 3 concentric octagons-type A) were applied with a nanosecond pulsed laser (active medium Nd: Fiber Diode-pumped) on the surface of a ferritic stainless steel (AISI 430). Micro texturing the surface of a material can modify its wettability behavior. A hydrophobic surface (contact angle greater than 90°) was obtained with different variations depending on the parameters. The analysis performed in this research (surface roughness, wettability) is critical for assessing the surface functionality, characteristics and properties of the stainless steel surface after the LST process. The values of the surface roughness and the contact angle are directly proportional to the number of repetitions and inversely proportional to the speed. Recommendations for the use of different texturing pattern designs are also made.     

Comparison of self-reported and observed water contact in an S. mansoni endemic village in Brazil

Estimates of exposure are critical for immuno-epidemiologic and intervention studies in human schistosomiasis. Direct observation of human water contact patterns is both costly and time consuming. To address these issues, we determined whether individuals residing in a Schistosoma mansoni endemic village in Brazil could accurately self-report their water contact patterns. We compared the results of a water contact questionnaire to the present gold standard, direct observation of water contact in 86 volunteers, aged 8--29. We administered a survey to estimate volunteers' frequency and type of water contact and directly measured each volunteers' water contact patterns during 5 weeks of detailed water contact observations. We found a poor correlation between self reported frequency of contact and directly observed exposure (rho=0.119, P=NS). The questionnaire data was supplemented by information about average body surface area of exposure and duration of contact for specific activities derived from observations of this cohort. This 'supplemented questionnaire' data was significantly correlated with their exposure index (rho=0.227, P=0.05). It provides a starting point from which questionnaires may develop to provide a more cost-effective and less labor intensive method of assessing water contact exposure at the level of the individual.     

A Wind Tunnel Experimental Study of Icing on NACA0012 Aircraft Airfoil with Silicon Compounds Modified Polyurethane Coatings

Ice formation on the aerodynamic surfaces of an aircraft is regarded as a major problem in the aerospace industry. Ice accumulation may damage parts, sensors and controllers and alter the aerodynamics of the airplane, leading to a range of undesired consequences, including flight delays, emergency landings, damaged parts and increased energy consumption. There are various approaches to reducing ice accretion, one of them being the application of icephobic coatings. In this work, commercially available polyurethane-based coatings were modified and deposited on NACA 0012 aircraft airfoils. A hybrid modification of polyurethane (PUR) topcoats was adopted by the addition of nanosilica and three-functional spherosilicates (a variety of silsesqioxane compound), which owe their unique properties to the presence of three different groups. The ice accretion on the manufactured nanocomposites was determined in an icing wind tunnel. The tests were performed under three different icing conditions: glaze ice, rime ice and mixed ice. Furthermore, the surface topography and wetting behavior (static contact angle and contact angle hysteresis) were investigated. It was found that the anti-icing properties of polyurethane nanocomposite coatings strongly depend on the icing conditions under which they are tested. Moreover, the addition of nanosilica and spherosilicates enabled the reduction of accreted ice by 65% in comparison to the neat topcoat.     

Fabrication of aligned microstructures with a single elastomeric stamp

The fabrication of complex patterns of aligned microstructures has required the use of multiple applications of lithography. Here we describe an approach for microfabrication that encodes the two-dimensional spatial information of several photomasks onto a single elastomeric stamp by mapping each photomask onto distinct heights on the surface of the stamp. Pressing the stamp against a surface collapses the topography of the stamp such that each recessed layer contacts the surface in stepwise sequence; the greater the applied pressure, the larger the area of the stamp that contacts the surface. After contact of each new layer with the surface, we use techniques of soft lithography (microcontact printing, microfluidics, and patterning through membranes) to pattern the surfaces that contact the stamp and those that do not with inorganic, organic, or living materials. Microfabrication through the use of multilevel stamps provides a promising alternative to conventional lithography for the construction of multicomponent, aligned surfaces; these structures may find use as components of microfluidic devices or biological patterns.     

Preparation of CNF/PDMS Superhydrophobic Coatings with Good Abrasion Resistance Using a One-Step Spray Method

Complex preparation methods and weak mechanical properties of superhydrophobic coatings hinder their applicability. To address these problems, cellulose nanofibers (CNFs) were used as structural materials to augment the roughness properties, while polydimethylsiloxane (PDMS) was used as the adhesive. Based on the results of previous studies, superhydrophobic coatings with good mechanical properties can be prepared by spraying the mixture onto a substrate surface; herein, the mixture comprised modified CNFs and PDMS. The resulting coating possessed excellent superhydrophobicity, which allowed a maximum water contact angle (WCA) of 158°. Furthermore, it exhibited great knife-scratch-resistance properties and good abrasion performance, which was evaluated by abrading with 800-grit sandpaper for 19 cycles (abrasion length of 380 cm) under a 100 g load. Based on the simple operation and abrasion resistance, the coating shows great potential for practical application.